Technology of heterolytic and homolytic oil refining processes: educational manual 9786010434974

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AL-FARABI KAZAKH NATIONAL UNIVERSITY

L.R. Sassykova

TECHNOLOGY OF HETEROLYTIC AND HOMOLYTIC OIL REFINING PROCESSES Educational manual

Almaty «Qazaq University» 2018

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UDC 665.6/7 LBC 35.514 S 23 Recommended for publication by the decision of the Academic Council of the Faculty of Chemistry and Chemical Technology and Editorial and Publishing Council of the Al-Farabi Kazakh National University (Protocol №6 dated 04.04.2018) Reviewer doctor of Chemistry, Professor Y.K. Ongarbayev

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Sassykova L.R. Technology of heterolytic and homolytic oil refining processes: educational manual / L.R. Sassykova. – Almaty: Qazaq University, 2018. – 269 р. ISBN 978-601-04-3497-4 The educational manual is constructed in accordance with the requirements of the credit technology program for masters enrolled in the specialty “Petrochemistry”. The course is designed to study the basic concepts: the role and importance of oil, oil refining, catalysis in oil processing, technology of catalytic synthesis of various products from one source ‒ petroleum raw materials, theoretical bases of action of catalysts in the catalytic homolytic and heterolytic processes of oil refining, the basic technological principles of catalytic refining processes, ecological problems of oil refining and petrochemistry. The educational manual contains a glossary that can help in mastering the basic terms used in the field of catalytic petrochemical industry. For better assimilation of educational material the questions to self-checking were added to each chapter. The educational manual is intended for students, masters, bachelors and doctoral students specializing in the field of petrochemistry", chemical technology of organic substances, catalysis and oil and gas business. Published in authorial release.

UDC 665.6/7 LBC 35.514 ISBN 978-601-04-3497-4

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© Sassykova L.R., 2018 © Al-Farabi KazNU, 2018

Oil and gas have no real alternative so far, so remains an actual need to develop oil and gas production and refining industries, as well as the priorities in training highly qualified specialists for these fields of science and technology. The purpose of this educational manual is an acquaintance with the theoretical basics of heterolytic and homolytic processes of catalytic synthesis of various products from oil, the review of modern theoretical concepts of the catalytic petrochemical industries, the study of basic scientific advances in the field of theory and technology of the catalytic petrochemical plants. The manual was designed to help students in mastering of discipline "Technology of heterolytic and homolytic oil refining processes" and preparation for exams. The manual presents materials from domestic and foreign literature on the technology of obtaining a variety of petroleum products from one raw materials ‒ oil, theoretical bases of action of catalysts in the catalytic homolytic and heterolytic processes of oil refining, the basic technological principles of catalytic refining processes, ecological problems of oil refining and petrochemistry. In the manual for the best learning of the educational material, questions for self-checking have been added to each chapter. The manual contains a glossary and a list of recommended literature. The publication of this training manual is timely and relevant, because in accordance with the reform of education in the RK and the need to teach disciplines in English an extreme shortage of manuals in English language is observed. Study of general regularities of catalytic homolytic and heterolytic petrochemical processes; basic reactions and reactors of catalytic petrochemical industries, scientific achievements in the field of technology of heterolytic and homolytic 3

oil refining processes are important to obtain the necessary amount of knowledge for the production of highly qualified specialists in the specialty "petrochemistry" for the oil and gas extraction and petroleum refining industry in Kazakhstan. This manual is due to its simplicity, logicality of presentation, visibility and availability of the represented material will allow the masters with the English learning system for one semester to familiarize with the content of the discipline “Technology of heterolytic and homolytic oil refining processes”. The manual can be useful for students studying in the specialty “Petrochemistry”, “Chemical Technology of Organic Substances”, doctoral students and university teachers to prepare for lectures, seminars and practical classes. The manual is intended for students, masters and bachelors, doctoral students specializing in the field of petrochemistry, catalysis, chemical technology of organic substances, catalysis and oil and gas business.

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1.1. The general concepts about oil and oil processing Oil is a mineral that is an oily liquid. It is a combustible substance, often black in color, although the colors of oil vary from region to region. It can be brown, and cherry, green, yellow, and even transparent. From a chemical point of view, oil is a complex mixture of hydrocarbons mixed with various compounds, for example, sulfur, nitrogen and others. Its odor can also be different, since it depends on the presence of aromatic hydrocarbons and sulfur compounds in its composition. The hydrocarbons that make up oil are chemical compounds consisting of carbon (C) and hydrogen (H) atoms. In general, the hydrocarbon formula is CxHy. The simplest hydrocarbon, methane, has one carbon atom and four hydrogen atoms, its formula is CH4. Methane is a light hydrocarbon, always present in oil. Depending on the quantitative ratio of the various hydrocarbons that make up oil, its properties also differ. Oil can be transparent and fluid like water. And it can be black and so viscous and slow-moving that it does not flow out of the vessel, even if it is turned over. Oil (and its accompanying hydrocarbon gas) lies at depths of several tens of meters to 5-6 kilometers. At that, only gas is found at depths of 6 km and below, and at the depths of 1 km and above only oil is found. Most productive reservoirs are at a depth between 1 and 5

6 km, where oil and gas are found in various combinations. Oil in mountain reservoir rocks is found. The formation of oil is a very long process. It passes in several stages and occupies, according to some estimates, 50-350 million years. According to the theory of the organic origin of petroleum (biogenic theory), oil was formed from the remains of microorganisms that lived millions of years ago in extensive water basins (mainly in shallow water). Dying off, these microorganisms formed at the bottom layers with the high content of organic substance. Layers, gradually plunging more and more deeply (this process takes millions of years), were affected by the amplifying pressure of the top layers and temperature increase. As a result of the biochemical processes happening without oxygen access, organic substance was transformed to hydrocarbons. Part of the formed hydrocarbons was in gaseous state (the lightest), a part was in liquid (heavier) and some part was in solid form. Respectively, mobile mixture of hydrocarbons in gaseous and liquid state under the influence of pressure gradually moved through permeable rocks towards smaller pressure (as a rule, upward). The movement continued until on their way the thickness of impenetrable layers hasn't met and the further movement was impossible. It is the so-called trap formed by reservoir-layer and the impenetrable layer-cover covering it. In this trap mixture of hydrocarbons gradually accumulated, forming what is called the oil field. Thus, the oil field actually isn't the birthplace of oil, but the place of its congestion. Oil is known to the person since the most ancient times. The term "oil" comes from the Persian language through the Turkish word "neft". There are data that 6,500 years ago the people living in the territory of modern Iraq added oil to the construction and cementing material at construction of houses to protect the dwellings from moisture penetration. Ancient Egyptians collected oil from a water surface and used it in construction and for lighting. Oil was also used for sealing of boats and as a component of the mummifying substance. At the time of ancient Babylon in the Middle East quite intensive business on the base of this "black gold" was done. Some cities already then literally grew on trade in oil. One of seven wonders of the world, the well-known Hanging gardens of Seramida (according to other version ‒ Hanging gardens of Babylon), have also 6

used oil as a sealing material. Not everywhere oil was collected only from a surface. In China more than 2000 years ago small boreholes were drilled using bamboo trunks with a metal tip. Initially wells were intended for extraction of salty water from which salt was extracted. But when drilling deeply from wells oil and gas were also extracted. It is unknown whether oil has found application in ancient China, it is known only that the gas was ignited for evaporation of water and salt extraction. Approximately 750 years ago, the famous traveler Marco Polo in his description of his travels to the East mentioned about the use of oil by the inhabitants of the Absheron peninsula as a remedy for skin diseases and fuel for lighting. The first mentions of oil in the territory of Russia belong to the 15th century. Oil was collected from a water surface on the river Ukhta. Just like other peoples, here the local population used it as a medicine and for economic needs. Russia is the birthplace of industrial oil refining. Fedor Pryadanov built the first oil refinery on the basis of Ukhta oil in 1745, giving annually up to a thousand poods of “pure transparent oil”. It represented a broad fraction in the amount of up to 60% of crude oil, similar to kerosene. This liquid was used for medical purposes and as lamp oil. Up to now original drawings of the plant of pioneers of oil processing ‒ brothers Vasily, Gerasim and Makar Dubinins, serfs of the countess Panina have remained. The plant has been constructed in 1823 in Mozdok and successfully used the Grozny oil. The distillation cube of periodic action with a capacity of 40 buckets (about 500 liters) was a basis of the plant. The yield of kerosene was about 40 % on oil. At these primitive plants from oil only lighting kerosene had been separating, and lighter fractions – gasoline and heavy – fuel oil had been burning in “black oil” pits as not finding applications. The first installations abroad were built in England in 1848, and in the USA in 1860. The first units for primary oil refining were made in the form of periodic batch cubes. The target product of these units was the lighting kerosene. The rest of the products were burned. But already in the 80’s. XIX century the cubes were replaced by batteries of cubes, which ensure the continuity of distillation of oil. 7

They were created by famous Russian engineers A.F. Inchik, V.G. Shukhov and N.I. Elin. With the invention in 1876 nozzles for liquid fuel, fuel oil was found to be used as fuel for boiler units. Another application of fuel oil was found by D.I. Mendeleev, who suggested using it as a lubricant instead of vegetable and animal fats. D.I. Mendeleev stressed the importance of oil as a valuable raw material for the synthesis of various products and said at a conference of Russian chemists in Moscow in 1887: “Burning oil and gas in furnaces is tantamount to burning the banknotes in the furnace”. According to some sources, the world’s first oil well was drilled in 1847 near the city of Baku on the shore of the Caspian Sea. Soon after, numerous oil wells were drilled in Baku, which was a part of the Russian Empire at that time, and this city was called as the Black City. Nevertheless, the year 1864 is considered to be the birth of the Russian oil industry. In the autumn of 1864 in the Kuban region, a transition was made from a manual method of drilling oil wells to a mechanical shock-rod with the use of a steam engine as a drive of a drilling rig. Start date of commercial world oil production, according to the majority of sources, it is considered to be on August 27, 1859. It is day when from the USA first oil well was drilled by “colonel” Edwin Drake inflow of oil with the fixed yield has been obtained. This well of 21,2 meters in depth had been drilled by Drake in the city of Taytusvil, State of Pennsylvania where drilling of water wells often was followed by oil presence. Although oil has been known since ancient times, it has found rather limited use. The modern history of oil begins in 1853, when the Polish chemist Ignaty Lukasevich invented a safe and easy-to-use kerosene lamp. He, according to some sources, discovered a way to extract kerosene from oil on an industrial scale and founded in 1856 an oil refinery in the vicinity of the Polish city Ulaszowice. In 1846 the Canadian chemist Abraham Gössner had thought up how to obtain kerosene from coal. But oil allowed to obtain cheaper kerosene and in much bigger amounts. The growing demand for the kerosene used for lighting had generated demand for initial material (fig.1). The second half of the 19th century had been called in history of oil industry as the “kerosene” period. 8

Virtually the entire period from the beginning of the oil industry (since 1859) is almost always the first two places were taken by the US and Russia. Until 1913, when the world’s first thermal cracking unit was launched in the United States, only the primary distillation of oil was produced in oil refineries, whose products ‒ gas, gasoline, kerosene, diesel fuel, fuel oil and others ‒ were the marketable products. From this time the epoch of secondary processes in oil refining began. The raw material for the newly introduced unit were gas oil fractions of the primary distillation of oil, cracking of which was carried out at elevated temperatures and pressures.

Figure 1. Oil production in the 19th century

In connection with ever increasing requirements to the quality of motor fuels, primarily to detonation properties, in the 20-30’s. XX century there is a rapid development of secondary processes of oil refining. Industrial processes of catalytic cracking of middle distillates, alkylation of alkenes, polymerization of lower alkenes were mastered. 9

In the USSR, the first refineries after the Civil War began to be built in the late 1920s. The rapid growth of oil refining was observed all over the world after the 2nd World War. In September, 1960 at a conference in Baghdad the international organization of the countries – exporters of petroleum (OPEC) was created. Initially OPEC consisted of five countries – Iran, Iraq, Kuwait, Saudi Arabia and Venezuela, and then were joined by another six ‒ Qatar (1961), Indonesia and Libya (1962), UAE (1967), Algeria (1969) and Nigeria (1971). The supreme body of OPEC is the Conference consisting of the delegations representing member states, headed by ministers of oil mining industry or a power engineering. Meetings of the Conference are held two times a year, in the headquarters ‒ OPEC apartment, located in Vienna (Austria). The purpose of OPEC is carrying out the coordinated policy for establishment of the accepted prices of oil for producers, ensuring efficient, regular and profitable supply with oil of consuming countries; ensure of fair receipt of income from investments by investors in the oil industry; environmental protection; cooperation with the countries ‒ not members of OPEC for realization of initiatives of stabilization of the world market of oil. For the members of the cartel’s high prices are the vital necessity, as the export of oil is not only a significant share of budget revenues, but gross national product of these countries. All OPEC countries are deeply dependent on the income of their oil industry. Perhaps the only country that represents the exception is Indonesia, which receives substantial revenues from tourism, forests, gas and other raw materials. For other OPEC countries, the level of dependence on oil exports varies from the lowest ‒ 48% in the case of the United Arab Emirates ‒ to 97% in Nigeria. The need for natural gas had arisen in comparison with the need for oil for 100 years later – in the 20th century, and had experienced rapid growth in its second half when development of economy without gas became impossible. Development of gas fields had allowed to bring quickly enough gas production to 2 trillion m3 a year that had turned oil and natural gas into the base of wellbeing of a modern civilization. This situation will remain also within the next century. The main milestones of history of world oil processing are briefly given in tab.1. 10

Today oil, as natural gas is the main and almost an unalternative source of energy, and its reserves are irretrievable. Thus to further processing are subjected only 10% of extracted crude oil, and the remaining 90% ‒ are incinerated. The reserves of petroleum and gas amount to several billion tons. In the list of countries with the largest reserves of oil are: Saudi Arabia, Iran, Iraq, Kuwait, Venezuela, the United Arab Emirates, Russia, Libya, Kazakhstan, Nigeria, the United States, Canada, Qatar, China, Angola. Consumption of petroleum in the world will grow according to forecasts to about 5.335 million tons by 2030. More than 80.0% of the growth in oil consumption from the total are the share of the developing countries of Asia and the Middle East, in which are expected higher economic growth rates. The main consumer of oil is transport sector (80%). The greatest growth in oil consumption is expected in developing countries in Asia: in China and India. On the increased volume of consumption of fluid hydrocarbons China wins first place in the world. China is the leading country of the world on use of oil in the chemical and petrochemical industry. Today China is the second largest importer of petroleum from the USA. As and the USA China have huge production of own oil. After China second place in terms of increasing in oil consumption occupy the Middle East, especially Saudi Arabia, Iran and Turkey. In Latin America: Brazil (more than half), Argentina (agricultural sector), and Venezuela (more than 60% of its oil will be spent on transport). Regardless of the forecast, the oil is to be the dominant source of energy. The main importers of oil in the medium term will be the countries of South-East Asia, Central and Eastern Europe. If to look at geography of oil and gas fields, then it is easy to notice that many of them sea. It is considered that potential marine resources of hydrocarbonic raw materials make more than a half of world. Today extraction of the offshore oil reaches about one third of its total extraction. The main part of initial explored reserves and the modern extraction of hydrocarbonic raw materials on the shelf belongs to five regions: The Persian Gulf, the lake Maracaibo (belongs to Venezuela and Colombia), the Gulf of Mexico, the Caspian and North Sea. 11

Oil industry is the branch of the heavy industry which is engaged in investigation of oil and gas fields, oil and petroleum gas production, processing, transportation and sale of petroleum and gas. The purpose of petroleum refining (oil processing) is production of oil products, first of all, various fuels (automobile, aviation, boiler etc.) and raw materials for the subsequent chemical processing. Oil products (fig.2) are the mixtures of hydrocarbons and some of their derivants; the individual chemical compounds obtained at petroleum refining and used as fuels, lubricants, insulant environments, solvents, road surfaces, petrochemical raw materials. The considerable proportion of oil products are the mixes of separate hydrocarbonic components containing various additives improving properties of oil products and increasing stability of their production characteristics. Fuel (gaseous and liquid) is one one of the main of oil products groups. Table 1 Brief history of world oil refining No Years 1 2 1 1862 2 1870

3

1913

4

1916

5

1930

6 7

1932 1932

8

1933

9 10

1935 1935

11

1937

12

Name of the process The process aim 3 4 Atmospheric distillation To produce kerosene Vacuum distillation To produce lubricants (original) and cracking feedstocks Thermal cracking To increase gasoline producing Desulfuration To reduce sulfur and odor Thermal reforming To increase octane number Hydrogenation Sulfur removal Coking Base gasoline production Solvent extraction To improve lubricant viscosity index Solvent dewaxing To improve pour point Catalytic polymerization To improve gasoline yield and octane number Catalytic cracking To obtain gasoline wth higher octane number

By-products 5 Naphtha, tar Asphalt, residual coker feedstocks Residual, bunker fuel Sulfur Residual Sulfur Coke Aromatics Waxes Petrochemical raw materials Petrochemical raw materials

1 12 13

2 1939 1940

3 Visbreaking Alkylation

14

1940

Isomerization

15

1942

Fluid catalytic cracking

16

1950

Deasphalting

17

1952

Catalytic reforming

18 19

1954 1956

20

1957

Hydrodesulfurization Desulfuration, demercaptanization Catalytic isomerization

21

1960

Hydrocracking

22 23

1974 1975

Catalytic dewaxing Residual hydrocracking

4 To reduce viscosity To increase octane number and yield of gasoline To produce alkylation raw materials To increase octane number and yield of gasoline To increase cracking feedstock To convert low-quality naphtha Sulfur removal Removal of mercaptans

5 Distillate, tar High-octane aviation gasoline

To produce molecules with high octane number To improve quality and to reduce sulfur content To improve pour point To increase gasoline yield from residual

Alkylation feedstocks

Naphtha Petrochemical raw materials Asphalt Aromatics Sulfur Disulfides

Alkylation feedstocks Waxes Heavy residuals

Hydrocarbon oils (petroleum oils) is the second on volume basis and on value group of oil products. Oil technical asphalts ‒ bitumen (road, structural asphalts) is the third on volume basis productions group of marketable oil products, widely used in the national economy. So-called solid hydrocarbons belong to oil products: paraffins, ceresines, vaselines, petrolatum, ozokerite, etc. Marketable oil products are also various solvents, refinery coke, soot, emulsion breakers (demulsifiers) and so forth. The oil products obtained by separation of fractions of a pyrolysis of petroleum (benzene, toluene, a xylol, naphthalene, green oil, etc.), are applied generally as the petrochemical feedstocks. As chemical raw materials also the oil-refinery gases are used.

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Oil Products

Hydrocarbon oils

Motor (engine) fuels

aviation, automotive gasolines

The petrochemical raw materials

reactive

Carbon, cementing materials

diesel

Energy Petroleum fuels products for special purposes

Gas turbine

For boiler installations

Figure 2. The oil products

1.2. Refinery: general information, refinery types Refinery is an enterprise for production, based on the transformation of oil and its fractions, and petroleum gases into marketable petroleum products and raw materials for the petrochemical industry. This production represents set of the physical and chemical and technological processes and operations including raw materials preparation, its primary and (or) secondary processing. The main function of the refinery is petroleum refining into gasoline, aviation kerosene, fuel oil, solar oil, lubricating oils. In addition at the modern oil refineries produce from petroleum approx. 12 ‒ 16 more principal components. In general, the refinery is characterized by the following key indicators: ‒ Processing volume (in thousands ton in a year) ‒ Depth of processing, the product range and its quality. At a design stage of oil refinery the second group of indexes defines the choice of technologies for producing the corresponding products. 14

The complete structure of the refinery comprises the sequence of basic processes (fig. 3): ‒ supply of petroleum crude ‒ fractional distillation ‒ chemical treatment ‒ cleaning and mixing ‒ storage of finished products ‒ products transportation Petroleum

Crude vacuum unit (ELOU-AVT)

Gasoline

Distillation into fractions

Gases

Propane, butane

Diesel fuel

Vacuum gas oil

Hydrotreating

Catalytic cracking

Reforming

Diesel fuel

Household gases

Gasoline Propylene

Polymerization Commodity park Polypropylene Figure 3. The approximate scheme of production cycle of the oil refinery

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Currently, the following products are manufactured at the refinery (tab.2): ‒ Gasoline ‒ Diesel fuel ‒ Fuel oil (masut) ‒ Construction bitumen ‒ Technological fuel ‒ Gases ‒ Sulfur ‒ Lubricating oils ‒ Petroleum coke ‒ Petrochemical feedstocks Table 2 Classification of the refinery, depending on the produced oil products Classification

Output goods

Fuel refinery

combustible gases, motor oil, bitumen, petroleum coke

Fuel and oil refinery

petroleum oils, lubricants, solid paraffins

Fuel and petrochemical oil refineries

different types of fuels, hydrocarbon materials, production of petrochemistry ‒ polymers, reagents, and so forth.

Refinery (Petrochemical Complex) of fuel and oilpetrochemical profile

different types of fuels, oils, lubricants, products of petrochemistry

Territorial position of oil refinery At the choice of a territorial arrangement of future oil refinery are guided by the following criteria: ‒ a proximity of large-scale deposits (for future increase in production capacities); ‒ a developed infrastructure (proximity to power lines, a little distance from the industrial centers, a great distance from the specially protected natural territories); ‒ climatic conditions of the territory; ‒ road location for product sales; ‒ the geographical location of competing companies. 16

The production cycle of oil refinery usually consists of preparation of raw materials, primary distillation of petroleum and secondary processing of oil fractions. Prices of oil products at various oil refineries differ from each other. The oil refinery represents set of the basic petrotechnological processes (installations, shops, blocks), and also the auxiliary and serving services providing normal functioning of the production enterprise (commodity and raw, mechanical-repair shops, the instrumentation and automated control systems shop, vapor-, water ‒ and power supply, shop and factory laboratories, etc.). A distinctive feature of the refinery is to produce a variety of products from the same source petroleum feedstock. It is characteristic that in most processes only produce mainly components or intermediates. The final marketable oil products obtained usually by compounding several components produced at this refinery and additives and dopants. Oil refining is a continuous production and working period of production between major overhauls in modern plants amounts to 3 years. There are two methods of oil refining: primary (separation) and secondary (conversion). In modern refineries basic primary process is the separation of crude oil into fractions, ie, its distillation. Distinguish distillation with a single, multiple and gradual evaporation. Raw materials for processes of secondary petroleum refining (conversion) are the oil products obtained at primary petroleum refining (separation processes). The source of raw materials for processes of conversion is presented in tab.3. The basis of the petrochemical plants constitute the installations on manufacture of hydrocarbon gases ‒ ethylene, propylene, butane, as well as the complexes for the production of aromatic hydrocarbons ‒ benzene, xylenes. Also productions of oxygen-containing substances ‒ alcohols, esters (methyl, t-butyl) are a part of petrochemical productions. The important place in structure of petrochemical productions is taken by productions of high-molecular compounds: polyethylene, polypropylene. The processes of the destructive petroleum refining intended for change of its chemical composition by thermal and catalytic influence belong to the second types (conversion processes): catalytic cracking, reforming, an isomerization, hydrotreating, etc. 17

According to their directions, all the conversion processes of refining can be divided into 3 types (tab.4): The deepening processes: catalytic cracking, thermal cracking, delayed coking, hydrocracking, bitumen production, etc. The ennobling (upgrading) processes: reforming, hydrotreating, isomerization, etc. Other processes: processes for the production of oils, MTBE, alkylation, aromatic hydrocarbons production, etc. Table 3 Products of the primary petroleum refining (separation processes) Name 1 Stabilization reflux

Boiling intervals (composition), ºC 2 Propane, butane, isobutane

Stable straightrun gasoline (naphtha) Stable light gasoline

b.b.*-180

Benzene

b.b.-62-85

Toluene

85-105

Xylene

105-140

b.b.-62

Raw materials of 85-180 catalytic reforming Heavy gasoline 140-180

Kerosene component Diesel

18

180-240 240-360

Where it is Application selected (in preference order) 3 4 Stabilization unit Gas fractionation, commercial products, technological fuel Gasoline Gasoline mixing, redistillation commercial products Stabilization unit Isomerization, gasoline mixing, commercial products Gasoline Production of the redistillation corresponding aromatic hydrocarbons Gasoline Production of the redistillation corresponding aromatic hydrocarbons Gasoline Production of the redistillation corresponding aromatic hydrocarbons Gasoline Catalytic reforming redistillation Gasoline redistillation Atmospheric distillation Atmospheric distillation

Mixing of kerosene, winter diesel fuel, catalytic reforming Mixing of kerosene, diesel fuels Hydrotreating, mixing of diesel fuels, fuel oils

Fuel oil

1

2 360- f.b.**

Vacuum gasoil

360-520

Tar

520- f.b.

3 Atmospheric distillation (residue) Vacuum distillation

Vacuum distillation (residue) * ‒ b.b.- boiling beginning, **- f.b.- final boiling point

4 Vacuum distillation, hydrocracking, mixing of fuel oils Catalytic cracking, hydrocracking, commodity products, mixing of fuel oils Coking, hydrocracking, mixing of fuel oils

Table 4 Processes of petroleum refining Process title

Method

1 2 Fractioning processes Atmospheric Thermal distillation Vacuum distilla- Thermal tion

Aim 3 Fractions separation

Initial raw mate- Products rials 4 5 Desalinated Gas, gasoline, petroleum crude distillate and the residue Rest of a column Gasoil, oil distilof atmospheric late, the residue distillation

Separation without splitting The conversion process ‒ decomposition Catalytic crack- Catalytic For gasoline Gasoil, distillate Gasoline, feed ing improving of coke stock of oil products Coking Thermal For the The residue, Naphtha, gas oil, vacuum heavy oil, tar coke residues convertion Hydrocracking Catalytic Convertion Gasoil, oil after The lighter and to lighter cracking and higher quality hydrocarresidues products bons Steam reforming Thermal/ Hydrogen Desulfonated Hydrogen, СО, of hydrogen catalytic production gas, O2, steam CO2 The steam crack- Thermal For splitting Heavy fuel / The crackinged ing of large distillate of a naphtha, coke molecules column of atresidues mospheric distillation

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1 Light cracking

2 Thermal

3 For the viscosity reducing

4 5 The residue from The distillate, the atmospheric cracking residue distillation column

Conversion processes ‒ Combining Alkylation Catalytic To combine Isobutane / Isooctane (alkylthe olefins olefins of crack- ate) and isopar- ing unit affins Preparation of Thermal To combine A lubricating oil, The lubricant the lubricant soaps and a fatty acid grease grease oils Polymerization Catalytic To combine Olefins of crack- High-octane naphtwo or more ing unit tha, components of olefins petroleum products The conversion process ‒ Change / regrouping Catalytic Catalytic To improve Naphtha of High-octane prodreforming the lowinstallation of a uct of reforming/ octane naph- coking/ aromatic compound tha hydrocracking plants Isomerization Catalytic To transform Butane, pentane, Isobutane/pentane/ a straight hexane hexane chain of hydrocarbons to branched Treatment processes (purification) Cleaning with AbsorpTo remove Sulphur dioxide, Acid-free gas amine tion acid hydrocarbons with and liquid hypollutants CO2 and H2S drocarbons Desalting AbsorpTo remove Crude oil Desalinated (pretreatment) tion pollutants crude oil Drying and AbsorpTo remove Liquid hydrocarPurified from cleaning from tion / H2O and bons, liquefied sulfur and dried the active sulfur thermal sulfur com- petroleum gas, the hydrocarbons pounds alkylated feedstock Extraction by AbsorpTo improve Circulating gas oil High-quality furfurol tion the middle and a feedstock of diesel and lubridistillate and oils cating oil oils Hydrodesulphu- Catalytic To remove High-sulphurous Desulphurisarisation sulfur and residue / gasoil tioned olefins pollutants

20

1 Hydrotreating

2 Catalytic

Extraction by phenol

Absorption / thermal

Deasphalting by solvent

Absorption

Dewaxing by solvent

Cooling/ filtering

Extraction by solvent

Cleaning from the active sulfur

3 To remove impurities / saturated hydrocarbons To improve an indicator of viscosity of oils, color Asphalt removal

4 The residues, the hydrocarbons of cracking

The basic components of the oil feedstock The residue of vacuum distillation column, propane Lubricating oil of vacuum distillation tower

For removing wax from the lubricating oil AbsorpSeparation Gasoil, reforming tion / of unsaturat- product (reforprecipitati ed aromatics mate), distillate on Catalytic For removal Crude distillate / H2S, mergasoline captans transformation

5 Raw materials for the cracking installation, distillate, lubricating oil High-quality lubricating oil

Heavy component of lubricating oil, asphalt Dewaxed lubricant base components

High-octane gasoline

High-quality distillate /gasoline

1.3. Oil refining in Kazakhstan. Kazakhstan refineries The oil industry of Kazakhstan is one of the main branches of Kazakhstan’s economy. About 200 oil and gas fields are located on the territory of Kazakhstan. The total amount of reserves is estimated at 11-12 billion tons. Almost 70% of these resources are located in the western regions of Kazakhstan. The Russian military, travelers and scientists noted the high probability of finding industrial oil reserves in this region. The first Kazakh oil was mined in November 1899 at the Karashungul deposit, in the Atyrau region. Further in the Emba area were discovered and developed two deposits of high-quality oil ‒ Dossor (since 1911) and Makat (since 1915). The geological condi21

tions of the sedimentary basins of Kazakhstan favor the expansion of the resource base of the oil and gas industry. Kazakhstan by the volume of proven oil reserves occupies 12-th place in the world. The country is a leading exporter of oil (per capita) among the CIS countries (fig.4). Nowday more than 3/5 of the country is occupied by oil and gas fields, and more than two hundred fields are known. Export of petroleum from Kazakhstan is one of important factor of expansion of world economic communications, inclusions of the country in globalization processes, realization not only economic interests. The largest oil fields of Kazakhstan are Kashagan, Tengiz, Karachaganak and Kashagan (location ‒ the north of the Caspian Sea) with the geological reserves, estimated to amount to 4.8 billion tons of oil. Tengiz field (location ‒ the Western Kazakhstan) is one of the world’s deepest producing super giant fields. The Karachaganak field’s oil and liquid condensates are estimated at approx. 1.2 bln. tons. The first-born of oil refining in Kazakhstan is the Atyrau refinery. The construction of the plant was started in 1943 under difficult wartime conditions, and in September 1945 the plant was put into operation. The technical design of the plant was developed by the American firm Badger and Sons, which supplied equipment for lendlease. Initial capacity of plant on oil refining was 800 thousand tons per year and was based on oil of the Embinsky field and imported Baku distillate. From the very beginning the plant developed according to the fuel variant, with the production of aviation and automobile gasolines, various motor and boiler fuels. Today Atyrau refinery is a large modern enterprise, which is located in the oldest oil producing region of the country. The Atyrau oil refinery processes heavy oil of fields of the Western region of Kazakhstan with the high content of paraffin. In assortment of products are gasolines, white spirit, diesel fuel, boiler fuel, fuel oil, coke. The Shymkent oil refinery is put into operation in 1985 and the design capacity of the plant on oil refining was 6 million tons per year. In 1994 the enterprise carrying the name of JSC “Shymkentnefteorgsintez” (ShNOS) was privatized, in 2000 was acquired by the Canadian company Hurricane. In 2000 reconstruction of section of hydrotreating of diesel fuel and kerosene was carried out. 22

Currently, the management of PetroKazakhstan Oil Products LLP (hereinafter ‒ PKOP) is carried out on a parity basis: the National Company KazMunayGas represented by JSC KazMunayGas ‒ Refining and Marketing, and the China National Petroleum Corporation CNPC. The processed raw materials of PKOP are mainly Kazakhstan oil from the Kumkol and Kenkiyak fields (oil mixture from the Kumkol field (80%), as well as West Siberian oil (20%).

Figure 4. A map of the main oil and gas fields of Kazakstan

Oil comes from Western Siberia through the Tyumen-OmskPavlodar-Shymkent pipeline. Oil is low-sulfur, one of the best in quality among the CIS countries. The depth of oil refining is 60.4%. The plant produces 30% of the total current volume of petroleum products produced by three refineries in Kazakhstan. The assortment of petroleum products includes various grades of gasoline, diesel fuel, aviation kerosene, liquefied gas, vacuum gas oil and fuel oil. The products of PetroKazakhstan are of high quality due to the application of a professional and high-tech refining process and the exceptionally high quality of Kumkol oil. Shymkent Oil Refinery (LLP PetroKazakhstan Oil Products) in 2016, with a plan of 4, 444, 623 tons, actually processed 4, 501, 467 tons of oil, the implementation of the plan was 101.28%. 23

The Shymkent oil refinery is the only oil refinery located in the south of Kazakhstan in the most densely populated part of the republic. Taking into account a favorable geographical arrangement and high technical capabilities the enterprise has all prerequisites for implementation of deliveries to the internal and external markets. The design capacity of the Shymkent oil refinery is 5.25 million tons, or about 40.65 million barrels of oil a year. The Pavlodar petrochemical plant was put into operation in 1978. In 1978-1994, it was called the Pavlodar Oil Refinery (POR), since 2009, JSC “POR” was included in the group of companies of the JSC National Company KazMunayGas, since March 2013 it is LLP “Pavlodar Petrochemical Plant”. The owner of the oil refinery is JSC National Company KazMunayGas. Pavlodar refinery is one of the best plants in terms of the ratio of primary and secondary processes. The plant is one of the most modern in technology in the Republic of Kazakhstan. The plant processes oil in a fuel variant and provides a processing depth of up to 77-85%, which corresponds to the level of the best producers of petroleum products. According to the technology, the plant is oriented to processing West Siberian oil. Oil for processing at the plant comes from Western Siberia through the Omsk-Pavlodar pipeline. The plant produces only unleaded gasoline, fuel for jet engines, summer and winter diesel fuel, boiler fuel, fuel oil, bitumen, petroleum coke, liquefied gases. The future of the oil and gas producing and oil refining industries in Kazakhstan is mainly related to the Kazakhstan sector of the Caspian Sea. Given the current global imbalance between the level of oil production and consumption, Kazakhstan has good potential to increase its oil production and, consequently, the export of hydrocarbon raw materials to the world markets every year. The most promising project for today is the development of the Karachaganak field, the total reserves of the field are 1.2 billion tons of oil and 1.35 trillion.m3 of gas. Production at the Tengiz field (whose total reserves are estimated at 2.7 billion tons of oil) is constantly increasing. Oil and gas still have no real alternative, and, therefore, there remains a need to develop oil and gas and oil refining industries, develop technology and technology based on modern standards, and 24

also to preserve the priorities in training highly qualified specialists for these fields of science and technology. Questions for self-checking: 1. Tell the history of use by mankind of oil and gas since the most ancient times. 2. Describe the history of the global oil industry until now. 3. What are the world’s recoverable reserves of oil, natural gas? 4. What countries are in the list of countries with the largest reserves of oil and gas? 5. Tell about the OPEC countries. 6. Tell about the history of OPEC. 7. What were the main purposes for OPEC organization creation? 8. How many countries were included into OPEC at the beginning of creation this organization? 9. Explain the role of oil in the fuel and energy balance. 10. What is oil industry? What are the oil products? 11. Tell about oil and gas as a valuable raw materials for petrochemistry. 12. Tell about Kazakhstan reserves of oil and the features of Kazakhstan oil. 13. Compare crude oil of Kazakhstan with that of another countries. 14. Tell about Kazakhstan reserves of gas. What are the main fields? 15. Describe the history of discovery of Kazakhstan's deposits. 16. What is the refinery? 17. List the main processes of the refinery. 18. Tell about classification of the refinery. 19. Tell about a territorial position of oil refinery. 20. What is the production cycle of oil refinery? 21. Explain the purpose of petroleum refining. 22. Give the definition of the primary and secondary methods of refining. Compare these methods of oil refining. 23. List the products of primary petroleum refining. 24. List the secondary refining processes. 25. List the conversion processes of oil (decomposition and change/ regrouping): aim, raw materials, products. 26. List the treatment processes (purification): aim, raw materials, products. 27. List the deepening processes, the ennobling processes of the refinery. 28. Tell about Kazakhstan refineries. 29. Tell about the prospects for the development of oil and gas technology in Kazakhstan. 30. Describe the prospects for the development of petrochemistry in Kazakhstan.

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2.1. Catalysis as phenomena. Catalysis preconditions. Catalytic activity Currently, up to 90% of all chemical products in the world are produced by catalytic methods. The technical progress of chemical, petrochemical, oil refining and other industries largely depends on the development of catalysis. Catalysis is a universal and very diverse phenomenon, widespread in nature and used by mankind for thousands of years before realizing the essence of catalytic processes. Catalysis is a phenomenon by which chemical reactions are accelerated by small quantities of foreign substances, called catalysts. The first generalizations of the facts of catalytic action have been made by L. Mitcherlikh and Y.Ya. Bertselius in 1834-1835. Mitcherlikh has for the first time united catalytic processes under the name of contact reactions in 1834: when initial substances aren’t exposed to changes in the chemical nature, but in the presence of small amounts of the contact material introduced therein, they undergo a chemical transformation. Opening of the phenomenon of a catalysis can be referred to one of the greatest achievements of the chemical science which has served to development of all modern chemical technology. According to some scientists, the phenomenon of catalysis could have been of decisive importance in the process of the origin of life. 26

The first known example of a non-biological catalytic process is the synthesis of ether from alcohol, with the participation of sulfuric acid (VIII-th century, Jabir ibn Khayyam): C2H5OH + HO-C2H5 → H2O + C2H5-O-C2H5

(1)

The first reports on the synthesis of sulfur ether and ethylene from ethanol with the use of acid catalysts date back to the 16th-17th centuries, however, the 19th century can be considered as a starting point in the history of catalysis. It is enough to tell that almost all outstanding physicists and chemists of the 19th century were engaged in a catalysis. In 1835, Berzelius, summarizing the accumulated experience, proposed a different way of considering catalytic reactions. It was he who proposed the term “catalysis” (from the Greek “katalisis” ‒ destruction) to describe the phenomena of non-stoichiometric interference of “third bodies”, catalysts, into chemical reactions. According to Bertselius, “catalytic ability” (catalytic activity in modern understanding) of many both simple, and complex bodies in a solid type and a form of solution, is one of manifestations of the electrochemical relations of matter. A great merit of Bertselius for development of prerequisites of emergence of kinetics and for its formation was that he has managed to generalize the researches performed earlier out of stoichiometric influence of substances on various reactions and to unite all these processes by a community of the reason of catalytic force. Bertselius called catalytic force as “the reason of chemical action” and has put forward the thesis about “thousands of catalytic reactions in an organism”. In 1839 the German chemist Yu. Libikh with his theoretical conclusions in the field of a catalysis had acted and offered an explanation of the nature of this phenomenon connected with gradual change of affinity of the reacting substances. In his work, he pointed out that “[the cause of catalysis] is the ability possessed by a body that is in a state of decomposition or connection, i.e. in the state of chemical action, in the ability to cause in the other body in contact with it the same chemical activity, or to make it capable of undergoing the same change that it itself experiences”. Libikh connected a deviation from a stoichiometry with a continuity of the chemical interaction begun 27

under the influence of these reasons, considering that the catalyst at the same time remains chemically invariable. B. Ostwald wrote that “catalyst is a compound that speeds up a chemical reaction without affecting the position of equilibrium”. P. Sabatier noted: “catalyst” is a substance or system that can change the rate of the reaction, by participating in the sequence of steps, but without turning into products. The most general definition of catalysis was given by academician A.A. Balandin (1898-1967): “Catalysis is the effect of a substance on a reaction that selectively changes its kinetics, but retains its stoichiometric and thermodynamic conditions; this effect consists in replacing some elementary processes by other, cyclic, in which the active substance participates. The introduced substance is called a catalyst, it does not change quantitatively as a result of the reaction and does not shift the equilibrium”. Catalysis is a well-established scientific discipline, dealing not only with fundamental principles or mechanisms of catalytic reactions but also with preparation, properties, and applications of various catalysts. A number of academic and industrial institutes or laboratories focus on the study of catalysis and catalytic processes as well as on the improvement of existing and development of new catalysts. A very significant feature of catalysis is the fact that the catalyst preserves its composition throughout intermediate chemical interactions with the reactants. The catalyst is not wasted in the course of catalysis. This means that the catalysis is not associated with changes in the free energy of the catalyst and hence the catalyst cannot influence the thermodynamic equilibrium of chemical reactions. Near balanced state the catalyst equally accelerates both direct, and inverse reactions. During removal from balanced state this condition cannot be carried out. In the course of catalytic reactions a catalyst does not undergo any transformations. In many cases these changes in the catalyst structure occurs, sometimes ‒ in its compositions as a result of interaction with the admixture, and even with the main components of the reaction mixture. In this regard in the commercial catalytic runs operations of replacement, periodic or continuous reactivation of the catalyst are provided. 28

For certain transformations and reactions the catalysts with the certain properties are used. Of course the catalyst composition and chemical structure are extremely varied. There is the positive catalysis, i.e. increase in reaction rate under the influence of the catalyst, and there is the negative catalysis, leading to decrease of speed of chemical transfomation. Positive catalysis: the intermediate interaction of reactants with the catalyst opens new, energetically more favorable (i.e. with the smaller height of an energy barrier), in comparison with a thermolysis, a reactionary path (route). Negative catalysis: on the contrary, the fast and energetically lighter stage of chemical interaction is suppressed (inhibited). It should be noted that the term “Catalysis” means catalysis predominantly only positive. Industrial catalysts on the whole contain different combinations of almost all elements. Most catalysts contain several elements. They can be in their elemental form: for example numerous metallic catalysts and activated carbon; or in the form of different compounds, both comparatively simple, like oxides, sulfides, halides; or as complex like metal complexes with organic ligands or polyatomic compounds of protein nature such as enzymes. In most of technical catalytic processes a small amount of catalyst promotes the transformation of rather significant amounts of reactants. Thus, one mass part of catalyst causes transformations in sulfuric acid production of ten thousand (104), in naphthalene oxidation into phthalic anhydride of thousand, and in nitric acid production – by ammonia oxidation of one million reactant mass parts. The biological catalysts generally named enzymes are complex compounds of protein nature. Some of enzymes increase the rate of chemical reactions by the order 1010-1012. Very important and characteristic property of the enzymes as catalysts is specificity of their action. Although catalytic phenomena are quite common in nature and man was faced with them long ago, large scale utilization of catalysis in industry began only in the last centure. A major landmark in the development of industrial catalysis was the elaboration of the contact process of sulphuric acid production based on oxidation of sulfur dioxide obtained in pyrites annealing or in sulfur burning in 29

atmospheric oxygen in the presence of platinum different supports. This process of concentrated sulfuric acid obtaining played an important part in the development of synthetic dye industry. Of great importance for the development of chemical industry was the solution on the basis of catalysis of the problem of fixing of atmospheric nitrogen. It was only with the help of catalysts that the chemical inertness of nitrogen was overcome and ammonia was synthesized from atmospheric nitrogen and hydrogen. Ammonia oxidation is an example of selective catalysis widely used in industry where the catalyst not only increases the rate of chemical transformation, but also directs it towards the formation of one particular product out of a number of possible products. In most cases in the presence of the given catalyst besides the basic reaction proceeds some more parallel and consecutive reactions and the initial substances turn to a mixture of various products. Content of the reacted initial substances, transformed at presence of given catalyst to desirable products, characterises it is selectivity. Selectivity of the catalyst is changed with the change of reactions conditions. Selectivity of catalyst is mean ability of catalyst selectively realize the primary one among another thermodynamically possible directions of reactions. This ability of catalyst is very important for organic catalysis. Selectivity depends also on a thermodynamic equilibrium. Sometimes selectivity conditionally express in oil processing as the relation of yields of target and by-products, for example such as gasoline/gas, gasoline/coke or gasoline/gas + coke. For example in tab. 5 the possible transformations of ethanol at presence of different catalysts are pesented. By the way from ethanol it is possible to obtain about 40 different products depending out the composite of catalyst. Table 5 Ethanol transformations

2C2H5OH→

30

Processes 2 C2H4+2H2O 2 CH3CHO+2H2O C4H9OH+H2O C4H8+H2+H2O CH3COOC2H5+2H2

Catalysts Al2O3, H2SO4 (oleum) Cu (reduced) Na metallic and alkaline promotors Zn.Al2O3 Cu-catalysts with additives

Very important feature of a catalysis is their specificity of operation. The catalytic activity is defined by the specific speed of this catalytic reaction, i.e. quantity of the product which is formed in unit of time per unit of volume of the catalyst or reactor. It is impossible to consider catalytic activity as the universal property of the catalyst. Many catalysts are active only with respect to one particular reaction or a narrow group of reactions. Especially specific is the reaction of biological catalysts i.e. enzymes. In a majority of cases enzymes catalyze the transformations of only a few chemical compounds from among the great number of compounds with similar structure, or even only one. Some catalysts not enzymes are active with respect to rather wide gtoups of reactions. For example, catalysts with acid nature are active with respect to a large number of reactions of isomerization, hydrolysis, alcohol dehydration, alkylation and many others. Also metallic nickel catalysts are very active in the different reactions of hydrogenation. Stability is one of the most important indexes of quality of the catalyst, characterizes its ability to keep the activity in time. It affects on the stability of the systems, the duration of their time between repairs, process design, catalyst consumption, material and economic costs, environmental issues and the technical and economic parameters of the process, and others.

2.2. Classification of catalysis and catalytic reactions Distinguish a homogeneous catalysis ‒ reagents and the catalyst are in one phase, and a heterogeneous catalysis ‒ the catalytic system includes several phases. In oil processing the heterogeneous catalysis, especially with the solid catalysts, is widespread much more, than homogeneous. Data on history of a homogeneous and heterogeneous catalysis are briefly presented in the tab. 6.

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Table 6 Brief history of catalysis Years Authors Process 1 2 3 Homogeneous catalysis 1746 J. Robek SO2 + 0.5 O2 → SO3 1782 K. Scheele RCOOH + R’OH → → RCOOR’ + H2O 1878 A.M. Butlerov m CnH2n → -(CnH2n)-m 1881 M.G. KuС2Н2 + Н2О → СН3СНО cherov 1928- Yu. Newland 2 С2Н2 → СН2=СНС≡СН 1929 1938 O. Roelen CnH2n + СО + Н2 → → CnH2n+1СНО 1939- V. Reppe 1. С2Н2 + СО + НХ→ 1945 → СН2=СНСОХ 2. С2Н4 + СО + НX → → СН3СН2СОХ (X – OH, OR, NR2, SR) 3. 4 С2Н2 → cyclooctatetraene 4. С2Н2 + 2 CH2O → → HOCH2C≡CCH2OH 1953- K. Ziegler, m α-CnH2n → -(CnH2n)-m 1955 D. Natta

1959 1960 1960 1970

1972

J. Smidt, I.I. Moiseyev I.I. Moiseyev The company BASF AG F.E. Paulik, D.F. Roz, the company “Monsanto” The company “Halkon”

С2Н4 + 0.5 О2 → СН3СНО

4 NO2 Mineral acids H2SO4 Hg2+ Cu(I) Со2(СО)8 1. Ni(CO)4 2. Ni(0), Co(0) 3. Ni(CN)2 4. Cu2C2

TiCl3-AlR3, TiCl4AlR3, homogeneous and heterogeneous catalysts for the polymerization of 1-alkenes and dienes PdCl2-CuCl2

С2Н4 + CH3COOH + 0.5 О2 → PdCl2-CuCl2→ СН2=СНОOCCH3 + H2O CH3COONa CH3OH + CO → СН3СОOH CoI2 CH3OH + CO → СН3СОOH

Rh(I)-CH3I

The conjugate process for the production of styrene and propylene oxide

Heterogeneous catalysis 1778 J. Priestley СnH2n+1OH → СnH2n + H2O

32

Catalyst

Clay (aluminosilicate)

1 1796 1831 1844 1863 1867 1867

2 M.VanMarum P. Phillips M. Faraday G. Debus G. Deacon A. Hoffmann

1877

M.M. Zaitsev

1890

?

1900s

P. Sabatye

1903

V. Ostwald

19081914

Mattiash, Haber, Bosch (BASF) Bosch (BASF) СО + 2 Н2 → СH3OН

1923 1930

E. Fisher, H. Tropsch

1931

T.E. Lefort

3 С2Н5ОН → СН3СНО + Н2 SO2 + 0.5 O2 → SO3 С2Н4 + Н2 → С2Н6 HCN + Н2 → СH3NН2 4 HCl + O2 → 2 Сl2 + 2 H2O CH3OH + 0.5 O2 → → СH2O + H2O Hydrogenation of organic compounds in the liquid phase СН3ОН+0.5 O2 → → СH2O + H2O ( Н2) Hydrogenation and oxidation of organic compounds 2 NH3 + 3 O2 → → NO + NO2 + 3 H2O 3 H2 + N2 = 2 NH3

Catalytic cracking, reforming

1940s

Catalytic hydrocracking The company “Halkon”

1960

The company “Sohio”

1967

The company “Bayer”

Pd, Pt metals: Ag,Cu Ni Pt FeO+Al2O3+Ca+K+Si O2 ZnO∙Cr2O3, ZnO∙CuO∙Cr2O3 1. Co 2. Fe

1. nСО + (2n+1)Н2 → → СnH2n+2 + n Н2O 2. 2n СО + (n+1) Н2 → → СnH2n+2 + n CO2 / Products contain alkenes and oxygencontaining compounds С2Н4 + 0.5 О2 → (СН2СН2)О Ag/carrier

1930s

1955

4 metals: Ag,Cu, Ce, Fe, Ni, Pb, Sn, Mn Pt Pt Pt Cu Pt

С6Н6 + 4.5 О2 → → maleic anhydride + 2 Н2О + 2 СО2 C3H6 + 1.5 О2 + NH3 → → CH2=CHCN + 3 Н2О + + 2 СО2 С2Н4 + CH3COOH + 0,5 О2 → → СН2=СНОOCCH3 + H2O

MoO3∙Al2O3, Pt/ Al2O3

V2O5 + promotors MoO3∙Bi2O3∙P2O5+ additives Pd(OAc)2-CH3COOK/ SiO2

By the nature of the intermediate chemical interaction of reactants and the catalysts catalysis can be subdivided into the following three classes: 33

1) hemolitic catalysis when chemical interaction proceeds on the homolytic mechanism; 2) heterolytic catalysis ‒ in case of the heterolytic nature of the intermediate interaction; 3) bifunctional (composite) catalysis including both types of chemical interaction. On homolytic, mainly so-called electronic catalysis reactions of redox type proceed (such catalysis therefore often call redox ‒ oxidation-reduction): hydrogenation, dehydrogenation, hydrogenolysis of heteroorganic compounds of oil, oxidation and reduction in the production of elemental sulfur, of steam conversion of hydrocarbons in the production of hydrogen, the hydrogenation of carbon monoxide to methane, and others. The transition metals (with unfilled d- or fshell) of the first subgroup (Cu, Ag) and group VIII (Fe, Ni, Co, Pt, Pd) of the periodic system of Mendeleev, their oxides and sulfides, mixtures thereof (nickel molybdates, cobalt, vanadates, tungstates, chromates), and metal carbonyls and others have catalytic activity with respect to such reactions. Heterolytic or so-called ionic catalysis, takes place in the reactions of catalytic cracking, isomerization, cyclization, alkylation, dealkylation, the polymerization of hydrocarbons, alcohol dehydration, olefin hydration, hydrolysis and many other chemical and petrochemical processes. Ionic catalysts for reactions include both liquid and solid acids and bases (on this sign a heterolytic catalysis is often called as acidbase) to catalysts of ionic reactions: H2SO4, HF, HCl, Н3РО4, HNO3, СН3СООН, AlCl3, BF3, SbF3, alumina, zirconia, aluminosilicates, zeolites, ion exchange resins, alkali and others. In technical catalysis (for example by catalytic reforming and hydrocracking) are widely used the bifunctional catalysts consisting of the carrier of acid type (the alumina, aluminosilicates promoted by haloids, zeolite, etc.) with the metal deposited on it ‒ the catalyst of hemolitic reactions (Pt, Pd, Co, Ni, Mo). The biological catalysts generally named enzymes are complex compounds of protein nature. The microheterogeneous catalysis takes the intermediate place between homogeneous and heterogeneous in which as the catalyst 34

big polymeric molecules are used. This group includes enzymatic reactions in which the catalysts are large proteinaceous molecules of complex structure and composition (enzymes). Therefore microheterogeneous catalysis is also called enzymatic. The microheterogeneous catalysis is a catalysis on macromolecules or colloidal particles (10-5 – 10-7 cm) which have a huge specific surface with a large number of the active centers, than is provided exclusively high activity of such catalysts. For example, colloidal Pt and Pd solutions show very high activity at the lowered temperatures (promote vigorous decomposition of peroxide of hydrogen at concentration of the catalyst of 10-8 g/l). Homogeneous and microheterogeneous catalysis are singlephase processes, and the regularity characteristic of homogeneous and gas-liquid chemical processes are applicable to them. The specifics of the mechanism of microheterogeneous catalysis are not yet fully understood. Microheterogeneous catalysis refers to the least studied region of catalysis, although colloidal catalysts by activity are many times higher than heterogeneous catalysts and are active already at room temperature. This is due to the difficulty of obtaining stable colloidal solutions and to the lability of colloidal particles, which change in size with time and are sensitive to traces of impurities. It is necessary to add the following two groups to them: ‒ the heterogenized catalysis, when a catalytically active fragment is attached to a surface or a molecule, for example, the ionized liquid of the second phase. The typical example is the catalysis on the basis of acid which is carried out by the anionically-modified polymers; ‒ an electrocatalysis, when some mechanisms which promote the speed of half-cell reactions on surfaces of electrodes are used.

2.3. Stages of heterogeneous catalysis Catalytic process is a set of catalytic reactions on the surfaces of the catalyst with processes of a supply of reagents into a reaction zone, and removal of products of reaction. The catalysis process on solid porous catalysts consists of the following elementary steps: 35

1. Diffusion of reactants from the center of the flow to the surface of the catalyst grains; 2. Diffusion of the reagents in the pores of the catalyst grain; 3. Activated adsorption (chemisorption) on the surface of the catalyst with the formation of surface chemical compounds ‒ activated complexes “reagents-catalyst”; 4. Rearrangement of atoms with the formation of surface complexes “product-catalyst”; 5. Desorption of the product from the surface; 6. Diffusion of the product in the pores of the catalyst grain; 7. Diffusion of the product from the surface of the catalyst grain to the center of the flow. In case of the catalysts like granules consisting of powders, or porous bodies it is important to deliver reagents to a surface. Kinetic area of catalysis is the area in which the speed of reaction is defined by directly chemical transformations on the surfaces. The area of external diffusion is the area in which the reaction is limited by the supply of reagents from the gas or liquid to the outer surface or their withdrawal from the outer surface of the catalysts. The area of internal diffusion is in the case when the ratelimiting step is the transfer of a substance in the pores within the catalyst grains. The overall speed of a heterogeneous catalytic process is determined by the relative rates of individual stages and can be limited by the slowest of them. Sometimes the slowest stage is one of the chemical interactions on the surface of the catalyst, and sometimes diffusion processes. One of the essential stages of heterogeneous catalytic reactions is the transfer of the reactants to the active surface of the porous catalyst. If the reaction proceeds quickly enough, the rate of the process can be limited by the supply of reagents from the center of the flow to the outer surface of the particle, and also by diffusion of the reagents in the pores of the catalyst grain. The real kinetic regularities of a heterogeneous catalytic process are determined both by the actual reaction kinetics on the active surface and by the conditions of mass and heat transfer. In the presence of a catalyst of a certain composition and structure, the temperature regime of the catalytic processes is of greatest practical importance. 36

The place of the heterogeneous catalytic reaction is the surface of the solid catalyst. To increase it, the porous catalysts are used, the inner surface area of which reaches tens and hundreds of square meters in one cubic centimeter. The outer surface of such a body is less than 10-3 m2, i.e. it is in 103-105 times smaller than the internal one, and therefore its contribution to the overall transformation rate can be ignored. First, the reagents diffuse out of the gas volume through the boundary layer to the outer surface of the catalyst particle (stage I), then penetrate into its pores (stage II), in which at the movement on their surface reaction (stage III) proceeds. The products are removed in the opposite way.

2.4. A role and features of a catalysis in industry and oil processing Almost all processes in the industry are catalytic and the importance and economical significance of catalysis is enormous. More than 80% of the present industrial processes in the chemical, petrochemical, and biochemical industries, as well as in the production of polymers and in environmental protection, use catalysts. Scientific research in the field of a heterogeneous catalysis has begun at the end of 19 ‒ beginning of 20-centuries with works on dehydration of alcohols on clays and on decomposition of ammonia and hydrogen peroxide on various solid bodies. In the 19th century a large number of heterogeneous catalytic processes had been discovered, and since the 20th century an active study of the mechanism of heterogeneous catalysis had begun. This was determined by the needs of the development of chemical technology, and, most of all, the processes of obtaining mineral acids and ammonia, and subsequently ‒ the enormous needs of the implementation of the processes of oil refining and petroleum synthesis. Awareness and understanding of the nature of heterogeneous catalysis was facilitated by the possibility of using a complex of physical and kinetic methods for studying heterogeneous-catalytic systems. Heterogeneous catalysts are used on a large scale in the following areas: 1. Production of organic and inorganic chemicals; 37

2. Crude oil refining and petrochemistry; 3. Environmental protection; 4. Energy conversion processes. The major factor defining the catalytic properties is the chemical composite. However even at the identical chemical composite the catalytic characteristics depending on a method and preparation conditions can change in rather wide limits. It takes place because of change of the nature of interaction of components of the catalyst, dispersion, porous structure, crystal chemical changes and other factors essentially influencing on course of catalytic reactions. Heterogeneous catalysts must meet certain requirements of the technology of the catalytic process, the main of which are as follows: 1. The catalyst should be very active. Efficiency of the catalyst for large-capacity processes usually should be above than 20 g/l·h. The high specific surface and optimum porous structure are necessary for activity of the catalyst. 2. The catalyst should have high selectivity. Otherwise costs of cleaning and separation of the final products increase. It is desirable that selectivity was equal to 100%, but it is the most difficult. It should be noted that for obtaining the catalyst with high selectivity for this purpose the high specific surface is insignificant. The required degree of selectivity for different processes is various; it is determined by the economic reasons proceeding from a raw materials cost share in the price of the final products. 3. The catalyst should possess sufficient stability to catalyst poisoning. Including it is desirable to minimize coke deposition on a catalyst surface in organic reactions, as much as possible to extend the period of work of the catalyst before regeneration. 4. The catalyst should not be too sensitive to overheats in the exothermic reactions. It is important, that the overheat on 50-100°С above the regulated temperature of process did not lead to irreversible loss of activity. 5. Catalyst preparation should be well reproduced. On structure and structure all weight of the catalyst and each granule separately, should be homogeneous. 38

6. The catalyst should be mechanically strong and the tablets should not be crushed under weight of a layer of the catalyst and collapse at free falling from the height some exceeding height of the contact device. At dot character of loading on grain in a high contact layer last can reach considerable sizes and carry, more likely, splitting, than crushing character. 7. The catalyst should have high mechanical durability on abrasion. Especially the high requirements to durability on abrasion are shown to the catalyst working in the conditions of a mobile layer with circulation or in the boiling layer. 8. The catalyst should not lose activity, selectivity or mechanical durability under the influence of the processes proceeding on its surface. 9. Operation time of the catalyst, irrespective of the reasons, its defining, should not be too small. At normal commercial operation the catalyst should not be overloaded more often, than once a month. 10. It is desirable, that technologies of preparation and manufacture of catalysts were not too difficult. In their manufacture it is desirable to use the pure materials. Impurity in initial raw materials, including an impurity in technological water, can strongly reduce activity and selectivity. In a number of catalyst' manufactures cleaned or even the distilled water is used. 11. Catalyst cost usually makes some percent from product cost. In some cases, for example for catalysts from noble metals or other scarce raw materials, the question of reduction of cost is one of the most important. Possibly, one of the first catalytic processes which the person learned to use is a fermentation. Recipes of preparation of alcoholic beverages were known for the Sumerians still for 3500 century BC.

Catalysis in production of inorganic substances Process of obtaining sulfuric acid by a nitrose method became the first commercial catalytic process. Process was carried out in lead chambers (a chamber way), and then – in special towers (a tower way). The sulfuric acid produces by this method contained a large amount of impurities. 39

An important achievement was the creation of the industrial catalysis process for producing ammonia. Using osmium and uranium catalysts, F. Haber opened ammonia synthesis reaction at a high pressure. The catalysis helped to solve a problem of transition from ammonia to oxygen-containing compounds of nitrogen. Oxidation of ammonia can lead to various products: 4NH3 + 3O2 →2N2 + 6H2O

(2)

4NH3 + 4O2 →2N2O + 6H2O

(3)

4NH3 + 5O2 → 4NО + 6H2O

(4)

At non-catalytic combustion of ammonia is formed mainly nitrogen (reaction 2). If use the catalyst based on manganese dioxide, the oxidation mainly proceeds according to the reaction (3). Use of special catalysts (Pt metal grids or Pt alloys with palladium and rhodium) allows to direct almost quantitatively process towards the formation of nitric oxide by the reaction (4). Currently oxidation of ammonia to nitric oxide is carried out on metal grids made of noble metals (Pt, Pd, Rh) at 750-900°C and atmospheric pressure. The oxidation of ammonia to nitric oxide allowed obtaining of large quantities of nitric acid, which is used in the chemical and other industries.

Catalysis in production of organic chemicals Assortment of chemical products of organic synthesis industry is diverse: monomers and, based on synthetic resins, rubbers, fibers, plastics, adhesives, dyes and a wide variety of paints and lubricants, solvents, surfactants, pesticides, flotation reagents, anti-freeze and anti-knock agents, explosives and drugs fotoreactants, fragrant compounds and so on. Today, almost all organic synthesis based on fossil organic raw materials: oil and natural gas, coal, shale. In the processes of physical and chemical transformations of the compounds 5 groups the starting materials used in the synthesis are obtained: 40

1) paraffinic hydrocarbons (CH4 to mixtures of C15-C40); 2) olefins (mainly C2H4, C3H6, C4H8); 3) acetylene; 4) carbon monoxide, and synthesis gas; 5) aromatics (benzene, toluene, naphthalene, etc.). Furthermore, in the organic technology in large quantities inorganic compounds: acids, alkalis, soda, chlorine et al. without which is not possible the implementation of many processes are also used. The term “basic” organic synthesis covers the tonnage production of organic compounds that serve as the basis for the rest of the organic technology. For the production of organic compounds the typical reactions of organic chemistry: oxidation and reduction, hydrogenation and dehydrogenation, dehydration, hydration, hydrolysis, alkylation, condensation, polymerization, etherification, nitration, halogenation, sulfonation are used. Depending on the parameters of technological mode (temperature, pressure, concentration of reactants, the used catalysts, the degree of mixing) from one and the same material can be prepared by a variety of products. In organic synthesis, as rule more than one chemical reaction took place, but several parallel and consecutive reactions. As a result, in addition to the expected product are obtained even by-products and waste products. Selectivity to the desired product is determined by the ratio of the rate constants of the target and by-product reactions. Therefore, in order to intensify the processes of organic synthesis the selective catalysts that increasing only the main reaction are used.

Catalysts and protection of the environment The use of catalysts for the reduction of air pollution began at the end 1940s. In 1952 A. Hagen-Smit found that the hydrocarbons and nitrogen oxides which are a part of combustion gases react on light with formation of oxidizers (in particular, ozone) which render irritant action on eyes and give other undesirable effects. Approximately in the same time of Yu. Khoudri developed a way of catalytic cleaning of exhaust gases by oxidation of CO and hydrocarbons to CO2 and Н2О. 41

In 1970 was formulated the Declaration on Clean Air (adjusted in 1977, extended in 1990), according to which all new cars starting from 1975 models, must be equipped with catalytic converters. Especially for automobile neutralizers were created catalysts in which the active components are applied on a ceramic substrate with honeycombed structure through their cells pass combustion gases. Block carrier on the base of ceramic (fig.5) is a highly porous cellular ceramic material with a mesh-cellular maze-arch structure, which has a number of distinctive advantages. The surface of the cellular carrier develops by applying a substrate on which the active component is applied. Group VIII metals and their mixtures with promoters are used as the active ingredient. The use of highly porous ceramic honeycomb block catalysts makes it possible to carry out the process in the liquid phase at sufficiently high rates due to the high degree of mixing and dispersion. As carriers of a catalytic layer use metal. So, for example, as the metal carrier take an aluminum, steel and titanic foil, oxidize it and obtain an oxide film on metal. The foil is rolled and the active layer is deposited on it. It allows to increase the area of a working surface, to obtain smaller counter-pressure, to accelerate a heating of catalytic converter up to the working temperature. The substrate is coated with a thin layer of metal oxide, such as Al2O3, onto which a catalyst ‒ platinum, palladium or rhodium is supported. Content of nitrogen oxides formed during the combustion of natural fuel in thermal power plants, can be reduced by adding small amounts of ammonia into flue gases and by passing them through a titanium-vanadium catalyst. Catalysis in oil processing Heterogeneous catalysis, especially with a solid catalyst, much more widespread than homogeneous. A wave of industrial use of catalytic processes accounted for 1930 and associated with the processing of oil. Petroleum refining consists of several catalytic processes: cracking, reforming, hydrosulphonation, hydrocracking, isomerization, polymerization and alkylation. Catalytic hydrotreating and hydrocracking are used also for production of high-quality hydrocarbon oils and paraffins. 42

The catalytic methods hold at present the leading position in petroleum processing. At present over 80% of oil is processed with catalytic processes of cracking, reforming, hydrogenolysis of sulfuric compounds, hydrocracking (tab.7). Due to catalysis the quantities and content of products obtained from oil was increased several times. It is very important to increase the extent of extraction of valuable products from oil which can be done through wider use of perfect catalysts. Table 7 Modern catalytic processes of oil processing No 1 2 3 4

5 6 7 8 9 10 11

12

Process Catalytic Cracking Reforming

Catalyst Zeolite-containing catalysts with additions of rare earth elements, Pt, Cr; 467-517ºC, 0.2-0.3 MPa Polymetallic catalysts: Pt, Re, Ir (Cl-, SO42-)/Al2О3; 467-517ºC, 0.8-1.5 MPa Hydrotreating Al-Co-Mo, Al-Ni-Mo-Si catalysts; 327-407ºC, 3.0-5.0 MPa Hydrocracking Zeolite-containing catalysts with additives Pt, Pd, Ni, Co and other metals; WS2/Al2O3; (Co-Mo)/Al2O3; 247-467 ºC, 5.0-15.0 MPa Isomerization Pt, Pd (Cl-, F-)/Al2О3 zeolites; 87-497ºC, 0.5-4.0 MPa Hydrogenation Nickel – skeletal, Pd, Ni/carrier Oxidic, sulphidic catalysts Dehydrogenation Cr2O3-Al2O3, oxide catalysts, Ni/carrier, copper catalysts Oxydation The put V2O5, Ag/carrier, Pt-Pd/carrier, polymetallic oxide Alkylation Acidic catalysts, acids Н2SO4, HF, H3PO4, AlCl3 Halogenation FeCl3, AlCl3 Synthesis based on carbon monoxide Condensation processes

Oxide catalysts CuO·Cr2О3, ZnO·CuO·Cr2О3, Со, Fe, rhodium complexes ZnCl2, HCl, acid catalysts

The use of catalysis in petroleum-processing paved the way for obtaining of cheap monomers and other products of petrochemical industry. Practically all monomers for obtaining of the elastomers, synththetic fibres, different plastics are produced by catalytic methods. Especially great is the role of catalysis in development of the new processes of organic synthesis. For example production of syn43

thetic rubber from ethanol carried out by academician Lebedev for the first time in the world should be recognized as the greatest success in this direction. Figure 5 shows samples of industrial catalysts with different shapes.

a

b

c

e

d

f

Figure 5. The industrial catalysts with different shape: a – the catalysts for the oxidation of sulfurous anhydride to sulfuric acid in the production of sulfuric acid; b – the main forms of industrial catalysts for the conversion of hydrocarbons; c – a general view of the catalytic neutralizers on metal block carriers for neutralization of exhaust gases of diesel generators and motor vehicles and waste gases of industry; d – ready-to-use catalytic neutralizers on metal block carriers for cars; e – a general view of ceramic block carriers; f – the catalysts for reforming for installations with continuous catalyst regeneration

44

So catalysis is the foundation for production of all substances which are the basic elements of production of new synthetic materials. Processes of polymerization are in a majority of cases also catalytic. The scientists Cygler and Nata discovered the catalytic polymerization and were awarded the Nobel prize in 1963. Catalysis is used to produce large amounts or a number of polymers. Complex compounds of transition metals both in solid and dissolved state are used as catalysts. Questions for self-checking: 1. Describe catalysis as the universal and very diverse phenomenon. 2. Describe the catalyst concepts, catalysis preconditions. 3. Tell about the first known example of a non-biological catalytic process. 4. Describe the main ideas of prominent scientists about nature of catalytic action. 5. Explain the features of reactions in the presence of catalysts. What is “catalytic activity”? 6. Explain the concepts “positive catalysis”, “negative catalysis”. 7. Explain the concept “catalyst selectivity”. Give the examples of processes and catalysts. 8. Explain the concept “spesificity of operation of the catalyst", “stability”. Give the examples of reactions and catalysts. 9. Describe brief history of catalysis. 10. Tell about classification of catalysis and catalytic reactions. 11. Explain the features of heterogeneous and homogeneous catalysis. 12. Explain the concepts: “hemolytic catalysis”, “heterolytic catalysis”. 13. Explain the concepts “bifunctional catalysis”, “ionic catalysis”. 14. Explain the features of microheterogeneous catalysis. 15. Explain the essence of the heterogenized catalysis. Give an example. 16. Tell about an electrocatalysis. Give an example. 17. List the stages of heterogeneous catalysis. 18. Give the description of the stages of heterogeneous catalysis. 19. Explain the concepts “kinetic area”, area of “external diffusion”, area of “internal diffusion”. 20. Explain the concept “adsorption” as the stage proceeding before the chemical reaction in heterogeneous catalysis. 21. Describe the place of the heterogeneous catalytic reaction. 22. What is the major factor defining the catalytic properties? 23. List the basic requirements to catalysts. 24. List the examples of large-tonnage processes in industry and oil refining with use of catalysts. 25. Tell about catalysis in production of inorganic substances. 26. Tell about ammonia production. 27. Tell about catalysis in production of organic chemicals. 28. Describe application of catalysts for protection of the environment. 29. Tell about catalysis in oil processing. 30. List the modern catalytic processes of oil processing.

45

3.1. Cracking of crude oil. Catalytic cracking 3.1.1. General information. Types of cracking. Thermal cracking Cracking (English cracking, splitting) is a high-temperature processing of oil and its fractions in order to produce, as a rule, products of lower molecular weight ‒ motor fuel, lubricating oils, etc., as well as raw materials for the chemical and petrochemical industries. Cracking occurs with the rupture of C-C bonds and the formation of free radicals or carbanions. Also, simultaneously with the rupture of the C-C bonds, dehydrogenation, isomerization, polymerization and condensation of both the intermediate and the starting materials occur. As a result of polymerization and condensation, a so-called cracking residue (a fraction with a boiling point of more than 350°C) and petroleum coke are formed. The world’s first industrial plant for continuous thermal cracking of oil was created and patented by engineer V.G. Shukhov (fig.6) and his assistant S.P. Gavrilov in 1891. Cracking is carried out by heating of oil raw materials or simultaneous impact on it of high temperature and catalysts, i.e. distinguish thermal and catalytic cracking. 46

Figure 6. Shukhov’s installation for thermal cracking

In case of catalytic cracking process is used for producing base components of high-octane gasolines, gasoils, hydrocarbon gases (catalytic cracking); petrol fractions, jet and diesel fuel, petroleum oils and also raw materials for processes of pyrolysis of oil fractions and catalytic reforming (hydrocracking). Thermal cracking is a non-catalytic cracking of hydrocarbons. It is carried out in the absence of a catalyst at high temperature through a free-radical mechanism. So thermal cracking is a process of decomposition of hydrocarbons of heavy fractions of oil under treating of high temperatures. At thermal cracking process is carried out for obtaining gasolines (low-octane components of automobile fuel) and gasoil fractions (components of naval distillate fuels and fuel oils, gas turbine and furnace fuel), the highly aromatized oil raw materials in production of technical carbon (soot) and also alpha olefins (thermal crack47

ing); boiler and also automobile and diesel fuels (viscosity breaking); oil coke and also hydrocarbon gases, gasolines and kerosine-gasoil fractions; ethylene, propylene and also aromatic hydrocarbons (pyrolysis of oil raw materials). Process of thermal cracking of vacuum gasoil, black oil or tar has received the name viscosity breaking. The decay mechanism of alkanes has radical character and it is based on various energy of bonds С-С and С-Н (accordingly, 335 and 394 kj/mol). Energy of bonds С-С is less, therefore destruction of the normal alkanes, as a rule, occurs owing to break of bonds С-С. The break place depends on pressure and temperature. The higher the temperature and the lower the pressure, the closer to the molecule end there is its rupture. Thus, it is possible to operate process of destruction. At temperature nearby 450°С alkanes destruction occurs in the middle of a chain. For example, octadecane C18H38, having temperature of boiling 317.5°С, breaks up on nonane С9Н20 with temperature of boiling 150.8 °С and on alkene С9 Н18 (nonene) with temperature boiling 146.9 °С: C18H38→ С9Н20+ С9Н18

(5)

Cyclanes at the cracking conditions lost the side chains, which are separated from the rings, are decomposed as alkanes; simultaneously cyclanes dehydrogenation took place. The process is carried out at 470-540°C under a pressure of 2-7 MPa. Cracked-gasoline has a low chemical stability due to its high content of alkenes and alkadienes. The stability of hydrocarbons to chemical transformations increases at thermal and catalytic cracking in the following series: Thermal cracking: Paraffins W> Ni> Fe> Pt> Co; 4) For the oxidation reactions platinum has maximum activity and silver has maximum selectivity. Thus, the transition metals possess by the high catalytic activity especially such as Pt, Pd, Rh, Co, Fe, Ni. On the surface of semiconductor oxides often are adsorbed molecules (with or without dissociation) in the form of ions. These oxides form the ionic crystals, and they are classified as the n- and ptype semiconductors. The conductivity of the n-type oxide is associated with free electrons linking with the anion vacancies in the crystal lattice. The conductivity of the p-type oxides is achieved by changing of charge of cations sequentially arranged in a lattice, which is equivalent to the movement of “positive holes” in the lattice. The active component of oxidic catalysts are products of thermal decomposition or interaction of compounds which were taken for preparation of oxide catalysts (hydroxides, carbonates, salts or other thermally unstable compounds). Texture of oxide formed by calcination of initial substance (the surface area and pore structure), depends on many factors: ‒ the chemical nature and texture of initial substances, ‒ the degree of purity from impurities, ‒ the composition of the gaseous medium, ‒ the temperature and duration of heating. 103

Considerable influence on texture oxides also have a porous structure and purity of initial substances: 1) fine-porous structure is less thermally stable than the large-pore, 2) in most cases, the introduction of impurities reduces the heat resistance of the surface. Since the magnitude of oxide crystals, formed by thermal decomposition is approximately the same, the magnitude of the surface oxide will be determined only by its density and conditions of calcination. A method of synthesis of oxide catalysts by pyrolysis of polymer-salt compositions based on introducing into a solution of thermally decomposable salts of the corresponding metals and the watersoluble polymer. As salts commonly are used nitrates and acetates, as well as polimers (the industrial polymers). The synthesized polymersalt compositions further are dried or thermally treated with the following annealing or are only heated for increase in temperature.

4.2. Processes of catalytic oxidation 4.2.1. Classification of reactions In organic chemistry and chemical technology transformations of substances under the action of certain oxidizing agents are called the processes of oxidation. There are complete (total or deep) and incomplete (partial) oxidation. At complete oxidation the substance is combusted with formation of carbon dioxide and water. For the synthesis are more important the processes of partial oxidation, which can be divided into three main groups: 1. Oxidation without breaking of the carbon chain (88) CH3 - CHOH - CH3

СН3 – СН2 – СН3

CH3 - C - CH3 O CH3 - CH2 - C

104

O H

(88)

2. Destructive oxidation proceeding with the splitting of carbon ‒ carbon bonds СН3 – СН2 – СН2 – СН3 СН3

"O"

benzene the maleic anhydride

СНО + СН3СООН

9"O"

(89)

+ 2 СО2 + 2 Н2О (90)

3. The oxidation, which is accompanied by the binding of molecules of the initial reactants (oxidation condensation or oxidative coupling): СН2 = СН2 + СН3СООН + 0.5 О2  СН2 = СН – О – С –СН3 + Н2О ║ (91) О RСН3 + NН3

+ 1,5 O2

RСN + 3 Н2О

(92)

The last reaction is called oxidative ammonolysis. The oxidizing agents may be: 1) Molecular oxygen 2) Nitric acid 3) Peroxide compounds Heterogeneous ‒ catalytic oxidation has become of great importance for realizing of a row of processes that cannot be successfully implemented using a radical ‒ chain oxidation reactions. Among them, the most important are the following: 1. Oxidation of olefins and their derivatives by saturated carbon atom with preservation of the double bond: СН2 = СН = СН3

"O2"

СН2 = СН – СНО + Н2О (93)

2. The oxidizing ammonolysis of olefins and other hydrocarbons with producing of nitriles: RСН3 + NН3 + 1.5 О2  RСN + 3 Н2О

(94)

105

3. Oxidation of aromatic and other hydrocarbons with formation of the internal anhydrides of di ‒ or tetra ‒ carboxylic acid: С6Н6 + 4.5 О2  the maleic anhydride + 2 СО2 + Н2О

(95)

The direct synthesis of ethylene oxide: СН2 = СН2 + 0,5 О2  СН2 – СН2О

(96)

4.2.2. Heterogeneous catalysts of oxidization Among the catalysts of heterogeneous oxidization of organic substances a practical value was purchased by the following: 1. The metals Cu and Ag, from which the more easily oxidized copper is probably operates as oxides formed in the surface layer. Other metals (Pt, Pd) lead to deep oxidation to CO2 and H2O. 2. The oxides of transition metals – СuО + Сu2О, V2О5. 3. Mixtures of oxides and salts of transition metals, especially V, stanattes, tungstates and molybdates, zinc, cobalt, and bismuth (ZnO·V2O5, CoO·WO3, Вi2О3·Мо3), which can contain as separate phases corresponding oxides and their compounds. In contrast, ferrites and chromites cause a complete oxidation. The listed catalysts are used in the form of shavings or grids (Cu), grains (V2O5) or applied on porous carriers (Ag, СuО, salts). In the mechanism of heterogeneous reactions of oxidation an important role is played by adsorption of reagents on a surface. On the metals oxygen is very quickly adsorbed with the following slower penetration into the surface layer. The base metals result in the oxides, and for silver the chemisorption process is limited with deep changes in the surface layer. It is believed that the oxygen is adsorbed on contact without dissociation or dissociation of molecules. Moreover, the metal provides the required electronic and transfers into a state of adsorbed oxygen ion ‒ radical. A similar type of oxygen chemisorption is carried out on the oxide and salt catalysts, where adsorption occurs by the transition metal ion. Last remains in the higher valence state. 106

Hydrocarbons are adsorbed on metals comparatively weak and reversible. More durable they are adsorbed on the oxide and salt catalysts. There are two main types of mechanism of heterogeneous ‒ catalytic oxidation: 1. The hydrocarbon is absorbed on the oxidized surface of the catalyst, at the beginning sorbing by an ion- radical of oxygen, and then interacting with it forming the oxidation products. The typical examples are the synthesis of ethylene oxide, the oxidation of benzene to maleic anhydride, carrying out through the intermediate formation of quinone. 2. The second common mechanism of heterogeneous ‒ catalytic oxidation is called the red ‒ ox. This mechanism is characteristic for the oxidation of olefins and methylbenzene. By this mechanism the adsorbed hydrocarbon on the metal ion is oxidized by oxygen of lattice of the catalyst; the metal wherein is reduced to the lower valence state and then again by interacting with oxygen, is passed into its initial state: 2 КtО + СН2 = СН – СН3  2 Кt + СН2 = СН – СНО + Н2О (97) 2 КtО + О2  2 КtО (98) It is possible to generally conclude that, in the kinetic field of reaction of oxidation is governed by the equation of Langmuir – Hinshelvud: W = kРRH РО2/(1 +  вiРi) (99)

4.3. Theoretical bases and technology of steam catalytic conversion of hydrocarbons for the hydrogen manufacturing Currently steam catalytic conversion (SCC) of hydrocarbons is the most common industrial process of hydrogen obtaining in the world oil refining and petrochemistry. As a raw material in the process of SCC are mainly used the natural and plant gases and also the directly distilled gasoline. 107

The conversion of hydrocarbon raw material CnHm by water vapor is carried out through the following equations: CnHm + nH2O → nCO + (n + 0.5 m)H2 – Q1 СО + Н2О →СО2 + Н2 + 42.4 kJ/mol,

(100) (101)

where n and m are the number of atoms of carbon and hydrogen in the molecule of hydrocarbon, respectively. The yield of hydrogen will be the greater, the higher the content of it in the molecule of hydrocarbon raw material. From this viewpoint, the most suitable raw material is methane in which molecule is contained 25% by weight of hydrogen. Sources of methane are the natural gases with the concentration of 94-99% vol. CH4. For the production of hydrogen it is also advantageous to use the cheap dry gases of oil refining. The aim of the conversion of methane with water vapor is to remove from these compounds as much as possible of hydrogen, using the least amount of energy (fuel). Reaction (100) is a strongly endothermic (at conversion of methane Q1 = 206,7kJ/ mol) and therefore thermodynamically the high temperature. Reaction (101) of SCC hydrocarbons takes place with release of heat and it is thermodynamically more favorable of low temperature. Therefore, in practice SCC processes are carried out in two stages at an optimum for each stage of temperature. Pressure has negative effect on balance of the main reaction of conversion of methane and therefore more high temperature for achievement of identical extent of transformation of hydrocarbon raw materials is required. However, preferred to conduct the process under increased pressure, as the produced hydrogen is then used in hydrogenation processes carried out under pressure. This reduces the costs for gas compression and further increases the productivity of the plant. In addition to temperature and pressure on the equilibrium reactions (100) and (101) the essential influence is rendered the mole ratio of water vapor (i.e.oxidant): carbon of raw materials (δN2O). It is found that in the products of the steam conversion of hydrocarbon feedstock at temperatures above 600°C there are no homologues of 108

methane. It is caused by that methane is the most heat-resistant hydrocarbon in comparison with its homologs. The equilibrium vapor composition of the products of hydrocarbon conversion at temperature over 600°C is usually calculated by the equilibrium constant of reactions (102) and (103). СH4 + H2O → CO+ 3H2

(102)

СО +Н2О → СО2 + Н2

(103)

In the process of vapor conversion of hydrocarbons, in addition to the main reactions (100) and (101), under certain conditions, the elemental carbon may be released due to thermal decomposition of hydrocarbon by the reaction (5): CnHm ↔ nC + 0.5 mH2 – Q3

(104)

The probability of release of this carbon increases at increase in number of carbon atoms (n) in hydrocarbon, increase of pressure and reduction of the relation δН2О. Industrial processes of SCC of hydrocarbons are carried out at two and more multiple excess of water vapor against the stoichiometric ratio of the necessary ratio. Steam reforming of methane with acceptable speed and depth conversion proceeds without catalyst at 1,250-1,350°C. The hydrocarbon conversion catalysts are intended not only to speed up the main reaction but also to suppress the side reactions of pyrolysis by reducing of the conversion temperature to 800-900°C. The most active and effective catalysts of conversion of methane ‒ nickel, applied on heat-resistant and mechanically strong carriers with the developed surface like aluminum oxide. For an intensification of reactions of gasification of carbon in small amounts usually enter alkaline additives (oxides of Ca and Mg) into nickel catalysts. The main production of installation is the high-purity hydrogen for installations of hydrogenation processes. The second product of the process is steam of high pressure. Vapor conversion of carbon oxide (101) is performed in two steps: 1step. At a temperature of 480-530°C on the medium temperature iron-chrome catalyst. 109

2step. At 400-450 °C on the low-temperature zinc-chromecopper catalyst. In the process of SCC of hydrocarbons takes place two types of homolytic reaction through chemisorption of reactants on the catalyst surface: 1. The oxidation-reduction reactions including stages of oxidation of the catalyst by oxidizers (H2O, CO2) and reduction of surface oxide by reducing agents (CH4, H2, CO): Z + Н2О→ Z0 + Н2

(105)

Z0 + СН4 → Z + СО + 2Н2

(106)

Z0 + СО → Z + СО2

(107)

2. Reactions of coal formation (carbidiration) ‒ of gasification, comprising the steps of formation of the surface carbon (metal carbide), methane and carbon monoxide and gasification of the surface carbon by oxidizers (H2O, CO2): Z + CH4 → Zc + 2H2

(108)

Zc + Н2О → Z + СО + Н2

(109)

Zc + СО2 → Z + 2СО,

(110)

where Z ‒ the active center of the catalyst; Z0 and Zc ‒ the centers of the catalyst occupied with the chemisorbed oxygen and carbon, respectively. The traditional process of hydrogen production by this method includes the following steps: 1) Purification of raw materials from the hydrogen sulfide and organic sulfur compounds. The organic sulfur compounds are the strong poisons for catalysts of steam reforming. The main parameters that characterize the process of desulfurization, are: a. temperature; b. pressure; c. catalyst. 110

2) Catalytic conversion of raw materials; 3) A two-step conversion of carbon monoxide; 4) Purification of process gas from the carbon dioxide by absorption with aqueous potassium carbonate; 5) Methanation of residues of carbon monoxide. The technological scheme of the installation of steam catalytic conversion at a pressure of 2.0-2.5 MPa is shown in fig.15. The raw material (natural or refinery gas) is compressed by the compressor to 2.6 MPa, heated in the preheater, in the convection section of the reactor furnace to 300-400°C, and fed to the R-1 and R-2 reactors for purification from sulfur compounds. In the reactor R-1, filled with an alumino-cobalt-molybdenum catalyst, hydrogenolysis of sulfur compounds takes place, and in R-2 takes place adsorption of the formed hydrogen sulphide on a granular absorber consisting mainly of zinc oxide to residual sulfur content in the raw materials 500 nm3/m3. Currently, three types of industrial processes of isomerization were developed: 1. The low temperature isomerization (360-440°C) on the alumina-platinum fluorinated catalysts; 2. Isomerization at medium-temperature (250-300°C) on zeolite catalysts; 3. The low temperature isomerization on alumina promoted by chlorine (120-180°C) and sulfated metal oxides (120-180°C). The high-temperature isomerization unit (fig.21) consists of two blocks ‒ rectification and isomerization. In the rectification block, isomers are isolated from a mixture of feedstock and stable isomerizate. The reactor block consists of two in parallel the working sections: in one the isomerization of n- pentanes, and in another ‒ the isomerization of n-hexanes is carried out. 148

Figure 21. Schematic diagram of the installation LI-150V (high-temperature isomerization of the fraction with b.b. ‒ 62°C): C-1 ‒ isopentane column; C-2 ‒ pentane column; C-3 ‒ butane column; C-4 ‒ isohexane column; C-5 ‒ adsorber-desiccant; C-6 ‒ stabilizer; C-7 ‒ absorber; 1 ‒ a reactor; 2 – a tube furnace; 3 – the steam heaters; 4 – the heat exchangers; 5 – the air coolers; 6 – the water coolers; 7 ‒ the compressor; 8 – the pumps; I ‒ raw materials; II ‒ isopentane fraction; III ‒ butanes; IV ‒ fresh hydrogen; V ‒ isohexane fraction; VI ‒ hexane fraction; VII ‒ fatty gas; VIII ‒ absorbent; IX ‒ fraction of n-pentane for isomerization; X ‒ circulating gas; XI ‒ stable isomerizate

When the process is carried out on a fluorinated aluminumplatinum catalyst of the IP-62 type at a pressure of 3.5 MPa and a temperature of 360-410°C at a molar ratio of hydrogen: raw material = 2:1 and a volumetric feed rate of n-pentane ~ 2.0 h -1, conversion more than 50% with a selectivity of 96-97% is provided. The most perspective, according to opinion of many authors, are the sulfated oxide catalysts. In the case of isomerization at high temperatures, the degree of conversion of C5 and C6 alkanes is about 50%, so isomerization in industrial plants is carried out with the rectification of the reaction mixture and the circulation of unconverted raw materials. The isomerization raw material is subjected to preliminary hydrotreating and drying. For the first time, a zeolite-containing catalyst for mediumtemperature isomerization of the pentane-hexane fraction was used in 149

“Hayzomer” process of Shell in 1970. The mordenite- containing HS-10 catalyst produced by Union Carbide at circulation of hydrogen under pressure of 1.4–3.3 MPa, at a temperature of 230-290°C and a feed rate of 1-4 h-1, made it possible to obtain isomerizate with octane number near 80 points (research method). The raw material was to be hydrotreated to remove impurities of sulfur compounds and water to a level of 0.001 and 0.003 wt. %, respectively. Under these conditions, the catalyst is stable and easily regenerated. To obtain iso-components with an octane number of about 90 points, a “TIP” technology (Total Isomerization Process) was developed that combines the processes of “Hayzomer” and “Isosiv” (gasphase separation of n-alkanes on zeolites) of the firm Union Carbide, currently licensed by UOP. Hydrogen was used in the process of isomerization and for the desorption of n-alkanes. This option is preferable for raw materials containing many heavy fractions or more than 60% of pentanes (fig.22). Isomerization is carried out on a desorbed mixture of n-pentane and n-hexane. Depending on the quality of the pentane-hexane fractions, the desired octane number and the yield of the isocomponent, the adsorption separation unit is placed before or after the isomerization unit. During the work with obtaining the maximum yield the raw materials is mixed up with a product of an isomerization and is directed to the adsorption block.

Figure 22. Principal block diagram of the process of “Total Isomerization Process”: 1 ‒ heaters; 2 ‒ section for separation of iso- and n-paraffins on zeolites; 3 ‒ isomerization reactor; 4 ‒ refrigerator; 5 ‒ section for the separation of desorbent and reaction products; 6 ‒ stabilization column; I, II ‒ raw materials; III ‒ stabilization gases; IV isomerizate

150

Because of the relatively high concentration of low-octane methylpentanes in the medium-temperature isomerisate (the fraction of high-alkane 2,2-dimethylbutane in the sum of hexanes is 15-20%) and the impossibility of their recycling in adsorptive separation, the “TIP” technology with complete isomerization of n-alkanes is quite expensive. Upon transition from the single-pass process “Hayzomer” to the process “TIP” necessary capital investments increase by 2.2 times, and specific energy consumption ‒ by 1.5–2.0 times. The processes of isomerization of pentane-hexane fractions on low-temperature alumoplatinum catalysts are more effective, due to the favorable operating temperature range (below 200°C) favorable for the formation of high-octane isohexanes. For the first time an aluminum-platinum catalyst of grade I-4, treated with aluminum chloride, was used in the process of “Penex” of the company “UOP” in 1958. The octane number of the isomerization product of pentane-hexane fraction “per pass” could be increased to 83-84 points, with recirculation of n-pentane ‒ up to 86 points, and with separation by distillation and recirculation in a reactor of isomerization of n-pentane, 2- and 3-methylpentane and nhexane ‒ up to 92 points. The yield of isocomponent “per pass” was about 99 wt.%. In the process of low-temperature isomerization of “British Petroleum”, the catalyst based on platinized alumina, supplied by “Engelhard”, was activated by an organochlorine compound directly in the reactors of isomerization units of pentane-hexane fractions. At a product yield “for pass” 99% the mass fraction of an isopentane in the sum of pentanes of the izomerizate could reach 77%, and contents 2,2 dimethylbutane in the sum of hexanes ‒ to exceed 35%. The octane number of such izomerizate is about 84 points (RM). Processes of low-temperature isomerization require hydrotreating and adsorption drying of raw materials, adding to it an organochlorine promoter and, accordingly, neutralizing the formed hydrogen chloride. Deep drying of raw materials makes it possible to use equipment made of carbon steel. Table 19 shows the characteristics and consumption indicators of the processes of isomerization of pentane-hexane fractions on chlorine-containing and zeolite catalysts of foreign firms (without the costs of hydrotreatment of raw materials). 151

Table 19 The main indicators of foreign processes of low- and medium-temperature isomerization of pentane-hexane fractions (CCC-chlorine-containing catalysts, ZCC-zeolite catalysts) Indicators

Catalyst Temperature, °С Pressure, MPa Volume feed rate of raw materials, h-1 Molar ratio hydrogen: raw materials С5+ yield, wt.% Octane number (RM) Capacity by raw materials, thousand tons per year

British Petroleum (CCC)

Penex (CCC)

Pt·Al2O3·Cl Pt· -Al2O3· AlCl 3 Process conditions: 90–160 120–205 2.7 2.1–7.0 2.0 2.0

Hayzomer (ZCC)

TIP (ZCC)

Pt·zeolite

Pt·zeolite

230–290 1.4–3.5 1–3

230–290 1.4–3.5 1–3

1.5

—

1–4

1–4

99.0 83.8 235

— 83.8 300

97.4 82.1 270

96.8 90.7 270

Due to higher activity and selectivity, as well as low operating costs, low-temperature processes of isomerization of pentane-hexane fractions occupy a leading place in the number of industrial plants. The improvement of processes, the development of new more efficient catalysts and the technology of liquid-phase adsorption separation of n-alkanes now make it possible to obtain isocomponents with an octane number up to 93 points (RM). However, for plants where a relatively low octane number of iso-components is required, a simpler technology for medium-temperature isomerization is also proposed with the use of new regenerable zeolite and metal oxide catalysts. Information about the composition of the offered catalysts and features of their operation are usually confidential. Firm “UOP” except low temperature catalysts I-8 and I-80 “Penex” process also provides a medium temperature isomerization catalysts. The leading foreign licensing firms of the C5-C6 hydrocarbons isomerization processes are “British Petroleum”, “UOP”, “Shell”, “Union Carbide”. The development of the technology and catalysts of the process is carried out by the “Kellog Company” (Isokel Process), “Atlantic Richfield” (Pentafining Process), “Pure 152

Oil” (Isomerate Process), “Linde”, “Sinclair”, “Chevron”, “Exxon”, French Institute of Petroleum and others. However, the leading position is occupied by the firm UOP (Penex and TIP processes). Most of the existing, designed and built isomerization units are based on the technologies of this company. The combination of “Penex” (isomerization) and Molex processes (selective liquid-phase adsorption on molecular sieves) by UOP makes it possible to increase the anti-knock characteristics of light straight-run gasoline by increasing the conversion of n-paraffins. The prime cost of izomerizat is about 3 times lower, than alkylates. And process of an isomerization has more extensive and reliable source of raw materials, than alkylation. In the long term process of an isomerization can be intensified by use of low-temperature catalysts, transfer of rectification to zeolite or membrane separation.

Combination of Reforming and Isomerization Processes Unlike catalytic reforming, the change in the rigidity of the mode of the isomerization process has almost no effect on the octane number of the isomerizate. Therefore if there is no need for substantial increase of octane number of light gasoline, then economically justified is an application of process of an isomerization in combination with process of catalytic reforming (with reduction of rigidity of the last). It promotes not only increase in the yield of gasoline at oil, but also decrease in content of benzene and aromatic compounds. Besides, combination of processes allows to reach more uniform octane number increasing for all fractions of commodity motor gasoline due to increase at an isomerization of octane number of light fractions. The combination of isomerization and catalytic reforming processes can significantly reduce investment (by 20-40%) compared to stand-alone installations due to the fact that such a complex has a common circulation system, a series of refrigerators and a stabilization section. With the introduction of new standards for the content of aromatic compounds, in particular benzene in environmentally friendly gasoline, the reduction in the rigidity of the operating mode of the reformer is of particular importance. 153

5.4. Fundamentals of catalytic hydrogenation processes of processing of oil raw materials 5.4.1. General information. Purpose and main parameters of the process On an industrial scale, the hydrogenation processes were developed by introducing in 1927 the world’s first installation of “estructive hydrogenation” of resins and coals in Germany, which did not have its own resources of oil and subsequently developed its fuel industry based on solid fossil fuels. Somewhat later, similar installations for the production of artificial liquid fuels from petroleum raw materials were built in England. The first studies on catalytic and non-catalytic hydrogenation of solid fuels were carried out at the beginning of the century by P. Sabatier in France, V.N. Ipatiev in Russia and F. Bergius in Germany. In the post-war years, in connection with the discovery of large oil fields and the rapid growth of its production in the world, the processes of obtaining motor fuels from coals lost their industrial importance due to the loss of competitiveness in comparison with petroleum fuels. In turn, in high-growth oil processing extraordinary widely began to use catalytic processes of hydrotreating of fuel fractions, then a destructive hydrogenation of the high-boiling distillates and the residues of oil (hydrocracking, see p.5.5 of this Educational manual). Good reason of intensive development of hydrocatalytic processes in post-war oil processing of the world was continuous increase in overall balance of a share sulphurous and high-sulphurous oils at simultaneous toughening of ecological requirements to quality of commodity oil products. It is known that in the course of cracking formation of coke which considerably reduces the yield of cracking gasoline takes place. Introduction of hydrogen in this process promotes coke production elimination and decomposition of the light products enriched with hydrogen. Therefore throughout usual cracking further cracking in the presence of hydrogen is technologically necessary. Such industrial processes are called hydrogenation processes. Hydrogenation from the point of view of process chemistry is a combination of catalytic reactions of hydrogen addition under appropriate conditions. Hydrogenation at normal pressure is not used in the 154

petroleum industry, because for this it is necessary to use catalysts that are easily poisoned by sulfur and other harmful compounds that are always present in petroleum products. In case of use of hydrogen at the elevated pressure and temperature there is no condensation of aromatic hydrocarbons, moreover in these conditions decomposition of the high-condensed aromatic hydrocarbons which availability is undesirable in such processes is carried out. Therefore one of the main directions of development of modern oil processing is modernization and building of installations of hydrotreating and hydrocracking. The hydrogenation processes applied in oil industry proceed in the presence of catalysts, in process there is a decomposition of highmolecular compounds which may contain sulfur and nitrogen, with formation of hydrogen sulfide and ammonia. The goals of hydroprocessing processes are very diverse. Motor fuels are hydrotreated to remove organo-sulfur compounds, nitrogen, oxygen, arsenic, halogens, metals and hydrogenation of unsaturated hydrocarbons, thereby improving their performance. In particular, hydrotreatment allows to reduce corrosive aggressiveness of fuels and their propensity to form precipitation, to reduce the amount of toxic gas emissions to the environment. Deep hydrotreatment of gasoline fractions is carried out to protect platinum reforming catalysts from poisoning by non-hydrocarbon compounds. As a result of hydrodesulfurization of vacuum gas oils, catalytic cracking feedstocks, the yield and quality of cracking products increase and the pollution of the atmosphere by sulfur oxides is significantly reduced. Petroleum oils subject to not deep hydrodesulphurization in order to change color, to reduce their coking ability, acidity and emulsification. With the replacement of solvent cleaning of high viscosity oil, for example, deasphalting, thanks to the use of hydrocracking, it became possible to produce oils with a high viscosity index (>105). Hydrotreated oil products meet the requirements of the standards for color, stability, odor, admissible content of impurities and other environmental and operational indicators. Hydrogenolysis of heteroorganic compounds in hydroprocessing processes occurs as a result of breaking of C-S, C-N, C-O bonds and hydrogen saturation of the formed heteroatoms and double bond at the hydrocarbon part of the molecules of the petroleum feedstock. In 155

this case, sulfur, nitrogen and oxygen are released as H2S, NH3 and H2O, respectively. The unsaturated hydrocarbons contained in the feed are hydrogenated to saturated paraffin hydrocarbons. Depending on the process conditions, partial hydrogenation and hydrocracking of polycyclic aromatic and tar-asphaltene hydrocarbons is possible. The organometallic compounds of the raw material are destroyed, and the released metals are deposited on the catalyst. Mercaptans are hydrogenated to hydrogen sulfide and the corresponding hydrocarbon: RCH +H2 →RH +H2S

(121)

Sulphides are hydrogenated through the formation of mercaptans: +H2 RSR’ +H2 → RSH+R’H → R’H +RH+H2S (122) Disulfides are hydrogenated analogously: +Н2 RSSR' + Н2 → RSH + S'SH → RH + R'H + H2S

(123)

Cyclic sulfides such as thiophane and thiophene are hydrogenated to form aliphatic hydrocarbons:

(124) Benzo- and dibenzothiophenes are hydrogenated according to the scheme:

(125, 126) 156

Nitrogen in oil raw materials is mainly in heterocycles in the form of derivatives of a pirrol and pyridine. Their hydrogenation proceeds generally similar to hydrogenation of sulfides:

(127, 128) Oxygen in the fuel fractions can be represented by compounds of the type of alcohols, ethers, phenols and naphtha acids. In gas oil fractions and oil residues, oxygen is mainly in bridge bonds and in cycles of polycyclic aromatic and resinous-asphaltene oil compounds. At hydrogenation of oxygen-containing compounds the corresponding hydrocarbons and water are formed:

(129) Hydrogenolysis reactions of all heteroorganic compounds are thermodynamically low-temperature. The pressure does not affect the equilibrium of gas-phase reactions or favor the formation of hydrogenolysis products. With an increase in temperature, the equilibrium constants of hydroginolysis reactions decrease, especially for thiophene and its derivatives, but in the temperature range of practical interest, the equilibrium of the reaction is almost completely shifted to the right for all heteroorganic compounds except thiophenes, for which the thermodynamic limitations are still perceptible, and their hydrogenation are carried out at low temperatures on highly active catalysts. Hydrogenation processes differ significantly from each other in the quality of raw materials and the target product, the process re157

gime and the properties of the catalyst. These processes are closely associated with the production of solid fats from liquid and the production of quality products from shale and coal tar, moreover they are also applicable for the synthesis of products such as ammonia and methyl alcohol. The development of the modern oil refining and petrochemical industry contributed to the strengthening of the trend of deepening of oil processing, achieved mainly as a result of the transition to the use of heavy types of raw materials, including residues, the intensification of existing processes. As a raw material of the process, almost any oil residue can be used, regardless of the sulfur content, organometallic and asphaltresinous compounds in them. In the process, a high conversion (8095%) of the feedstock can be achieved at a pressure of 7 MPa, a temperature of up to 450°C and a ratio hydrogen: raw material equal to 500-1,500 nm3/m3 or a low (up to 30%) yielding a low-sulfur component of boiler fuel. Effective direction of upgrading the residual raw materials and increasing the depth of oil processing is the process of hydrotreating heavy oil residues, based on the splitting of high-molecular raw materials and its partial desulfurization, producing light and medium distillate fractions. The use of such processes has made it possible to solve one of the important problems of processing sulphurous and sour crude, associated with the production of high-quality petroleum products and sulfur or sulfuric acid. Improving the quality of the product without significantly changing its hydrocarbon composition is the main goal of hydrogenation (or hydrotreatment). But sometimes it is required to obtain products with the changed hydrocarbon composition by the processes of destructive hydrogenation and hydrocracking.

5.4.2. Catalysts of hydrogenation processes All known catalysts of hydrogenation processes for processing of heavy oil fractions can be divided into two groups: the put (deposited) catalysts and disperse massive catalysts. Today all industrial 158

catalysts of hydrogenation processes belong to the first group, i.e. they are put. Catalysts of hydrogenation processes perform two main functions: hydrogenating and cleavage. The former is characterized by reactions with sulfurous, oxygen and nitrogenous compounds, while the latter performs a directly cracking function. The catalysts used in industrial hydrogenation processes are complex compositions, and as a rule they contain the following components: 1) Metals og Group VIII: Ni, Co, Pt, Pd, sometimes Fe; 2) Oxides or sulphides of group VI: Mo, W, sometimes Cr; 3) The heat-resistant carriers with developed specific surface and high mechanical durability, inert or possessing acid properties. Nickel, cobalt, platinum or palladium give the catalysts dehydrohydrogenating properties, but are not resistant to the toxic effects of contact poisons and can not be used alone in hydrogenation processes. Molybdenum, tungsten and their oxides are n-semiconductors (like Ni, Co, Pt and Pd). Their catalytic activity with respect to oxidation-reduction reactions is due to the presence of free electrons on their surface that promote adsorption, chemisorption, and to the hemolytic decomposition of organic molecules. However, Mo and W are significantly inferior to the dehydrohydrogenating activity of Ni, Co, and especially Pt and Pd. The sulfides Mo and W are p-semiconductors (hole). Their hole conductivity causes the occurrence of heterolytic (ionic) reactions, in particular, the cleavage of C-S, C-N and C-O bonds in heteroorganic compounds. The combination of Ni or Co with Mo or W gives their mixtures and alloys bifunctional properties ‒ the ability to simultaneously perform both homolytic and heterolytic reactions and, most importantly, resistance to the poisoning effect of sulfur and nitrogen compounds contained in the petroleum feedstock. Use of carriers allows to reduce the content of active components in catalysts that is especially important in case of use of expensive metals. Depending on type of reactors catalysts on carriers are made in the form of tablets, balls or microspheres. Carriers of a neutral nature (oxides of aluminum, silicon, magnesium, etc.) do not impart to catalysts on their basis additional cata159

lytic properties. Carriers having acidic properties, such as synthetic amorphous and crystalline aluminosilicates and zeolites, magnesium and zirconium silicates, phosphates, impart additional isomerizing and cracking properties to the catalysts. In world practice the greatest distribution in hydrogenation processes was gained by aluminum-cobalt-molybdenum (Al-Co-Mo), aluminum-nickel-molybdenum (Al-Ni-Mo) and mixed aluminonickel-cobalt-molybdenum (Al-Ni-Co-Mo), as well as alumino-nickel-molybdenum-silicate (Al-Ni-Mo-Si) catalysts. In the processes of deep hydrogenation of nitrogen-containing and aromatic compounds of paraffins and oil fractions, aluminum-nickel or aluminum-cobalttungsten catalysts (Al-Ni or Al-Co-W) are used. In recent years, zeolite-containing catalysts for hydrodesulfurization and hydrocracking have been distributed. Al-Co-Mo and Al-Ni-Mo hydrotreating catalysts contain 2-4% by wt. Co or Ni and 9-15% by wt. MoO3 on active γ-aluminum oxide. At the stage of starting operations or at the beginning of the feed cycle, they are subjected to sulfidation (sulphiding) in a stream of H2S and H2, their catalytic activity increases substantially. Despite the long-term studies carried out in many countries of the world with the use of a complex of various physical and chemical methods, it has not yet been established which structures and phase composition of the hydrogenation catalysts correspond to their catalytically active state. Cobalt (nickel) and molybdenum (tungsten) form complex bulk and surface compounds such as cobalt (nickel) molybdates (wolframates), which during sulfonation form catalytically active structures of sulfide type CoxMoSy (NixMoSy, CoxWSy, NixWSy). It is also possible the formation of Al2O3 on the surface of the carrier ‒ of a catalytically inactive cobalt spinel-type aluminate phases (nickel) and molybdate (tungstate) aluminum. The most likely structure in the sulphided Al-Co-Mo catalysts responsible for their difunctional catalytic properties is CоMоS2 phase. By analogy with the mechanisms of reactions carried out in the processes of catalytic reforming on platinum and the steam conversion of hydrocarbons, it can be assumed that the hydrogenolysis of heteroatomic hydrocarbons on Al-Co-Mo and Al-Mo-Ni catalysts 160

also proceeds multistagely through the chemisorption of the reactants on the active sites of both cobalt (nickel) and molybdenum. At the same time on cobalt (nickel) is carried activation H2 and spillover atomic active hydrogen, and on molybdenum occur sulfonation (sulphidation), nitriding and oxidation with formation of surface compounds Mo (S), Mo (N) and Mo (O), which under the action of the activated hydrogen are subjected to desulfurization (desulfurization), denitrogenation and reduction. Z' + Н2 → Z'(Н) + Z' → 2Z'(Н) → 2Z' + 2Н

(130)

Z + RSH → Z(RSH) → Z(S) + RH

(131)

Z + RNH → Z(RNH) → Z(N) + RH

(132)

Z + ROH → Z(ROH) → Z(O) + RH

(133)

Z(S) + 2H → Z + H2S

(134)

Z(N) + 3H → Z + NH3

(135)

Z(O) + 2H → Z + H2O,

(136)

where Z' and Z are respectively the active centers of Co (Ni) and Mo. During operation, the catalyst gradually loses its activity as a result of coking and deposition of raw materials on its surface. To restore the original activity, the catalyst is regenerated with oxidative coke firing. Depending on the composition of the catalyst, a gas-air or vapor-air method of regeneration is used. Zeolite-containing hydrodesulfurization and hydrocracking catalysts cannot be subjected to steam-air regeneration. Gas-air regeneration is usually carried out with a mixture of an inert gas and air at a temperature of up to 530°C. In this case, the regenerated catalyst accelerates the combustion reactions of coke. The steam-air regeneration is carried out with a mixture heated in the furnace to the start temperature of coke burning. The mixture enters the reactor, where the layered combustion of coke occurs, after which the gases are discharged into the chimney. 161

5.4.3. Installations. Processes examples The raw materials of the hydrotreating processes are gasoline, kerosene and diesel fractions, vacuum gas oil and lubricating oils containing sulfur, nitrogen and unsaturated hydrocarbons. The content of heteroatomic hydrocarbons in the feedstock varies very significantly, depending on the fractional and chemical composition of the distillates. As raw materials become heavier, not only the total content increases, but also the share of the most thermostable with respect to hydrogenolysis hetero-organic compounds increases. For each type of feedstock and catalyst, there is an optimal range of operating parameters. Although the hydrogenolysis reactions of the heteroorganic compounds are exothermic, the hydrofining processes of the fuel fractions are usually carried out in an adiabatic reactor without removing heat from the reactions, since the temperature gradient usually does not exceed 10 ºC. In industrial hydrogenation plants, two methods of separating hydrogen-containing gas from hydrogen gas are used (fig.23): cold, low-temperature (a), and hot, high-temperature (b).

a

b Figure 23. Cold (a) and hot (b) separation schemes for hydrogen containing gas (HCG): HCG ‒ hydrogen containing gas, SHP-separators of high pressure, SLP ‒ Separators of low pressure, CS ‒ cold separators, HS ‒ hot separators

162

Cold separation of HCG consists in cooling of the gas-product mixture leaving the hydrotreating reactors, at first in heat exchangers, then in refrigerators (air and water) and separating of HCG in a separator at a low temperature and high pressure. In a separator of low pressure separate the low-molecular hydrocarbonic gases. It is applied on hydrotreating installations of: ‒ petrol fractions, ‒ kerosene fractions, ‒ sometimes diesel fractions. At hot separation the gas-product mixture after partial cooling in heat exchangers is fed to a hot separator; HCG separated in it and hydrocarbonic gases are cooled up to the low temperature in air and water refrigerators and then they are sent to a cold separator where HCG with rather high concentration of hydrogen is selected. Hot separation of HCG is applied mainly on installations of hydrodesulphurization of the high-boiling fractions of oil: ‒ diesel fuels, ‒ vacuum gas oils, ‒ oil distillates, ‒ paraffins. Cold separation of HCG, compared to hot separation, provides a higher concentration of hydrogen in HCG. The main advantage of the hot separation option is a lower consumption of both heat and cold.

5.4.3.1. Installation of hydrotreating of diesel fuel The circulating HCG (fig.24) is mixed with the feed, the mixture is heated in the raw heat exchangers and in the tube furnace F-1 to the reaction temperature and fed to the reactor R-1. After the reactor, the gas mixture is partly cooled in raw heat exchangers (to a temperature of 210-230°C) and sent to the HCG hot separation section consisting of separators S-1 and S-2. HCG, withdrawn from the cold separator S-2 after purification with MEA absorber C-2 is fed to the circulation. The hydrogenates of the hot and cold separators are mixed and directed to a stabilization column C-1, whereby the hydrocarbon gases and the distillate (gasoline) are removed from the purified product by the circulating of the preheated into the furnace F-1 HCG. 163

Table 20 shows data on the material balance of hydrotreater units for gasoline (I), kerosene (II), diesel fuel (III), and hydrodesulfurization of vacuum distillate, a feedstock of catalytic cracking (IV). Table 20 Material balance of hydrotreating units No

1 2

Data of process

Raw materials Hydrogen 100% on the reaction * TOTAL

Raw materials I II III It is taken, %: 100.00 100.00 100.00 0.15 0.25 0.40

100,15 100,25 100,40 It is obtained,%: 1 Hydrotreated fuel 99.00 97.90 96.90 2 Diesel fraction 3 Distillation 1.10 1.3 4 Hydrocarbon gas 0.65 0.65 0.6 5 Hydrogen sulphide 0.2 1.2 6 Losses 0.5 0.4 0.4 TOTAL 100,15 100,25 100,40 * Total consumption taking into account dissolution losses.

IV 100.00 0.65 100,65 86.75 9.2 1.3 1.5 1.5 0.4 100.65

Figure 24. Principal technological scheme of the hydrotreating unit for diesel fuel: I ‒ raw materials; II ‒ fresh HCG; III ‒ hydrogenate; IV ‒ gasoline; V ‒ hydrocarbon gas for cleaning; VI ‒ blow-off HCG; VII ‒ regenerated MEA; VIII ‒ solution of MEA for regeneration

164

5.4.3.2. Hydrotreating of vacuum distillates Vacuum distillates are traditional raw materials for processes of catalytic cracking and hydrocracking. The quality of vacuum gas oils is determined by the depth of selection and the clarity of rectification of fuel oil. Vacuum gas oils 350-500°C practically do not contain organometallic compounds and asphaltenes, and their coking ability usually does not exceed 0.2%. The effect of metals contained in raw materials, nitrogenous compounds and sulfur is manifested in a decrease in the activity of the catalyst due to the deposition of coke and irreversible metal poisoning. Hydrotreatment of vacuum gas oil 350-500°C does not present significant difficulties and is carried out in conditions and equipment similar to those used for hydrotreating diesel fuels. At a pressure of 4-5 MPa, a temperature of 360-410°C and a feed speed of 1-1.5 h-1, the desulfurization depth is reached up to 89-94%; the nitrogen content is reduced by 20-30%, metals by 75-85%, and coking by 65-70%. The hydrotreatment of heavy distillates of destructive processes (coking, visbreaking) is usually carried out in a mixture of straightrun distillates in an amount up to 30%. Hydrotreating of oil raffinates is mainly used for color clarification and improvement of their stability against oxidation; simultaneously reduces their coking ability and sulfur content (desulfurization depth is 30-40%); the viscosity index slightly increases (by 1-2 units); the pour point of the oil rises by 1-3°C. The yield of base oils of distillate and residual raffinates is more than 97% by wt. Installations for hydrotreating oils differ from the hydrotreating of diesel fuels only in the way of stabilizing hydrogenation: stripping of hydrocarbon gases and gasoline vapors is carried out by the supply of water vapor; then the stable oil is dried in a vacuum column at a pressure of 13.3 · 103 Pa. 5.4.3.3. Processes of hydrotreating oil residues. Hydrodesulfurization of oil residues by the method of the French Institute of Oil In modern world oil refining, the most urgent and complex problem is refining (demetallization, deasphalting and desulfurization) and catalytic processing (catalytic cracking, hydrocracking) of oil 165

residues ‒ tar and fuel oil, the potential content of which in the oils of most fields is 20-55%. The most important quality indicators of oil residues as raw materials for catalytic processes, their refinement and processing are the content of metals (determining the degree of deactivation of the catalyst and its consumption) and coking ability (causing coking of catalytic cracking regenerators or hydrogen consumption in hydrogenation processes). These indicators were the basis for the classification of residual raw materials for catalytic cracking processes accepted abroad. The content of metals and coking in accordance with this classification of oil residues are divided into the following four groups (tab.21). Table 21 Classification of oil residues Group I II III IV

Coking ability, % wt. Less than 5 5-10 10-20 More than 20

The content of metals, g/ton Less than 10 10-30 30-150 More than 150

I. High-quality raw materials (for example, mazut of Mangyshlak or Grozny oil). It can be processed without preliminary preparation in installations of CCF (catalytic cracking fluid) of lift-reactor type with passivation of metals and heat removal in regenerators. II. Medium-quality raw materials. It can be processed in the CCF plants of the latest models with a two-stage regenerator and removal of excess heat without preliminary preparation, but with an increased consumption of a metal-resistant catalyst and passivation of the poisoning effect of raw metals. III and IV. Low quality raw material (e.g., fuel oils and asphalts of West-Siberian, Romashkinskoye, Arlanskoe oils). Catalytic processing requires obligatory preliminary preparation ‒ demetallization and deasphalting. For the processing of fuel oil in low-sulfur boiler fuel, the following methods of “indirect” hydrodesulphurization were proposed and implemented: 1. Vacuum (or deep vacuum) distillation of fuel oil followed by hydrodesulfurization of vacuum (deep vacuum) gas oil and mixing of the latter with tar (sulfur content in boiler fuel 1.4-8%); 166

2. Vacuum distillation of fuel oil and deasphalting of tar, followed by desulfurization of vacuum gas oil and deasphalted oil and mixing them with deasphalting residue (sulfur content in boiler fuel 0.4-1.4%); 3. Vacuum distillation of fuel oil and deasphalting of tar, followed by hydrodesulfurization of vacuum gas oil and deasphaltizate and their mixing (the sulfur content in the boiler fuel is 0.2-0.3%), the deasphalting residue is subjected to gasification or separate processing to produce bitumen, pitch, binders, fuel coke, etc. Modern foreign industrial installations of hydrodesulfurization of oil residues can be divided into the following options: 1) Hydrodesulfurization in one multilayer reactor using the large-porous metal-intensive catalysts at the beginning of the process and then catalysts with high hydrodesulfurization activity; 2) Hydrodesulfurization in two and more step reactors with a stationary catalyst bed, of which the head (preliminary) reactor is designed for demetallization and deasphalting of raw materials on cheap metal-intensive (often not regenerated) catalysts, and the latter for hydrodesulfurization of demetallized raw materials; 3) Hydrodesulfurization in a reactor with a three-phase fluidized catalyst bed. The fluidized bed allows for more intensive mixing of the contacting phases, an isothermal reaction regime, and maintaining the conversion of the feedstock and the equilibrium activity of the catalyst at a constant level by continuously withdrawing part of the catalyst from the reactor and replacing it with fresh or regenerated. However, due to significant drawbacks, hydrodesulfurization and hydrocracking processes in a fluidized bed have not yet been widely used in oil refining. From industrially mastered processes original, the most technologically flexible and rather effective is the process of hydrodesulphurization of heavy oil residues “Hayval” developed by the French Institute of Petroleum. The process flow diagram is shown in fig. 25. The reactor block of installation consists of serially working protective R-1 and R-2 reactors, two consistently working main R-3 and R-4 reactors of a deep hydrodemetallization and two consistently working reactors of hydrodesulphurization ‒ R-5 and R-6. Protective reactors R-1 and R167

2 operate in an interchangeability mode: when the catalyst in the operating reactor loses its demetalizing activity, switch to another standby reactor without stopping the installation. The duration of continuous operation of the reactors is: for protective reactors ‒ 3-4 months, and for the rest ‒ 1 year. The feedstock (fuel oils, tars) is mixed with hydrogen-containing gas, the reaction mixture was heated in the furnace F-1 to the desired temperature and subsequently fed to the main reactor and to the protective reactors of hydrodemetallization and hydrodesulfurization. Products of hydrodesulphurization are subjected to hot separation in hot and cold gas separators, then to stabilization and fractionation on atmospheric and vacuum columns. As the catalyst is used the alumina modified by metals for hydrogenation. The catalyst has a rough surface with the pores in the form of “hedgehog”.

Figure 25. Process Flow Diagram of Installation of hydrodesulphurization of oil residues of the French Institute of Oil: CS – cold separators, HS – hot separators, HCG – hydrogen containing gas, AS – amine scrubber, AR ‒ Atmospheric rectification, VR ‒ Vacuum rectification, F-1 – furnace

168

5.5. Bases of hydrocracking of oil raw materials Hydrocracking is an effective and extremely flexible catalytic process that allows to solve the problem of deep processing of vacuum distillates in a complex way to obtain a wide range of motor fuels. Hydrocracking allows obtaining a wide range of high-quality petroleum products with high yields from virtually any crude oil by selecting suitable catalysts and process conditions: ‒ liquefied gases С3-С4, ‒ petrol, jet and diesel fuel, ‒ components of oils. Hydrocracking is one of the most dangerous oil refining processes, because the output of the temperature regime from under the control, there is a sharp increase in temperature, leading to the explosion of the reactor block. The hydrocracking process is characterized by higher pressures and temperatures. Thus there is at the same time a splitting and hydrogenation of components of raw materials. A distinctive feature of hydrocracking – products obtaining with considerable smaller molecular weight, than initial raw materials. For this cause process of hydrocracking has much in common with process of catalytic cracking, but its main difference – the hydrogen presence which is slowing down the reactions proceeding on the chain mechanism. As a result, the hydrocracking products are practically absent or contained in small amounts the lower hydrocarbons ‒ methane and ethane. Hydrocracking also has all the basic reactions of hydrotreating process. The most important hydrocracking reactions: ‒ rupture and saturation (hydrogenolysis) of paraffinic hydrocarbons along the C-C; ‒ hydrogenation of olefins presenting in the feedstock and other unsaturated compounds; ‒ hydrodealkylation and isomerization; ‒ hydrogenation of mono-, bi- and polycyclic aromatic hydrocarbons; ‒ breaking and saturation of oxygen, sulfur and nitrogen compounds along the C-O, CS, and CN; 169

‒ decomposition of organometallic compounds; ‒ polimerization and coke formation on the surface and in the bulk of the catalyst. The prevailing reaction is hydrogenolysis of C-C bond. If hydrocracking is carried out at a pressure of 10-15 MPa, together with the separation of side chains is possible hydrogenation of aromatic rings. The mechanism of hydrocracking reactions is carbonium ionic, i.e, the mechanism of catalytic cracking reactions, combined with isomerization and hydrogenation reactions. Hydrocracking catalysts are substantially at least trifunctional, and of selective hydrocracking ‒ tetra-functional, considering their molecular sieving properties. Usually they consist of the following three components: 1) acid, 2) dehydro-hydrogenating, 3) binding, providing mechanical mechanical durability and a porous structure. As the acid component, performing the cracking and isomerization functions, are used solid acids which are a part of cracking catalyst: zeolite, silica-alumina and alumina. To enhance the acidity of the catalyst halogen is sometimes added. As hydrogenating component are generally used those metals which are included in the hydrotreating catalysts: metals of VIII group (Ni, Co, sometimes Pt or Pd) and group VI (Mo or W). To activate the hydrocracking catalysts various promoters, rhenium, rhodium, iridium, and rare-earth elements are used. A binder functions often performs acidic component (alumina, aluminosilicates), and oxides of silicon, titanium, zirconium, magnesium- and zirconium silicates. Stages of hydrocracking of n-paraffin on the bifunctional catalyst: 1. Adsorption of n-paraffin on the metal centers; 2. Dehydrogenation with formation of n-olefins; 170

3. A desorption from the metal centers and diffusion to the acid centers; 4. A skeletal isomerization and/or cracking of olefins on the acid centers through the intermediate carbonium-ions; 5. A desorption of the formed olefins from the acid centers and diffusion to the metal centers; 6. Hydrogenation of n-and iso-olefins on the metal centers; 7. A desorption of the produced paraffins. The ratio of iso-paraffins to n-paraffins in the product is increased with decreasing of reaction temperature, because with increasing temperature the rate of cracking of iso-paraffins is increased faster than that for the n-paraffins. The ratio of iso-paraffins to nparaffins is also increased if the catalyst contains a weak hydrogenation component and a strong acid component. The single-stage hydrocracking scheme for vacuum gas oil is shown in fig.26. The feed (350-500°C) and the recycle hydrocracking residue are mixed with hydrogen-containing gas (HCG), heated first in heat exchangers, then in the oven to the reaction temperature and fed to the reactors. The reaction mixture is cooled in raw heat exchangers, then in air coolers and at a temperature of 45-55°C, it is sent to a highpressure separator where separation into HCG and unstable hydrogenation occurs. HCG after purification from H2S in the absorber by the compressor is circulated. The unstable hydrogenate through a pressure reducing valve is sent to a low pressure separator where part of the hydrocarbon gases are separated and the liquid stream is fed through heat exchangers to a stabilization column for stripping hydrocarbon gases and light gasoline. The stable hydrogenate is then separated in an atmospheric column into heavy gasoline, diesel fuel (via stripper) and a fraction of >360°C, part of which can serve as a recycle, and the balance amount as a raw material for pyrolysis, a base of lubricating oils, etc. Two-stage process of hydrocracking The block (fig.27) consists of the following sections: ‒ Furnace ‒ Section of reactors of the first stage. ‒ Second step of the reactor 171

‒ Reactor of the third step ‒ Fractionation section ‒ Recovery section

Figure 26. Diagram of a single-stage hydrocracking

The preheated material is first hydrotreated in a desulfurization and denitriding reactor in the presence of a catalyst followed by hydrocracking in a second reactor in the presence of a strong acid catalyst with relatively low hydrogenation activity. In the first-stage reactor, sulfur and nitrogen compounds are converted to hydrogen sulphide and ammonia with limited hydrocracking. In the two-stage process, an interstage separation of products is used, which removes H2S and NH3. In the case of a two-stage process, the hydrocracking catalyst operates at low concentrations of H2S and NH3. One of the important developments in the field of hydrocracking is mild hydrocracking and residual hydrocracking. Mild hydrocracking (MHC) is characterized by rather low conversion (20-40%) in comparison with traditional hydrocracking which gives 70-100% of conversion of heavy distillates with a high pressure. 172

Figure 27. Diagram of two-stage hydrocracking process Questions for self-checking: 1. Describe the classification of hydrocatalytic processes. 2. What are the purpose and significance of hydrocatalytic processes? 3. List the signs of hydrocatalytic processes of processing of oil raw materials. 4. What is the aim of catalytic reforming? 5. List the target processes in catalytic reforming. 6. Describe the catalysts of reforming. 7. Tell about bimetallic catalysts of reforming. 8. List 3 main industrial reforming processes. What is the most preferable? 9. What is platforming? 10. Describe technological scheme of the catalytic reformer (platforming) on platinum catalyst. 11. What units are included in the catalytic reformers of all types? 12. What is zeoforming? 13. Explain the concept “isomerism”. List the examples. 14. Who and when entered the term “isomerism” into organic chemistry? 15. What is the aim of the catalytic isomerization in modern oil-processing? 16. What causes of the actuality of improving the technology of isomerization processes and increasing the productivity of the process? 17. Isomerization of which feedstock is currently the largest industrial isomerization process? 18. In what country the process of isomerization is mainly carried out on previously inactive catalytic reforming units? 19. Tell about mechanism of isomerization.

173

20. What are the similarities and differences in the process of reforming and isomerization? 21. What is the role of hydrogen during process? 22. What catalysts are used for isomerization of pentane ‒ hexane mixture? 23. What catalysts are especially effective in the course of the isomerization process? 24. Tell about ideas of G.K. Boreskov. 25. Describe the laboratory researches for produce of standard isoalkanes. 26. Describe two technological schemes of isomerization of alkanes. 27. List the comparative characteristics of different options of the isomerization process. 28. Describe the possible schemes of the process isomerization with recycle. 29. Give the examples of isomerization processes and catalysts. 30. List three types of the developed industrial processes of isomerization. 31. Explain schematic diagram of the installation LI-150V. 32. Describe principal block diagram of the process of “Total Isomerization Process”. 33. List the different options of isomerization process developed by various firms. 34. Indicate the main trends of modern development of isomerization processes. 35. Describe the main indicators of foreign processes of low- and mediumtemperature isomerization of pentane-hexane fractions (on example of British Petroleum, Penex, Hayzomer, TIP). 36. What is the need for the process of joint catalytic isomerization and reforming of petroleum fractions? In what cases is the combined catalytic process economically beneficial and why? 37. When and where were on an industrial scale developed the hydrogenation processes for the first time in the world? 38. What is hydrogenation from the point of view of process chemistry? 39. List the goals of hydroprocessing processes. 40. Describe the mechanism of transformations different substances during hydroprocessing. 41. Tell about raw materials of hydrogenation processes in oil processing. 42. List two groups of catalysts for hydrogenation processes. 43. Explain the mechanism of hydrogenation processes on Al-Co-Mo and AlMo-Ni catalysts. 44. Explain the features of two methods of separating hydrogen-containing gas from hydrogen gas. 45. What are the main advantages of cold separation? 46. What is the main advantage of the hot separation? 47. Describe the principal technological scheme of the hydrotreating unit for diesel fuel. 48. List the data of material balance of hydrotreating units in case of the hydrotreating of diesel fuel.

174

49. Describe process of hydrotreating of vacuum distillates: the aim of the process, the raw materials, installations, technological parameters. 50. Describe classification of oil residues. 51. Tell about methods of “indirect” hydrodesulphurization. 52. List the options of the modern foreign industrial installations of hydrodesulfurization of oil residues. 53. Describe the process of hydrodesulphurization of heavy oil residues “Hayval” developed by the French Institute of Petroleum. 54. What is hydrocracking? 55. Why hydrocracking is one of the most dangerous oil refining processes? 56. List the most important hydrocracking reactions. 57. Tell about hydrocracking catalysts. 58. Explain a diagram of a single-stage hydrocracking. 59. Describe a two-stage process of hydrocracking. 60. What are the mild hydrocracking and the residual hydrocracking?

175

Oil and petroleum products are among the most harmful chemical pollutants, as indicated in the International Convention for the Prevention of Marine Pollution by Dumping of Wastes, adopted in late 1972. In connection with the growth of production, transportation, processing and consumption of oil and oil products, the scale of environmental pollution is expanding. Existing refineries are designed to process millions of tons of oil and are therefore an intense source of environmental pollution. The air pollution zone of powerful refineries extends over a distance of 20 km or more. The amount of released harmful substances is determined by the capacity of the refinery and is (percentage of the plant’s capacity): hydrocarbons 1.5 -2.8; hydrogen sulphide 0.0025 ‒ 0.0035 for 1% sulfur in oil; carbon monoxide, 30 ‒ 40% by wt. of combusted fuel; sulfurous anhydride ‒ 200% of the mass of sulfur in the combustible fuel. Most of the losses of hydrocarbons enter the atmosphere (75%), water (20%) and soil (5%). Sources of harmful substances in the oil refining industry are technological installations, apparatuses, units, pipes, ventilation shafts, reservoir breathing valves, open surfaces of treatment plants. Refining related to the production and use of substances with a number of specific properties (explosiveness, flammability, toxicity), which is often caused by situations, the consequences of which nega176

tively affect the human health and the environment. The vast majority of substances used in oil refining and petrochemicals have fire and explosive, harmful (toxic) and carcinogenic properties. The main feature of the enterprises for processing hydrocarbon raw materials is the presence of fire and explosion hazard products and raw materials that create the danger of major accidents. To assess the fire and explosion hazard of technological installations, a statistical analysis of major accidents, fires and explosions occurring at hazardous enterprises is required. Note that, despite the improvement of fire and explosion safety systems, the number of accidents is constantly increasing. In tab.22, 23, statistical data on major accidents in the oil refining and petrochemical industries of various countries are given as an example. It has been established that major accidents and accompanying fires and explosions in industries associated with the processing of hydrocarbon feedstock are in most cases due to leaks of combustible liquid or hydrocarbon gas. The impact on megacities at application of hydrocarbon systems is manifested in two ways. First, from the motor transport side ‒ contamination with combustion products of motor fuels, fuel spills, lubricating oils, etc. In addition to pollution of the city’s atmosphere, the automobile complex contributes significantly to the pollution of water and soil (suspended particles, petroleum products, organic solvents, heavy metals and their salts). Secondly, there is a powerful impact on the part of enterprises for processing hydrocarbon systems. The development of cities and industrial regions, as well as urban policy of the last decades, led to the fact that most of the enterprises for processing hydrocarbon systems, including oil refining and petrochemical industries, were in the urban metropolitan areas. The negative role of technogenic pollution considerably affects human health. According to statistical data, owing to technogenic air pollution health of the population worsens for 43-45%. Therefore for such productions environmental protection and increase in industrial safety should become priority activities. Enterprises of the oil refining industry emit significant amounts of gases and vapors (sulfur oxides, carbon monoxide (II), nitrogen oxides, hydrogen sulfide, ammonia, hydrocarbons, oxygen and nitro177

gen containing organic compounds, organic and inorganic dust, resinous substances) into the atmosphere. The largest are the emissions of hydrocarbons into the atmosphere. Fight with such emissions is hampered by the fact that they come from a huge number of sources dispersed over a large area, therefore, the use of any treatment facilities is excluded and the task of reducing emissions must be addressed by technological measures, for example: ‒ replacement of tanks with hipped roofs on tanks with floating roofs or pontoons; sealing of technological equipment and communications; ‒ application of automatic control of technological processes, which does not allow violation of parameters that regulate pressure and therefore prevents the activation of safety valves; ‒ use of a safety valve monitoring system; application of a developed flare system with full collection and use of waste gases; ‒ sealed discharge-filling in railway tanks; ‒ replacement of open oil traps with sealed and other. Table 22 Major accidents at the enterprises for processing of hydrocarbonic raw materials Place 1 Germany, Ludwigshafen Germany, Ludwigshafen France, Faisen

United States, Port Hudson South Africa, Potchefstroom United States, Decatur

178

Substance, nature of Emission, t Number of Number of accident deaths injured 2 3 4 5 Explosion of a cloud of 20 57 439 butadiene and butylene Explosion of a cloud of 30 207 300 dimethyl ether Explosion of the storage 200 18 81 of liquefied petroleum gas Explosion of the storage 70 0 7 of liquefied petroleum gas Leakage of liquid am18 64 monia from the storage Propane leak 63 7 152

1 Netherlands, Beck

2 Explosion of a cloud of propane England, Explosion of a cloud of Fliksborough cyclohexane USA Propylene emissions Colombia, Catagena Ammonia leak Colombia, SantaExplosion of methane Cruz Spain, San Carlos Explosion of a cloud of propylene Mexico, Mexico Explosion of the tank City (liquefied gas) Brazil, Cubatão Explosion of gasoline Russia, Yaroslavl Explosion of hydrocarbon gases Russia, Krasnoyarsk Explosion of hydrocarbon gases Russia, Россия, Ufa Emission and explosion of hydrocarbon gases

3 3-5

4 14

5 107

30-50

28

89

5.5 -

14 30 52

45 22 -

38

215

780

-

452

5,250

3.3

500 6

7,000 13

-

4

5

-

2

8

Table 23 Direct economic losses from major accidents at the US refineries City, state

Installation, process

Linden, New Jersey Billing, Montana Avon, California Avon, California Baton Rouge, Louisiana Texas City, Texas Texas City, Texas Borger, Texas Avon, California Torrance, California Norco, Louisiana Richmond, California Martinez, California Warren, Pennsylvania Chalmette, Louisiana Port Arthur, Texas Lake Charis, Louisiana Sweeny, Texas Beautmont, Texas Wilmington, California

Hydrocracking Alkylation Coking Coking Catalytic cracking Alkylation Alkylation Alkylation Catalytic cracking Alkylation Catalytic cracking Hydrocracking Catalytic cracking Catalytic cracking Hydrocracking Atmospheric-vacuum tube (AVT) Catalytic cracking Hydrotreating Atmospheric-vacuum tube (AVT) Hydrotreating

Direct losses, mln. USD 94.6 14.5 22.9 13.9 18.2 99.6 40.3 53.8 60.7 16.9 327.0 100.7 53.0 26.3 15,8 27.5 23.5 51.0 15.3 72.7

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Fire and explosion hazard of individual blocks of external process units is determined by the nature of the raw materials and finished products, the parameters of the process and the features of the equipment. Separate plant elements, for example, open tube furnaces, are sources of not only the formation of explosive mixtures, but also their ignition. The distribution of the number of accidents by certain types of technological equipment is presented in tab.24. Very topical is the detection of the gassed air environment of the territory of enterprises in the early stages of the accident. Table 24 Distribution of the number of accidents by types of process equipment Equipment Technological pipelines Pump stations Capacitive apparatus (heat exchangers, dehydrators) Furnaces Rectification, vacuum and other columns Industrial sewerage system Tank Farms

Number of accidents, % 31.2 18.9 15.0 11.4 11.2 8.5 3.8

Similar is the situation with emissions into the atmosphere of combustion products from process units and flare facilities. And here technological measures should be provided to protect the atmosphere from carbon monoxide (II) and sulfur dioxide. Emissions of carbon monoxide (II) can be reduced by ordering the combustion process, as well as catalytic afterburning to carbon dioxide. Reduction of sulfur dioxide emissions can be achieved by preliminary desulfurization of the fuel burnt. On the accepted technology of processing sulphurous oil in the course of catalytic hydrotreating hydrogen sulfide and other sulphurous compounds are extracted in the form of commodity products – sulfur or sulfuric acid and emission of hydrogen sulfide in the atmosphere is considerably excluded. Release of hydrogen sulfide from barometric condensers can be eliminated with their replacement by superficial condensers. Other sources of emission of hydrogen sulfide can be reduced by sealing improvement. 180

Dust emissions are more local than gas and are easier to catch. Dust is formed during the transportation of catalysts and adsorbents, their regeneration, grinding, drying, etc. When carrying out processes in fluidized bed reactors (catalytic cracking, dehydrogenation of butane), the catalyst particles in case of repeated use are reduced in size and are taken out with the gas flow. In oil refineries for the removal of dust particles apply dust precipitation chambers, cyclones, rotary apparatus. Measures to protect the air basin in oil refineries should be aimed at increasing the production culture, strict adherence to the technological regime, improving technology to reduce gas generation, maximizing the use of generated gases, reducing hydrocarbon losses at the facilities of the general plant, reducing emissions of harmful substances during adverse weather conditions, development and improvement of methods for monitoring and cleaning emissions into the atmosphere. The chemical, oil refining and petrochemical industries are among the most water-intensive sectors of the national economy. The complexity of solving the problem of rational use of water resources and preventing pollution of reservoirs by sewage is due to the peculiarities of these sectors: ‒ huge quantities involved in the production of material resources and manufactured products; ‒ diversity of applied technologies, manufactured products and resulting wastes; ‒ widespread use of water for production purposes and lack of technological solutions for its replacement. The composition of production sewage depends on the nature of use of water in technological process. At the sewage which is formed at modern oil refineries (oil refinery) there are impurity which don’t belong to the category of strongly toxic: chlorides, sulfates, nitrates and phosphates of sodium, potassium, calcium, ammonium, magnesium, iron, copper, organic products, suspended substances, oil products, surfactants, oils, etc. Wastewater from oil refining, petrochemical and chemical industries, in addition to dissolved organic and inorganic substances, may contain colloidal impurities, as well as suspended substances, the density of which may be more or less than the 181

density of water. In some cases, the wastewater contains dissolved gases. Sewage may contain in their composition fire- and explosive substances and also compounds, aggressive in relation to pipelines, collectors, the cleaning equipment. In certain cases sewage contains the substances possessing a pungent unpleasant smell or the surfactants leading to foaming, etc. At the solution of environmental problems the significant role is played by such processes as processing of oil residues, rational use of by-products of the main production and obtaining target products that provides the decision not only economic problems, but also decrease in ecological tension at the enterprise. The task of maximizing the involvement of heavy oil residues in processing is very relevant in the face of increasing demand for petroleum products and increasing demands on their quality, increasing safety and protecting the environment. In this aspect, the concept of a systematic approach to the solution of the problem should be adopted, which consists not only in reviewing the raw materials and products of oil refining processes as disperse systems, which allows to optimally optimize the processing of oil residues, but also to choose the direction for obtaining materials with improved environmental parameters. At the enterprises of oil-processing industry various chemical products, adsorbents which aren’t subject to regeneration, the ashes and the solid products which are turning out at heat treatment of sewage, various sediments, pitches and caught dust when cleaning emissions, etc. are among solid waste. The simplest utilization of this waste, if it is permissible, is the destruction by burning in different types of furnaces. Formed ash and slag can sometimes be used as a filler in the production of building materials, less often as fertilizer, even less often as raw materials for the allocation of certain components. If ash can not be used and the slag is directed to be stored in dumps, there are also incombustible unused solid waste products. The approach which is most traditionally applied today at the organization of fight against environmental pollution is construction of treatment facilities. However it is expedient only for adaptation of the existing productions to new requirements of ecology as leads to 182

significant increase in capital and operational expenditure and reduces real waste a little. The main direction of a solution of the problem of ecological safety should be considered greening of chemical productions, i.e. creation of environmentally friendly, waste-free, more precisely, low-waste technological productions in which all components of raw materials and energy are most rationally and in a complex used and normal functioning of the environment and natural balance aren’t broken. It is necessary to distinguish the following main directions in the implementation of environmentally friendly technological processes, including petrochemical processes: 1. Complex use and deep processing of raw materials. Production should be as resource-consuming as possible (resource-saving technologies), carried out with a minimum of raw material and reagent costs per unit of output. The resulting semi-finished products should be transferred as raw materials to other industries and completely processed. An example of this approach is the technology of deep oil refining. 2. Optimal use of energy and fuel. Production should be carried out with minimum energy and fuel consumption per unit of output (energy-saving technologies) and, consequently, thermal pollution of the environment is also minimal. Energy saving is promoted by integration and energy-technological combination of processes; transition to continuous technologies; improvement of processes of separation; use of the active and selective catalysts allowing to carry out processes at the lowered temperature and pressure; the rational organization and optimization of thermal schemes and schemes of recovery of energy potential of the waste streams; decrease in hydraulic resistance in systems and losses of heat to the environment, etc. Petroleum refineries and petrochemical enterprises are major consumers of fuel and energy. In their energy balance, direct fuel accounts for 43-45%, heat energy ‒ 40-42% and electric -13-15%. The useful use of energy resources does not exceed 40-42%, which leads to over-consumption of fuel and the formation of thermal emissions into the environment. 3. Creation of fundamentally new low-waste technological processes. This can be achieved by improving catalysts, machinery and 183

technology production. Low-waste processes are more efficient than processes with expensive wastewater treatment plants. It is more economical to obtain a small amount of very concentrated waste that can be recycled or disposed of by special technology than a large volume of highly diluted waste discharged into the biosphere. 4. Creation and implementation of closed water use systems, including (or minimizing) fresh water consumption and wastewater discharge into water bodies. 5. Ensuring high operational reliability, tightness and durability of functioning of the equipment and all systems of productions. Minimizing or exception of probability of accidents, explosions, fires and emissions of toxic agents in environment. Development of the automated systems of ensuring ecological safety of productions and complexes. 6. Ensuring high quality of targeted products used in the national economy. Ecologically clean should be not only the technological processes themselves, but also the products produced in them. Thus, motor fuels must satisfy the increased environmental requirements for the content of sulfur compounds, aromatic hydrocarbons, harmful additives, for example, ethyl liquid, etc. 7. Use of new environmentally friendly products from alternative sources of raw materials, for example, oil and natural gas, oxygencontaining hydrocarbons (alcohols, ethers) and hydrogen in road transport. The transfer of a part of vehicles to alternative fuels is considered in many countries of the world as a radical measure of reducing harmful emissions of cars, improving the air basin of large cities, while simultaneously significantly expanding the resources of motor fuels. Improvement of the environment is promoted by also constructive improvement and ecologization of the mobile equipment thanks to preferential use of diesels, in comparison with petrol cars; to increase in fuel efficiency of vehicles ‒ preferential production of cars of small and especially very small classes, mini-tractors. Questions for self-checking: 1. List two ways of manifestation the impact on megacities at application of hydrocarbon systems. 2. What are the main causes of major accidents and accompanying fires and explosions in industries associated with the processing of hydrocarbon raw materials?

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3. List as examples some major accidents at the various enterprises for processing of hydrocarbonic raw materials. 4. Tell about direct economic losses from some major accidents at the US refineries. 5. Describe the distribution of the number of accidents by certain types of technological equipment. 6. What are the main causes of accidents in installations for processing hydrocarbon systems? 7. What are the main causes of leaks of flammable liquids and gases? 8. List the main sources of ignition of fuel-air mixtures. 9. Indicate the main stages and characteristics of the development of accidents at production facilities associated with the emissions of combustible gases. 10. What is the specificity of accidents of open process units in oil refining and petrochemical industry? 11. Tell about the dust emissions. When they are formed? Describe the specifics of eliminating dust emissions. 12. Tell about industrial wastewater when processing organic products. 13. Describe the main directions of solving the problem of environmental safety in the processing and production of hydrocarbons. 14. List the main directions in the implementation of environmentally friendly technological processes, including petrochemical. 15. List radical measures for decrease in harmful emissions of cars and improvement of the air basin of large cities.

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Oil and products of its processing are the source of the main types of liquid fuel: gasoline, kerosene, jet, diesel and boiler. Oil is used to produce lubricating oils and special oils, petroleum pitch, coke, bitumen, grease for various purposes, petrochemical raw materials ‒ individual alkanes (paraffin hydrocarbons), alkenes (olefins) and arenes (aromatic hydrocarbons), liquid and solid paraffin. From petrochemical raw materials, in turn, produce a number of important products for various areas of industry, agriculture, medicine and life: plastic masses; synthetic fibers, rubbers and resins; textile-auxiliary substances; detergents; solvents; protein-vitamin concentrates; various additives to fuels, oils and polymers; сarbon black. Modern oil refineries differ in the big single power of installations, deepening of processes of separation of oil products and their catalytic processing. Oil refining is carried out in two main directions ‒ on installations of fuel and oil blocks where produce different types of motor fuels and oils and also paraffin, ceresin, bitumens. Besides, the modern plants include the productions of the chemical block intended for obtaining synthetic fatty acids, synthetic oils, additives, diemulsifiers, sulfuric acid, sulfur, various hydrocarbons, etc. In the modern oil processing it is accepted to subdivide oil refinery into two types: 186

‒ with no deep petroleum refining (NDPR); ‒ the deep petroleum refining (DPR). On the basis of concentrating of the residue it is convenient to classify oil refinery on 4 types (tab.25): 1) Oil Refinery of NDPR; 2) Oil Refinery of Deepened petroleum refining (DPR); 3) Oil Refinery of deep petroleum refining; 4) Oil Refinery of WRPR (without residue petroleum refining) Table 25 Relationship between the type of Oil Refinery and the efficient use of petroleum The indicator of oil

Type of Oil Refinery 1

2

3

4

Residue type

Fuel oil

Tar

Yield of the residue, % for oil of an average quality The deep of oil refining, % wt.

40 ‒ 55

20 ‒ 30

10 ‒ 15

0

45 ‒ 60

70 ‒ 80

85 ‒ 90

100

The effectiveness of the use of oil, points

2

3

4

5

Heavy tar No residue

The quality of the processed oil feedstock has a significant impact on the technological structure and technical and economic indicators of Oil Refinery. It is easier and cheaper to process lowsulfurous and light petroleum with high potential content of light than the sulfurous and high sulfurous (especially with high content of resin-asphaltene substances), which processing requires more intensity Oil Refinery with upgrading processes. The overestimated costs of processing of low grade oils should be compensated understated prices of them. There are three main directions of petroleum refining: 1) fuel; 2) fuel-oil; 3) petrochemical or complex (fuel and petrochemical, or fuel and oil and petrochemical). 187

At the fuel direction petroleum and gas condensate are generally processed on engine and fuel oils. Petroleum refining at oil refinery of a fuel profile can be deep and not deep. At the deep processing tend to produce the highest possible yield of high-quality motor fuels by involving them in the production of residues of atmospheric and vacuum distillation and refinery gases. The yield of boiler fuel in this option is minimized. Oil processing depth is achieved with 70-90% by wt. By fuel oil option of petroleum refining along with engine fuels produce various grades of lubricating oils. For the production of lubricating oils are generally selected oils with the high potential content of oil fractions with regard to their quality. Petrochemical and complex petroleum refining provides along with fuels and oils production of raw materials for petrochemistry (aromatic hydrocarbons, paraffin, raw materials for a pyrolysis, etc.), and in some cases – the production of products of petrochemical processing. The most important characteristic of the refinery are the amount of light oil extraction and the Oil Refining Depth. The separation of light (L) is determined by the formula: L = (G + K+ D + A + LP + LG +S)/P,

(137)

where G are the amounts of gasoline (automobile and aviation), Kkerosene, D-diesel fuel, A-aromatic hydrocarbons, LP- liquid paraffins, LG-liquefied gases, S-solvents, P ‒ power, thousand tons/year. Deep degree of petroleum refining is reached by wide use of secondary processes, such as catalytic cracking (36%), catalytic reforming (19%), hydrotreating (41%), hydrocracking (9.3%), coking, an alkylation, an isomerization, etc. The Oil Refining Depth (ORD) is the indicator characterizing efficiency of use of raw materials. By the magnitude of ORD it’s possible indirectly judge about the intensity of oil refineries by secondary processes and the structure of production of petroleum products. Certainly that the oil refinery with a high proportion of secondary processes have greater opportunities for the production from each ton 188

of raw material bigger quantity of more valuable, than an oil residue, oil products and, therefore, for more profound oil refining. The world refining still does not have commonly accepted and unambiguous definition of this indicator. In oil processing of the CIS countries depth of oil refining is meant as a total yield as a percentage to oil of all oil products, except unconverted residue used as the boiler fuel (BF): ORD=100-BF-(T+L), (138) where T and L are respectively specific costs of fuel of processing and loss of oil at oil refinery as a percentage on raw materials. In other countries a depth of oil refining is determined mainly as the total yield of light oil products from oil, i.e. depth of fuel oil refining it means. It has been proposed to characterize ORD by magnitude selection of light oil only by secondary processes (hydrocracking, catalytic cracking, and so on) from oil fractions boiling at temperatures above 350°C (i.e. from fuel oil). In accordance with this method refining by atmospheric distillation corresponds to zero depth processing. The depth of oil processing in Kazakhstan is low compared with developed countries. With rare exceptions for various refinery complex it is 50-60 (70)%. Oil Refinery capacities are loaded on average over the year by 60-65%. Improving the quality of catalysts for cracking, reforming, hydrotreating allows to increase the yield of target products, but does not solve the problem of a deep processing. In the territory of the former USSR the share of processes of deep processing makes less than 20% of volumes of primary processing. Approximate commodity balances of standard oil refineries with various schemes of oil refining are given in tab. 26. Table 26 Commodity balance of standard oil refineries by oil refining options Name of oil product

Fuel-oil option

Yield, in % on crude oil: 2 Automotive gasoline 15.25 The kerosene hydropurified 9.72 1

Fuel option Deep Not deep processing processing 3 22.65 9.72

4 15.19 9.72

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1 Diesel fuel for winter use Benzene Xylene Toluene Solvent Liquefied gases, including: Propane Isobutane n-Butane Propane-propylene fraction Propane and butane-pentanes of alkylation Isopentane for petrochemistry Liquid paraffin Petroleum coke Road and building bitumens Raw materials for production of technical carbon Boiler fuel Lubricating oils Solid paraffins and ceresin Sulfur elemental Fuel gas Carbon dioxide Waste and losses

2 15.46 7.06 0.57 0.58 0.14 1,58 0.66 0.49 0.43 0.40 0.41 5.76 -

3 25.35 7.06 0.57 0.58 0.14 2.56 0.80 0.60 0.42 0.60 0.14 0.60 0.41 2.40 5.76 0.95

4 21.26 0.57 0.58 0.14 1.58 0.66 0.49 0.43 0.40 5.76 -

40.08 0.14 2.05 0.80

15.59 -

37.33 3.86 0.88 0.14 2.19 0.90

0.63 3.10 1.80 1.88

The oil consumption for petrochemicals varies from 2 to 10% in different countries. It is believed that by the middle of the 21st century the development of new energy sources and the development of thermonuclear synthesis will lead to the fact that all oil will be directed to petrochemical needs. Today one of the most actual problems of the world economy will be the exhaustion of oil reserves. The recoverable reserves in the world of it while maintaining the current level of production will be enough for about 40 years. Reserves of it little in the last decade were performed by new geological discoveries of deposits, and besides, they were exhausted as a result of the inefficient design and superficial processing. In the next two or three decades, we are doomed to work with hard marginally profitable reserves, low debits fields with a high degree of depletion of the initial oil reserves. Oil must be completely and completely reprocessed to produce only 190

high-quality and environmentally friendly products, particularly motor fuels, high viscosity lubricants and raw materials for petrochemical synthesis. The strategic direction of development of oil refining should be considered (to legitimize) deep and without residue oil processing and a significant reduction in exports. Still an insurmountable technical barrier for deep without residue and its processing are the problems which associated, firstly, with an excess of carbon and, secondly, with a high content of metals in the petroleum residues that are not reversible catalyst poisons. On total capacity of the refinery and the amount of the processed crude oil the leading place belongs to the United States. Ultradeep degree of refining, a clearly expressed “gasoline” US refineries profile achieved by the widespread use of the secondary processes, such as catalytic cracking (more than 35%), catalytic reforming (about 20%), hydrotreating (more than 40%), hydrogen (more than 9%), coking, alkylation, isomerization, etc. The most mass product of oil refinery of the USA – automobile gasoline (about 42% for petroleum). Ratio gasoline: diesel (solar) oil is equal to 2:1. Fuel oil is produced in the minimum quantities – only 8% for petroleum. Deep (more than 92-93%) degree of petroleum refining in the USA is caused by application first of all of catalytic cracking of vacuum gasoil and fuel oil, hydrocracking and coking. On the power of these processes the USA significantly advance other countries of the world. From industrialized countries the largest capacities of oil refinery have: in Western Europe ‒ Italy, France, Germany and Great Britain; in Asia ‒ Japan, China and South Korea. The oil refineries of developed countries of Western Europe and Japan are characterized by the smaller depth of petroleum refining, than at the USA that is caused by need on climatic conditions of production of a large amount of furnace fuel. Ratio gasoline: diesel (solar) oil at oil refinery of Western Europe in favor of diesel (solar) oil as in these countries the intensive dizelization of motor transport is carried out. By saturation of oil refineries by secondary processes, primarily to deepen oil refining, Western European countries considerably inferior to the United States. Share of deepening oil refining processes (catalytic cracking, heavy cracking, hydrocracking, alkylation) at the oil refin191

ery of the US and Western Europe is respectively approx.72% and 43%. To increase the yield of motor fuels in a number of countries is implementing a program of wide capacity increase of deep oil refining processes, especially catalytic cracking units. In the oil-exporting countries the biggest refinery capacity have Saudi Arabia, Mexico, Brazil, Venezuela and Iran. In world oil processing the technological processes based on removal from oil residues of excess of carbon and redistribution of the hydrogen containing in the initial oil is prevailed. Calculations with the balances of hydrogen show that for production of motor fuels theoretically it will be required to remove from the average oil 5.3% of absolute carbon or 5.5% of carbon in the form of oil coke, coke on the catalyst, adsorbent or contact. Thus, the limit yield of motor fuels will make of average oil about 93%. The actual yield of motor fuels will be caused by quality of the recycled oil, first of all element, fractional and its chemical composition. Of course, during the processing light oil and gas condensate this figure is above 93%, and sulfur from heavy and high sulfur crude oils (such as of Kazakhstan) yield of motor fuels will not exceed 90%. The greatest difficulty in refining is qualified tars processing (vacuum residues, and in recent years ‒ deep vacuum distillation) with high content of asphalt-resinous substances, metals and hetero compounds requiring significant capital and operating costs. In this regard, at a number of refineries around the world are often limited to superficial processing of tar to produce non-fuel petroleum products such as bitumen, petroleum pitch and fuel oil. From processes of deep chemical processing of the tars based on removal of excess of carbon in world practice the greatest distribution was gained by the following: 1) The slowed-down coking (SDC) intended for production of the lumpy oil coke used as carbonaceous raw materials for the subsequent production of anodes; 2) Thermocontact coking (TCC), so-called continuous process of coking in the boiling layer (or “a fluid cracking”, the target purpose ‒ producing of distillate fractions, gases and the byproduct powdered coke used as invaluable power fuel; 192

3) The combined process of TCC with further steam-oxygen (air) gasification of powdered coke (a process of “Flexycoking” to produce in addition to distillates synthesis gas; 4) The processes of catalytic cracking and hydrocracking of petroleum residues after their preliminary deasphalting and demetallization (DA and DM) by the following non-catalytic processes: the process of “Demex” the firm UOP, “Roze” company “Kerr-McGee”. Many refineries in some countries are being constructed the unpromising visbreaking process. In this process does not remove excess of carbon of goudron and occurs only a slight decrease in viscosity of the residue that allows to reduce slightly consumption of the distillate diluent in the preparation of a boiler fuel. For non residual processing of heavy oil residues into motor fuels the most acceptable are thermo-contact processes carried out at elevated temperatures of cracking and low contact time on the surface of cheap natural adsorbent in new generation reactors and regenerators-boilers to produce distillate intermediates sent for ennobling and catalytic processing. The structure of perspective oil refineries should to include the following processes of new generation: 1) the thermo-adsorptive deasphaltizing and a dimetallization of fuel oil or tar (TDA, TDM, mastered in industrial or trial scale; 2) light hydrocracking (LHC) and hydrocracking (HC) of dimetallized gasoil, gasoline of process of TDA and light gasoil of catalytic cracking; catalytic cracking like LHC gasoil and unstable gasoline of process of LHC, and also the processes of production of high-quality gasolines ‒ alkylation and production of methyl tertbutyl ether (MTBE). Such schemes of perspective refineries allow to obtain highoctane components of gasoline, such as isomerizate, reformate, alkylate, MTBE, gasoline of catalytic and hydrocracking and selective hydrocracking, liquefied gases C3-C4, a much needed for the production of unleaded high-octane gasoline with a limited content of aromatic hydrocarbons, and diesel and reactive fuel with low content of sulfur of summer and winter varieties. The depth of refining at this refinery will be about 90%. In the oil-processing and petrochemical industry one of the main solid-phase waste are the acid tars which are formed in processes of 193

sulfuric acid purification of a number of oil products (oils, paraffin, kerosino-gasoil fractions, etc.) and by production from additives, synthetic detergents, flotoreagent. Acid tars are highly viscous resinous mass varying degrees of mobility, containing mainly sulfuric acid, water and various organic substances. The content of organic substances is in the range from 10 to 93%. The composition of acid tars determines the possible directions of their use. They can be processed into ammonium sulfate, used in the form of fuel (directly or after washing the acid contained in them) or as a reagent for cleaning petroleum products. Processing of acid tars for the purpose of obtaining dioxide of sulfur, high-sulphurous coke, bitumens and some other products is perspective. It is easier to transport and spray the obtained mixture with the nozzles. Thermal splitting of mixture of acid tars and the spent sulfuric acid is carried out in burning furnaces at 800-1,200ºC. In these conditions there is a formation of dioxide of sulfur and total combustion of organic substances. Organic part of acid tar contains various sulfur compounds, resins, solid asphalt-like substances ‒ asphaltenes, carbenes, carboids and other components, which allows to process them into bitumen, widely used as road-building materials. When the acid tars are heated, the sulfonic compounds and free sulfuric acid present in them are cleaved and, oxidizing the organic part, cause mass consolidation to form a heterogeneous mixture with a high content of carboides. Solid impurities present in processed and auxiliary materials at refineries and petrochemical plants, and a number of other substances lead to the formation of such a common type of waste as oil sludge. Their yield is about 7 kg per 1 ton of processed oil, which leads to the accumulation of huge masses of these wastes in the earth barns of oil refineries. Such slurries are heavy oil residues containing on average 1056% of oil products, 30-85% of water and 1.3-46% of solid impurities. When stored in sludge collectors (barns), such waste is stratified to form an upper layer, mainly consisting of an aqueous emulsion of petroleum products, a middle layer comprising water contaminated with oil products and suspended particles, and a lower layer, about 3/4 of which falls on a wet solid phase impregnated by oil products. Oil sludge can be used as a valuable raw material for petrochemicals. 194

The use of oil sludge is possible in several ways. In particular, during dehydration and drying of these wastes, it is possible to return them to production with the purpose of further processing according to the existing schemes into the targeted products. If there is oil production in the structure of the plant, the asphalts formed during the deasphalting of the tar and the extracts of the selective purification of the oil fractions can also be referred to oil residues. If the refinery does not have processes for the specialized processing of these heavy products, they are utilized as components of boiler fuel. The presence in the nomenclature of commercial products of fuel oil, wholly or partly consisting of the remainder of atmospheric distillation of oil, indicates a low level of enterprise development, weak utilization of the potential of processed raw materials. It is much more favorable to process the straight-run fuel oil containing valuable gasoil fractions at the enterprise with obtaining expensive motor fuels and lubricant oils. Such approach is especially relevant because the share heavy oils constantly increases in world oil processing. Tar, asphalt, oil purification extracts are good raw material for the production of oxidized and compounded bitumens used in the construction of roads, buildings and structures. Therefore, most refineries have bituminous plants. At present, there is no shortage of technical solutions for the processing of heavy sour oil residues in the world oil refining, however, most of these solutions require significant capital investments. Therefore, the efforts of many researchers today are aimed at finding methods that will improve the efficiency of processes already in widespread use. To intensify the processes of thermal destruction, the crude oil is subjected to activation, using physical and chemical methods. Thus, the use of various chemical additives makes it possible to take into account the characteristics of raw materials from the point of view of intermolecular interactions and, thereby, influence the speed and direction of chemical transformations in the system. Along with the development of hydrogenation processes for the processing of heavy oil residues in modern oil refining, the thermodestructive processes also remain relevant: thermocracking, visbreak195

ing, coking. The use in such processes of additives of chemical compounds fulfilling the functions of oxidizing agents / reducing agents, initiators / inhibitors of free radical processes, compensators of paramagnetic centers, regulators of phase transitions in a dispersed system, etc., makes it possible to exert a significant influence on the regime and results of thermodestructive processing of petroleum raw materials, leading to an increase in the yield of light distillates and vacuum gas oils and a decrease in coke formation. At the same time, to introduce successful promotional compositions into the industry, there is no need for a significant change in the technological scheme and equipment design. Questions for self-checking: 1. The essence of the modern strategic direction of petroleum refining and gas in the developed countries of the world. 2. What are the most important characteristic of the refinery? 3. What is the Oil Refining Depth (ORD)? 4. Prove need of deepening of petroleum refining. 5. List the main directions of petroleum refining. Give concrete examples of the countries. 6. What is the dynamics of the world extraction of oil and gas? 7. Specify the reasons for the decline in growth and the volume of oil production. 8. Compare processes of oil and gas processing in USA and European countries. 9. List the processes of new generation. 10. What processes of the new generation should include the structure of prospective oil refineries?

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A Acid-base catalysis is a catalytic reaction, where acids or bases are involved as catalysts. In general, this term can refer to both Brönsted and Lewis acids and bases. However, more specific terms for electrophilic and nucleophilic catalysis are also used for Lewis acids and bases. In the case of Brönsted acids and bases, the specific and general acid-base catalysis are distinguished, which are determined by the features of the mechanism of the catalytic process. Acidic center is the grouping of atoms in the structure of a macromolecule or on the surface of a solid body, which is capable of attaching a base with transferring it to a conjugated acid. Acidity is the ability of a substance to interact with a base. In this case, the base passes into the conjugate acid. The activation energy, for an elementary chemical transformation, is the minimum energy of the reagents, sufficient to overcome the barrier at the surface of the potential energy that separates the reactants from the products. If the reaction is complex (consisting of several stages), this term usually indicates an effective (apparent) activation energy. Activation of the catalyst is a technological stage which prepares the catalyst for work with reactionary mixture. In some cases it is convenient to carry out activation of the catalyst after its loading into the reactor. At a stage of activation there is a final formation of necessary phase structure of the catalyst, for example, reduction, sulfonation, oxidation, dehydroxylation (removal of water), addition of the activator and other processes are carried out. Activation of chemical reactions is a phenomenon of increasing the rates of chemical reactions in the presence of acids or bases, accompanied by their consumption. Such processes are sometimes called pseudo-catalytic processes. For such reactions, the mechanism of intermediate reaction of the reactants with the acid or base is similar to the true catalytic reaction, however, catalyst regeneration does not occur at the end of the catalytic cycle. Example: hydrolysis of carboxylic acid esters is accelerated in the presence of acid and represents a true catalytic reaction. The hydrolysis of amides of carboxylic acids should be considered as a pseudo-catalytic reaction, since it is also accelerated in the presence of an acid, but at the end of the catalytic cycle, an ammonium ion is formed instead of H+.

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Activated adsorption is a chemical adsorption characterized by a significant activation energy. In this case, the adsorption equilibrium is reached very slowly or is not achieved at all. The activator is a substance which interacts with the catalyst and causes increase in speed of catalytic reaction, but itself at the same time isn’t spent. For example, the rate of polymerization of α-olefins on metallocene catalysts increases significantly when methylaluminoxane is added to the system. The active center is an ensemble of atoms in the structure of the catalyst (complex compound or part of the surface) containing the minimum sufficient number of atoms of specific elements for the catalytic process to proceed. The active centers in the heterogeneous catalyst can be, for example, clusters from adjacent surface atoms, or particles adsorbed on the catalyst surface. In the case of a homogeneous metal-complex catalyst, the active center is usually considered to be the central metal atom together with the ligand environment. Active phase ‒ this term has the same meaning as the active component. It is used in those cases when it is required to specify the phase composition of the active component under catalytic process conditions. Example: the melt of potassium pyrosulfonadate is the active phase in the vanadium catalyst for the oxidation of SO2 into SO3. Active component is the substance which is a component of the multicomponent catalyst and directly carrying out catalytic transformation. Other components of the catalyst perform support functions, for example, are the carrier or the promotor. Example: for the put (deposited) catalyst of hydrogenation Ni/SiO2 an active component ‒ metal nickel, while silicon oxide ‒ the carrier. The Adams catalyst is a catalyst for reduction and hydrogenolysis in organic synthesis. The active phase of the catalyst is platinum black, formed in situ from platinum dioxide hydrate under the action of hydrogen H2. Additives are chemicals added to petroleum products in small amounts to improve quality or add special characteristics. They are non-hydrocarbon compounds added to or blended with a product to modify fuel properties (octane, cetane, cold properties, etc.). Examples: oxygenates: alcohols (methanol, ethanol), ethers such as MTBE (methyl tertiary butyl ether), ETBE (ethyl tertiary butyl ether), TAME (tertiary amyl methyl ether); esters (for example, rapeseed or dimethyl ether, etc.); chemical compounds (tetramethyl lead, tetraethyl lead and detergents). It must be remembered that the quantities of ethanol listed in this category should refer to amounts intended for fuel use. Adhesion coefficient is the relation of quantity of the adsorbed molecules for a unit of time to the frequency of concussions of molecules with the surface of adsorbent. The coefficient of adhesion depends on fill factor of a surface, temperature, structure of a surface of adsorbent and other parameters. Adiabatic reactor is a reactor in which chemical transformations are carried out in adiabatic mode. In such a reactor, there are no systems for removing heat, or such systems do not contact directly with the catalyst bed. Adiabatic reactors are used in large-scale production, if the process proceeds relatively slowly and is not accompanied by a significant release of heat.

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Adsorbate is a substance (molecule, ion or atom) adsorbed on the surface of a solid due to physical (physical adsorption) or chemical (chemisorption) interaction between a solid and a substance. Adsorbed substance ‒ see adsorbate. Adsorbent is a condensed substance on the surface of which adsorption takes place. Adsorption is a process in which a substance (molecule, atom, ion) accumulates on the surface of a solid (or, more rarely, a liquid) due to physical (physical adsorption) or chemical (chemisorption) interactions between matter and the surface. The number of adsorbed molecules is determined by the adsorption equilibrium. Depending on the type of interaction, physical and chemical adsorption is distinguished. The adsorption center is a specific place on the surface of the adsorbent, where the adsorption of the molecule takes place. Adsorption centers can be surface defects or surface functional groups (for example, the Brönsted acidic center). The adsorption complex is a group of atoms including an adsorbed substance and a part of the adsorbent surface that directly interacts with the adsorbate. Adsorption equilibrium is a thermodynamic equilibrium established between a substance in a homogeneous phase and in an adsorbed state on the adsorbent surface. The adsorption equilibrium is characterized by the adsorption constant, the temperature dependence of which is determined by the heat of adsorption. Adsorption isobar is the dependence of the equilibrium amount of adsorbed molecules on the temperature, measured at a constant partial pressure of the adsorbent in the gas phase. Adsorption impregnation is an impregnation method in which the application (putting) of a substance is achieved by adsorption of the precursor (the predecessor) of the active component from the solution onto the surface of the carrier. This method makes it possible to obtain a different distribution of the active component along the grain of the catalyst, including the "crust" catalysts widely used in industry (the active component is distributed in the outer layer of the carrier granules). Adsorption isotherm is the dependence of equilibrium quantity of the adsorbed molecules on the partial pressure of an adsorbtive in a gas phase measured at a constant temperature. The adsorption isotherm of Langmuir is an adsorption isotherm constructed for a monolayer adsorption model on a homogeneous surface in which the interaction between adsorbate molecules can be neglected. The adsorption isotherm of Langmuir is the simplest kind of isotherm and is often used as an assumption for constructing kinetic models. Adsorption with charge transfer is a chemisorption, accompanied by the reduction or oxidation of the adsorbent. For example, the adsorption of triphenylamine on aluminosilicate is accompanied by transfer of charge to the adsorption center of the aluminosilicate. Adsorptive is a substance that is in a homogeneous phase and is potentially capable of adsorption on the phase interface. Agglomerates are particles of matter obtained by combining smaller particles, for example, associates from primary particles.

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Aging of the catalyst is a slow and irreversible decrease in the catalytic activity as a result of a change in the structure of the catalyst. Aging of the precipitate is a transformation in the precipitated substance that occurs while the sediment is under the mother liquor. With the aging of the sediment, various physical and chemical processes take place, leading to crystallization, coarsening of particles, changes in phase and chemical composition. As a rule, aging is accompanied by a decrease in the surface area of solid particles in the sediment. Afterburn is the combustion of carbon monoxide (CO) to carbon dioxide (CO,); usually in the cyclones of a catalyst regenerator. Air fin coolers is a radiator-like device used to cool or condense hot hydrocarbons. Air pollution is the discharge of toxic gases and particulate matter introduced into the atmosphere, principally as a result of human activity. Air sweetening is a process in which air or oxygen is used to oxidize lead mercaptides to disulfides instead of using elemental sulfur. Alicyclic hydrocarbon is a compound containing carbon and hydrogen only, which has a cyclic structure (e.g., cyclohexane); also collectively called naphthenes. Aliphatic hydrocarbon is a compound containing carbon and hydrogen only, which has an open-chain structure (e.g., as ethane, butane, octane, butene) or a cyclic structure (e.g., cyclohexane). Alkanes (paraffins, saturated hydrocarbons) are a homologous series of noncyclic hydrocarbons that do not contain double or triple bonds. The simplest alkane is methane, the subsequent terms of the series (propane, butane, pentane, etc.) are obtained by adding to one ethylene one carbon atom ‒ a methyl group. The general formula for the series is CnH2n+2. Alkenes (unsaturated hydrocarbons, olefins) is a homologous series of noncyclic hydrocarbons containing double bonds. The simplest member of the series contains two carbon atoms ‒ ethylene. Next followed by propylene, butylenes, etc. The general formula for the series is CnH2n. Alkylate is the product of an alkylation process. Alkylate bottoms are residua from fractionation of alkylate; the alkylate product which boils higher than the aviation gasoline range; sometimes called heavy alkylate or alkylate polymer. Alkylation is the process of introducing an alkyl substituent into an organic molecule. It is used, for example, in the production of ethylbenzene: in this case, benzene is alkylated with ethylene. A process using sulfuric or hydrofluoric acid as a catalyst to combine olefins (usually butylene) and isobutane to produce a highoctane product known as alkylate. Alpha-scission is the rupture of the aromatic carbon-aliphatic carbon bond that joins an alkyl group to an aromatic ring. Alumina (A12O3) is oxide of aluminium and it is used in separation methods as an adsorbent and in refining as a catalyst. Amine washing is a method of gas cleaning whereby acidic impurities such as hydrogen sulfide and carbon dioxide are removed from the gas stream by washing with an amine (usually an alkanolamine). Aniline point is the temperature, usually expressed in ºF, above which equal volumes of a petroleum product are completely miscible; a qualitative indication of

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the relative proportions of paraffins in a petroleum product which are miscible with aniline only at higher temperatures; a high aniline point indicates low aromatics. Antiknock is resistance to detonation or pinging in spark-ignition engines. Antiknock agent is a chemical compound such as tetraethyl lead which, when added in small amount to the fuel charge of an internal-combustion engine, tends to lessen knocking. Antistripping agent is an additive used in an asphaltic binder to overcome the natural affinity of an aggregate for water instead of asphalt. API Gravity is an arbitrary scale expressing the density of petroleum products. Apparent density is the density of a solid porous substance, which is calculated as the ratio of the mass of the particle to its volume. Since part of this volume falls on the pores inside the particle, the apparent density of the porous substance is less than its true density. Apparent bulk density is the density of a catalyst as measured; usually loosely compacted in a container. Apparent viscosity is the viscosity of a fluid, or several fluids flowing simultaneously, measured in a porous medium (rock), and subject to both viscosity and permeability effects; also called efective viscosity. Aromatic hydrocarbons are organic compounds containing in their structure a cycle with conjugated double bonds. In the petrochemical industry under this name usually involve benzene, toluene and xylenes (ortho-, meta- and para-). Aromatics are organic compounds with one or more benzene rings. Aromatization is the conversion of nonaromatic hydrocarbons to aromatic hydrocarbons by: (1) rearrangement of aliphatic (noncyclic) hydrocarbons into aromatic ring structures; (2) dehydrogenation of alicyclic hydrocarbons (naphthenes). ART process is a process for increasing the production of liquid fuels without hydrocracking. Asphalt is the nonvolatile product obtained by distillation and treatment of an asphaltic crude oil with liquid propane or liquid butane; usually consists of asphaltenes, resins, and gas oil; a manufactured product. Asphalt cement is an asphalt especially prepared as to quality and consistency for direct use in the manufacture of bituminous pavements. Asphalt emulsion is an emulsion of asphalt cement in water containing a small amount of emulsifying agent. Asphaltene is that fraction of petroleum, heavy oil, or bitumen that is precipitated when a large excess (40 volumes) of a low-boiling liquid hydrocarbon (e.g., pentane or heptane) is added to (1 volume) of the feedstock; usually a dark brown to black amorphous solid that does not melt prior to decomposition and is soluble in benzene or aromatic naphtha or other chlorinated hydrocarbon solvents. Asphaltenes are the asphalt compounds soluble in carbon disulfide but insoluble in paraffin naphthas. They are the most high-molecular components of oil. Asphaltene association factor is the number of individual asphaltene species which associate in nonpolar solvents as measured by molecular weight methods; the

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molecular weight of asphaltenes in toluene divided by the molecular weight in a polar nonassociating solvent, such as dichlorobenzene, pyridine, or nitrobenzene. Asphalt flux is oil used to reduce the consistency or viscosity of hard asphalt to the point required for use. Asphaltics is a general term usually meaning the asphaltene fraction plus the resin fraction. Asphaltite is a variety of naturally occurring, dark brown to black, solid, nonvolatile bituminous material that is differentiated from bitumen primarily by a high content of material insoluble in n-pentane (asphaltene) or other liquid hydrocarbons. Asphaltoid is a group of brown to black, solid bituminous materials of which the members are differentiated from asphaltites by their infusibility and low solubility in carbon disulfide. Associated petroleum gas, APG is an oil product. In reservoir conditions, it is dissolved in oil and released when the fossil is extracted to the surface. The composition of associated gas varies greatly, but its main component is methane, as well as a certain amount of ethane, pentane and butanes, etc. Associative adsorption ‒ see nondissociative adsorption. Associative desorption is the reverse process of dissociative adsorption. Asymmetric catalysis is the production of optically active substances by catalytic reactions from optically inactive raw materials. The catalyst in this case must be a chiral substance, for example, a metal complex compound with chiral ligands. This can also be the case when a chiral modifier is added to a conventional catalyst that does not have optical properties. Asymmetric catalysis is widely used in the industry for the synthesis of biologically active substances, drugs, etc. Atactic polymer is a polymer in which the orientation of the side fragments of the molecular chain relative to the axis of the chain and each other is chaotic. Atmospheric Column is a distillation unit which operates at atmospheric pressure. Autocatalysis is the acceleration of a chemical reaction under the influence of a product or an intermediate of this reaction. Example: hydrolysis of esters, leading to the accumulation in the reaction system of an acid having a catalytic effect in hydrolysis. Aviation gasoline is any of the special grades of gasoline suitable for use in certain airplane engines. It is motor spirit prepared especially for aviation piston engines, with an octane number suited to the engine, a freezing point of –60°C and a distillation range usually within the limits of 30°C and 180°C. B Barrel is the unit of measurement of liquids in the petroleum industry; equivalent to 42 U.S. standard gallons or 33.6 imperial gallons. The base state is the state of the chemical substance associated with the lowest energy. Photochemistry usually refers to the electronic base state. The base center is a group of atoms in the structure of a macromolecule or on the surface of a solid that is capable of attaching an acid with transferring it to a conjugate base.

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Basic nitrogen is nitrogen (in petroleum) which occurs in pyridine form. Basic sediment and water (bs&w, bsw): the material which collects in the bottom of storage tanks, usually composed of oil, water, and foreign matter; also called bottoms, bottom settlings. Basicity is the ability of a substance to interact with an acid. At the same time the acid passes into the conjugate base. Battery is a series of stills or other refinery equipment operated as a unit. Bauxite is a mineral matter used as a treating agent; hydrated aluminum oxide. Bender process is a chemical treating process using lead sulfide catalyst for sweetening light distillates by which mercaptans are converted to disulfides by oxidation. Bending of the zone is the bending of the valence band or the conduction band in semiconductors on the surface due to the presence of the surface potential of the charge due to the adsorption of the substance (donor or acceptor) or due to the different distribution of defects in the near-surface region and in the volume of the substance. Bending is also formed due to a drop in potential when the semiconductor contacts the electrolyte. Bentonite is montmorillonite (a magnesium-aluminum silicate); used as a treating agent. BET is the method of determination of specific surface area of solid bodies based on model of physical adsorption of molecules of gases (nitrogen, argon, etc.) with use of the accepted value of molecular cross section. The method has received the name on names of three scientists (S. Brunauer, P. Emmett, E. Teller) who have developed the corresponding model for polymolecular adsorption. Despite some shortcomings in the theoretical description, this method is widely used as a standard technique for determining the surface area of catalysts and adsorbents. Benzene is an unsaturated, a colorless, six-carbon ring, basic aromatic liquid compound (C6H6). Bifunctional catalysis means catalytic reactions involving a bifunctional catalyst. Bifunctional catalyst is a catalyst, which contains two types of active centers, differing in their functions. Bifunctional catalysts are used when the reaction proceeds in two elementary stages, and these stages are catalyzed on active centers of different types. Example: for the hydrocarbon reforming process, bifunctional supported Pt/Al2O3 catalysts with acidic and dehydrogenating properties are effective. Bioelectrocatalysis is an acceleration of the electrochemical reaction in the presence of enzymes. Enzymes immobilized on the electrode carry electron transport directly between the electrode and the substrate, which does not require the participation of low molecular weight carriers. Biofuels are bioethanol, biodiesel, biomethanol, biodimethylether, biooil. Liquid biofuels are mainly biodiesel and bioethanol/ETBE used as transport fuels. They can be made from new or used vegetable oils and may be blended with or replace petroleum-based fuels. The natural plant feedstock includes soya, sunflower and oil seed rape oils. Under some circumstances, the spent vegetable oils may also be used as feedstock for the process.

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Biogas is a gas composed principally of methane and carbon dioxide produced by anaerobic digestion of biomass, comprising: landfill gas, formed by the digestion of landfilled wastes; sewage sludge gas, produced from the anaerobic fermentation of sewage sludge; other biogas, such as biogas produced from the anaerobic fermentation of animal slurries and of wastes in abattoirs, breweries and other agro-food industries. Bitumen is a solid, semi-solid or viscous hydrocarbon with a colloidal structure, being brown to black in colour, obtained as a residue in the distillation of crude oil, by vacuum distillation of oil residues from atmospheric distillation. Bitumen is often referred to as asphalt and is primarily used for construction of roads and for roofing material. This category includes fluidised and cut back bitumen. Bituminous is containing bitumen or constituting the source of bitumen. Bituminous sand is a formation in which the bituminous material (see Bitumen) is found as a filling in veins and fissures in fractured rocks or impregnating relatively shallow sand, sandstone, and limestone strata; a sandstone reservoir that is impregnated with a heavy, viscous black petroleum-like material that cannot be retrieved through a well by conventional production techniques. Black acid(s) is a mixture of the sulfonates found in acid sludge which are insoluble in naphtha, benzene, and carbon tetrachloride; very soluble in water but insoluble in 30% sulfuric acid; in the dry, oil-free state, the sodium soaps are black powders. Black oil is any of the dark-colored oils; a term now often applied to heavy oil. Black strap is the black material (mainly lead sulfide) formed in the treatment of sour light oils with doctor solution and found at the interface between the oil and the solution. Blast-furnace gas is the gas obtained as a by-product in operating blast furnaces; it is recovered on leaving the furnaces and used partly within the plant and partly in other steel industry processes or in power stations equipped to burn it. Blending is the process of mixing two or more petroleum products with different properties to produce a finished product with desired characteristics. A block (honeycomb) catalyst is a heterogeneous catalyst in which a carrier is used in the form of a monolithic block. Usually the block has a set of the parallel not crossed channels and is manufactured of ceramic silicate or metal materials. The active component is applied to the surface of the channels. The block catalyst is used in such processes where a large pressure drop is undesirable, for example, in the neutralization of exhaust gases in automobiles. Blowdown is the removal of hydrocarbons from a process unit, vessel, or line on a scheduled or emergency basis by the use of pressure through special piping and drums provided for this purpose. Blower is an equipment for moving large volumes of gas against low-pressure heads. Boiling range is the range of temperature usually determined at atmospheric pressure usually at atmospheric pressure in standard laboratory over which the boiling (or distillation) of a hydrocarbon liquid commences, proceeds, and finishes. Bottled gas is usually butane or propane, or butane-propane mixtures, liquefied and stored under pressure for domestic use.

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Bottoms are the liquid which collects in the bottom of a vessel (tower bottoms, tank bottoms) either during distillation; also the deposit or sediment formed during storage of petroleum or a petroleum product. Tank bottoms are the heavy materials that accumulate in the bottom of storage tanks, usually comprised of oil, water, and foreign matter. Bubble column is a fractionating (distillation) tower in which the rising vapors pass through layers of condensate, bubbling under caps on a series of plates. Broad (wide) fraction of light hydrocarbons (BFLH or WFLH) is a product of processing associated petroleum or natural gas. It is a mixture of volatile hydrocarbons with a number of carbon atoms from 2 to 5 and a valuable petrochemical raw materials. The Brönsted acidic center (BCC) is a group of atoms as a part of any substance, capable to chip off H+ proton. Example: a bridging OH group on the surface of various oxides. The Brönsted acid is a substance capable of cleaving a proton of H+. Brönsted's base is the substance capable to attach H+ proton. Bulk composition is the make-up of petroleum in terms of bulk fractions such as saturates, aromatics, resins, and asphaltenes; separation of petroleum into these fractions is usually achieved by a combination of solvent and adsorption processes. Bulk density is density of solid-phase material calculated by division of mass of a sample into the volume occupied by a sample. At the same time volume considers the free space which is available in particles and between particles. Thus, bulk density depends both on porosity of individual particles, and on density of their packing which in turn depends on a geometrical form of particles (powder, granules, tablets, etc.). Burner fuel oil is any petroleum liquid suitable for combustion. Burning oil is an illuminating oil, such as kerosene (kerosine) suitable for burning Burning-quality index is an empirical numerical indication of the likely burning performance of a furnace or heater oil; derived from the distillation profile and the API gravity, and generally recognizing the factors of paraffinicity and volatility. Burton process is an older thermal cracking process in which oil was cracked in a pressure still and any condensation of the products of cracking also took place under pressure. Butane dehydrogenation is a process for removing hydrogen from butane to produce butenes and, on occasion, butadiene. Butane vapor-phase isomerization is a process for isomerizing n-butane to isobutene using aluminum chloride catalyst on a granular alumina support and with hydrogen chloride as a promoter. Butane-butylene fraction (BBP) is a gaseous product of a catalytic cracking process containing normal (unbranched) alkanes and alkenes with 4 carbon atoms. C C1, C2, C3, C4, C5 fractions is a common way of representing fractions containing a preponderance of hydrocarbons having 1, 2, 3, 4, or 5 carbon atoms, respectively, and without reference to hydrocarbon type.

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Calcinating is a heat treatment of the catalyst at the increased temperatures. Calcinating is carried out as one of stages of preparation of the catalyst for the purpose of transfer of predecessors of various components to the necessary chemical composition. Also, the finished catalysts are subjected to calcination to carry out activation or regeneration processes. CANMET hydrocracking process is a hydrocracking process for heavy feedstocks that employs a low-cost additive to inhibit coke formation and allow high feedstock conversion using a single reactor. The capacity of a monolayer is the maximum amount of a substance (molecules, atoms or ions) per unit of regular surface centers, which can be adsorbed upon monolayer adsorption. In the case of chemisorption, the capacity of the monolayer is determined by the structure of the adsorbent and the chemical nature of the adsorbent. In the case of physical adsorption, it is assumed that the whole surface of the adsorbent is coated with a layer of tightly packed adsorbate molecules. Capillary impregnation is a method of impregnation in which the application (putting) of a substance is carried out by absorbing the solution into empty pores of the carrier under the action of capillary forces. Carbene is the pentane- or heptane-insoluble material that is insoluble in benzene or toluene but which is soluble in carbon disulfide (or pyridine); a type of rifle used for hunting bison. Carboid is the pentane- or heptane-insoluble material that is insoluble in benzene or toluene and which is also insoluble in carbon disulfide (or pyridine). Carbon residue is the amount of carbonaceous residue remaining after thermal decomposition of petroleum, a petroleum fraction, or a petroleum product in a limited amount of air; also called the coke- or carbon-forming propensity. Carbonate washing is processing using a mild alkali (e.g., potassium carbonate) process for emission control by the removal of acid gases from gas streams. Carbonylation is a catalytic process, the addition of carbon monoxide CO to a molecule of an organic compound (acetylenes, olefins, alcohols, aldehydes, etc.). The process is carried out in the liquid phase with the participation of nucleophilic molecules (water, alcohol) and in the presence of homogeneous catalysts (salts or metal complexes of Rh, Co, Ni, Fe, Ir, Os, etc.). Typical conditions are temperatures of 80-300°C and a CO pressure of 50-300 atm. Carbonization is a formation of coke on the surface of heterogeneous catalysts. Deposits of coke block the surface of the catalyst therefore activity can significantly decrease and change selectivity of the catalyst. Coking is one of the main reasons for the deactivation of catalysts used in refining processes (cracking, reforming, dehydrogenation, etc.). It is the removal of all lighter distillable hydrocarbons that leaves a residue of carbon in the bottom of units or as buildup or deposits on equipment and catalysts. The carrier is a solid phase component in the deposited (supported) catalyst, on the surface of which the active component is located. The main functions of the carrier are maintenance of an active component in a disperse state, creation of porous system, ensuring mechanical durability of granules of the catalyst. As carriers simple and complex oxides, and also materials on the basis of carbon are widely used. As a rule, the carrier in pure form doesn’t show catalytic activity in relation to

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reagents and is inert substance. But also many examples when the carrier enters chemical interaction with the reactionary medium, or with an active component are known. Catagenesis is the alteration of organic matter during the formation of petroleum that may involve temperatures in the range 50°C (120°F) to 200°C (390°F). Catalytic cracking is a secondary process of oil refining which essence consists in splitting of long hydrocarbonic molecules on shorter. The process of breaking up heavier hydrocarbon molecules into lighter hydrocarbon fractions by use of heat and catalysts. It is a source of petrochemical raw materials, such as propanepropylene fraction. Catalytic reforming is a secondary process of oil refining, the essence of which is the conversion of hydrocarbon chains into aromatic compounds ‒ components of fuels and petrochemical raw materials. Catalysis is the phenomenon of initiation of chemical reactions or change of their speed under the influence of substances – the catalysts which are repeatedly entering intermediate chemical interaction with participants of reaction and restoring the structure after each cycle of intermediate interactions. At the same time the catalyst doesn't displace chemical balance of reactions. The catalyst is a substance that changes the rate of chemical reactions without shifting their chemical equilibrium, which repeatedly enters into an intermediate chemical interaction with reagents and regenerates its chemical composition after each cycle of such interactions. An important feature is that the catalyst is regenerated in each catalytic cycle, which allows the conversion of large amounts of reagents in the presence of a relatively small amount of catalyst. As a rule, for each chemical reaction it is required to select the specific catalyst. Practical application as catalysts is found by the most various substances – from solutions of acids and complexes of metals to complex solid-phase multicomponent compounds of strictly specified composition and a structure. Catalyst plugging is the deposition of carbon (coke) or metal contaminants that decreases flow through the catalyst bed. The catalyst productivity is the amount of product produced per unit time, referred to the mass or volume of the catalyst. Catalyst durability is ability of particles of the solid-phase catalyst to maintain mechanical loadings. There are various experimental techniques for determination of durability (for example, durability on attrition, durability on crush). For commercial catalysts high durability allows to minimize losses during catalytic process, and also when transporting the catalyst and its loading in the reactor. Catalyst poisoning is the deposition of carbon (coke) or metal contaminants that causes the catalyst to become nonfunctional. Catalyst selectivity is the relative activity of a catalyst with respect to a particular compound in a mixture, or the relative rate in competing reactions of a single reactant. Catalyst stripping is the introduction of steam, at a point where spent catalyst leaves the reactor, in order to strip, i.e., remove, deposits retained on the catalyst. Catalytic activity is the rate of a chemical reaction, referred to the number of active catalyst centers or to a unit of mass or volume of the catalyst. The activity of

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the catalyst is determined by the nature and strength of the chemical bonds that are formed when reactants and reaction intermediates are bound to the catalyst. For a correct measurement of the catalytic activity should exclude the impact of mass and heat transfer. Also it is the ratio of the space velocity of the catalyst under test to the space velocity required for the standard catalyst to give the same conversion as the catalyst being tested; usually multiplied by 100 before being reported. The catalytic center is the center on which there are catalytic chemical transformations. If the number of the catalytic centers is unknown, for example, in case of a heterogeneous photocatalysis, for determination of specific parameters use BET surface measured on nitrogen adsorption. Catalytic combustion is a technology developed to produce thermal energy by oxidizing combustible compounds with oxygen in the presence of a catalyst. In the presence of catalysts, oxidation occurs at lower temperatures (without open flame). Multicomponent catalysts containing Cu, Cr, Pd, Mn and other components are used. Catalytic combustion is used in catalytic heat generators (KGT). The catalytic converter (neutralizer) of exhaust gases is a catalyst that provides removal of a number of harmful substances from exhaust gases in internal combustion engines. The main catalytic processes are oxidation of CO, postcombustion of hydrocarbons to CO2 and the reduction of nitrogen oxides. The most suitable are noble metal catalysts (Pt). The neutralization process is complicated due to temperature fluctuations in the exhaust gases (from 200 to 1000°C) and changes in the composition of the gas mixture (from oxidizing with excess oxygen to reducing with oxygen deficiency). Catalytic cracking is a catalytic hydrocarbon cracking process carried out in the presence of acid catalysts. The main catalytic cracking reaction is cleavage of the C-C bond in particles with an electron-deficient carbon atom, which leads to the formation of an alkane and an alkene. Also are carried out an intensive skeletal isomerization in hydrocarbons and process of transfer of hydrogen which reduces quantity of the formed olefin due to formation of aromatic hydrocarbons and coke. Catalytic cycle is a system of elementary reactions with participation of the catalyst at which the sequence is closed, a cyclic process of binding and regeneration of the catalyst occurs and the conversion of the starting materials to the products. An important feature is that after completion of the catalytic cycle, the catalyst passes to the initial chemical state and the catalytic cycle can be repeated many times with the same catalyst. Catalytic erosion is the destruction of the catalyst in the dendritic mechanism of coke formation. Separate components of the catalyst are mechanically separated and carried away with the growth of primary dendrites, which can lead to the complete destruction of the catalyst. Catalytic poison is a substance that forms strong chemical bonds (usually covalent) with atoms and ions entering the active sites of the catalyst to form catalytically inactive centers and, thus, leads to deactivation of the catalyst. In most cases, the catalytic activity and/or selectivity cannot be restored without significant change in reaction conditions. Special regeneration procedures are required, and most often the characteristics can only be partially recovered. The catalytic poison may be pre-

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sent as an impurity in a mixture of reagents, or it may enter the catalyst during the preparation stage. Typical poisons are sulfur and arsenic compounds, also the compounds of transition metals contained in raw materials can act as catalytic poisons. Catalytic photochemical reactions mean increase (change) in the efficiency of photochemical reactions during direct excitation of photosensitive reagents through the intermediate interaction of these reagents with certain compounds that act as catalysts (promoters) of the appropriate chemical transformation of the reagents. Sometimes this process may be identical to photocatalysis. The catalytic reaction is a chemical reaction proceeding through a sequence of stages forming a catalytic cycle. The catalytic route of the reaction is proved by the fact that the catalytic cycle can be realized several times (the number of revolutions exceeds unity). Currently, more than 80% of all industrial chemical processes are carried out using catalytic reactions. Catalytic reforming is rearranging hydrocarbon molecules in a gasolineboiling-range feedstock to produce other hydrocarbons having a higher antiknock quality; isomerization of paraffins, cyclization of paraffins to naphthenes, and dehydrocyclization of paraffins to aromatics. Catforming is a process for reforming naphtha using a platinum-silicaalumina catalyst which permits relatively high space velocities and results in the production of high-purity hydrogen. Caustic wash is a process in which distillate is treated with sodium hydroxide to remove acidic contaminants that contribute to poor odor and stability. Cetane index is an approximation of the cetane number calculated from the density and mid-boiling point temperature. Cetane number is a number indicating the ignition quality of diesel fuel; a high cetane number represents a short ignition delay time; the ignition quality of diesel fuel. Chemical adsorption (chemisorption) is a kind of adsorption, as a result of which a chemical bond is formed between the adsorbent and the adsorbate. Chemisorption implies the rearrangement of electrons in the adsorbed molecule and is therefore characterized by sufficiently large values of the heat of adsorption (more than 80-100 kJ/mol), as well as specificity for the adsorbent-adsorbate pair. In addition, unlike physical adsorption, chemical adsorption can have activation energy, proceed irreversibly and be accompanied by dissociation of adsorbate. In processes involving a heterogeneous catalyst, it is assumed that chemisorption of at least one of the reagents is an obligatory step, without which a catalytic conversion cannot occur. The chemical theory of a catalysis is the theory of a catalysis considering the catalyst as chemical compound with characteristic properties which is capable to contact reagents and to form unstable intermediates which destruction leads to products. Clay is silicate minerals that also usually contain aluminum and have particle sizes are less than 0.002 micron; used in separation methods as an adsorbent and in refining as a catalyst. Clay refining is a treating process in which vaporized gasoline or other light petroleum product is passed through a bed of granular clay such as fuller’s earth.

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Clay regeneration: a process in which spent coarse-grained adsorbent clays from percolation processes are cleaned for reuse by de-oiling them with naphtha, steaming out the excess naphtha, and then roasting in a stream of air to remove carbonaceous matter. Clay wash is a light oil, such as kerosene (kerosine) or naphtha, used to clean fuller’s earth after it has been used in a filter. Closed pores are pores that do not communicate with the outer surface of the particle. Molecules from the surrounding space cannot penetrate into the closed pores, therefore, such pores can not participate in adsorption and catalysis. Cloud point is the temperature at which paraffin wax or other solid substances begin to crystallize or separate from the solution, imparting a cloudy appearance to the oil when the oil is chilled under prescribed conditions. Coagulation is the process of combining (cohesion) of small particles in a dispersed system with the formation of larger particles. Example: as a result of coagulation, the sol passes into the suspension. Coalescence is the process of merging droplets or gas bubbles in disperse systems. Coenzymes are compounds with a small molecular weight that are located in the active center of the enzyme and participate together with the enzyme and substrate in the formation of the activated complex. Coenzymes can be various organic compounds or inorganic ions (K+, Mg2+, Mn2+, etc.). Some coenzymes form a strong complex with the structure of the enzyme (for example, flavin coenzymes) and remain in the structure of the enzyme at all stages of the catalytic process. Also weakly bound enzyme-coenzyme complexes are known in which the coenzyme can carry the substrate to another enzyme. Coke means the condensed aromatic hydrocarbons whose structure approximates to graphite. The formation of coke on the surface of catalysts is a harmful byproduct of hydrocarbon processing. It is also a high carbon-content residue remaining from the destructive distillation of petroleum residue. Coke-oven coke is the solid product obtained from carbonisation of coal, principally coking coal, at high temperature; it is low in moisture and volatile matter. Coke-oven coke is mainly used in the iron and steel industry acting as energy source and chemical agent. Coke breeze and foundry coke are included in this category. Semi-coke, the solid product obtained from carbonisation of coal at low temperature, should be included in this category. Semi-coke is used as a domestic fuel or by the transformation plant itself. This heading also includes coke, coke breeze and semicoke made from lignite/brown coal. Coke-oven gas is the gas obtained as a by-product of solid fuel carbonisation and gasification operations carried out by coke producers and iron and steel plants. Coking as a process is a thermal transformation and upgrading heavy residual into lighter products and by-product petroleum coke. Cold pressing the process of separating wax from oil by first chilling (to help form wax crystals) and then filtering under pressure in a plate and frame press. Cold settling is processing for the removal of wax from high-viscosity stocks, wherein a naphtha solution of the waxy oil is chilled and the wax crystallizes out of the solution.

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A colloidal solution is a dispersed system occupying an intermediate position between true solutions and coarsely dispersed systems. The particles of the dispersed phase in the colloidal solution have a size from 1 to 100 nm. Color stability is the resistance of a petroleum product to change color due to light, aging, etc. Combustible gases are the natural gases having ability to burn. Usually consist of gaseous hydrocarbons (methane, ethane, etc.) and are satellites of oil although also purely gas fields are known. If combustible gas contains a significant amount of vapors of natural gasoline (gasoline), such gas is called fat, at very small content of natural gasoline or at its absence gas is called dry. Combustible liquid is a liquid with a flash point in excess of 37.8ºC (100°F) but below 93.3ºC (200°F). Combustion zone is the volume of reservoir rock wherein petroleum is undergoing combustion during enhanced oil recovery. Compensation is an effect of simultaneous increase in a pre-exponential multiplier of k0 and the seeming energy of activation of Ea. Such effect can be observed for a series of the different catalysts used for the same reaction. Compressed natural gas (CNG) is natural gas for use in special CNG vehicles, where it is stored in high-pressure fuel cylinders. CNG’s use stems in part from its clean burning properties, as it produces fewer exhaust and greenhouse gas emissions than motor gasoline or diesel oil. Condensate is a natural mixture of mainly light hydrocarbon compounds that are in a dissolved gas and are converted into a liquid phase, with a decrease in pressure, below the condensing pressure. It is the liquid hydrocarbon resulting from cooling vapors. Condenser is a heat-transfer device that cools and condenses vapor by removing heat via a cooler medium such as water or lower-temperature hydrocarbon streams. Condensation is transition of substance from gaseous state into a liquid or solid phase. In case of disperse system this term designate formation of heterogeneous system from homogeneous as a result of association of molecules, atoms or ions in units. Condenser Reflux is condensate that is returned to the original unit to assist in giving increased conversion or recovery. A conduction band is a set of a plurality of closely spaced free or only partially occupied electronic levels that occurs in an array of a large number of atoms that form a solid body in which electrons can move freely. The term is used for the description of electrical properties of metals, semiconductors and dielectrics. In terminology of semiconductors and a photocatalysis the conduction band specifies the lowest level of a conduction band to which the electrons located at the highest level of the valence band are transferred with energy of high energy of the forbidden band. Conjugated diene hydrocarbons (dienes) are non-cyclic hydrocarbons containing two double bonds separated by a single bond. A homological series is formed with the general formula CnH2n-2. The simplest representative is 1,3butadiene.

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Contaminant is a substance that causes deviation from the normal composition of an environment. Continuous contact filtration is a process to finish lubricants, waxes, or special oils after acid treating, solvent extraction, or distillation. Conventional recovery is primary and/or secondary recovery. Conversion is the ratio of the amount of reagent converted into products to the total amount of reagent fed to the reactor inlet. At the same time the amount of reagent can be measured in various units (mol number, weight, etc.). Also it is the thermal treatment of petroleum that results in the formation of new products by the alteration of the original constituents. Conversion factor is the percentage of feedstock converted to light ends, gasoline other liquid fuels, and coke. Cooler is a heat exchanger in which hot liquid hydrocarbon is passed through pipes immersed in cool water to lower its temperature. A copolymer is a polymer consisting of monomers of different types. Copolymerization is the process of formation of polymer chains from monomers of different types. Copper sweetening is processes involving the oxidation of mercaptans to disulfides by oxygen in the presence of cupric chloride. Cracking is the process of breaking C-C bonds in a hydrocarbon molecule to form fragments with a lower molecular mass by the application of heat and pressure, with or without the use of catalysts. This is one of the most important processes in oil refining, used to convert high-boiling oil fractions to components with a higher octane number. There are catalytic cracking and thermal cracking. Crude assay is a procedure for determining the general distillation and quality characteristics of crude oil. Crude oil is a naturally occurring mixture of hydrocarbons that usually includes small quantities of sulfur, nitrogen, and oxygen derivatives of hydrocarbons as well as trace metals. It exists in the liquid phase under normal surface temperature and pressure and its physical characteristics (density, viscosity, etc.) are highly variable. Crystallization is a process of formation of a crystal phase of solution, steam or other solid phase, usually by decrease in temperature or evaporation of solvent. Cumene is a colorless liquid [C6H5CH(CH3)2] used as an aviation gasoline blending component and as an intermediate in the manufacture of chemicals. Curing (vulcanizing, vulcanization) is the process of rubber formation from rubber under the influence of vulcanizing agents, for example, sulfur. It consists in the crosslinking of polymer chains of rubber with each other into a single spatial grid. Cut point is the boiling-temperature division between distillation fractions of petroleum. Cutback is the term applied to the products from blending heavier feedstocks or products with lighter oils to bring the heavier materials to the desired specifications. Cutback asphalt is asphalt liquefied by the addition of a volatile liquid such as naphtha or kerosene that, after application and on exposure to the atmosphere, evaporates leaving the asphalt.

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Cutting oil is oil used to lubricate and cool metal-cutting tools. Cycle gas oil means the process when the cracked gas oil returned to a cracking unit. Cycle stock is the product taken from some later stage of a process and recharged (recycled) to the process at some earlier stage. Cyclic steams injection is the alternating injection of steam and production of oil with condensed steam from the same well or wells. Cyclization is the process by which an open-chain hydrocarbon structure is converted to a ring structure, e.g., hexane to benzene. Cyclone is a device for extracting dust from industrial waste gases. It is in the form of an inverted cone into which the contaminated gas enters tangential from the top; the gas is propelled down a helical pathway, and the dust particles are deposited by means of centrifugal force onto the wall of the scrubber. D Deactivation of the catalyst is a partial reduction or complete loss of catalytic activity during the operation of the catalyst. This term unites a fairly wide range of different processes and phenomena responsible for reducing catalytic activity. The most frequent reasons for the deactivation of catalysts are the change in the chemical composition of the catalyst under the conditions of the reaction medium, the volatility of the active component, the interaction of the active component with the carrier to form new phases, the change in the dispersion of the active component, poisoning, crystallization, sintering, coking and catalyst contamination. Dealkylation is the removal of an alkyl group from aromatic compounds. Deasphaltened oil is the fraction of petroleum after the asphaltenes have been removed using liquid hydrocarbons such as n-pentane and n-heptane. Deasphaltening is a removal of a solid powdery asphaltene fraction from petroleum by the addition of the low-boiling liquid hydrocarbons such as n-pentane or n-heptane under ambient conditions. Deasphalting is a process of removing asphaltic materials from reduced crude using liquid propane to dissolve nonasphaltic compounds. Debutanization is distillation to separate butane and lighter components from higher boiling components. Debutanizer is a fractionating column used to remove butane and lighter components from liquid streams. Decant oil is the highest boiling product from a catalytic cracker; also referred to as slurry oil, clarified oil, or bottoms. Decarbonizing is a thermal conversion process designed to maximize coker gasoil production and minimize coke and gasoline yields; operated at essentially lower temperatures and pressures than delayed coking. Decoking is a removal of petroleum coke from equipment such as coking drums; hydraulic decoking uses high-velocity water streams. Decolorizing is a removal of suspended, colloidal, and dissolved impurities from liquid petroleum products by filtering, adsorption, chemical treatment, distillation, bleaching, etc.

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De-ethanization is distillation to separate ethane and lighter components from propane and higher-boiling components; also called de-ethanation. De-ethanizer is a fractionating column designed to remove ethane and gases from heavier hydrocarbons. The degree of filling the surface (the degree of surface coverage) is the ratio of the amount of adsorbed material to the capacity of the monolayer. If the degree of filling is >1, the adsorption is multilayer. Sometimes the degree of surface filling is calculated as the ratio of the number of adsorbed molecules to the number of surface atoms. The degree of use of the inner surface, a dimensionless parameter, indicates the share of the inner surface in the catalyst granules that reacts with the reagents under the given process conditions. It depends on the specific catalytic activity, the effective diffusion coefficient and the shape of the catalyst granules. It can be calculated by division of observed speed of reaction to the speed of the reaction corresponding to the intra kinetic mode of course of reaction. Dehydrating agents are the substances capable of removing water (drying) or the elements of water from another substance. Dehydrogenation is the process of splitting off a hydrogen molecule from an organic compound. It is he removal of hydrogen from a chemical compound; for example, the removal of two hydrogen atoms from butane to make butene(s) as well as the removal of additional hydrogen to produce butadiene. In industry it is used to convert ethane, propane, and butane into olefins (ethylene, propylene, and butenes). Dehydrocyclization is any process by which both dehydrogenation and cyclization reactions occur. Demethanization is the process of distillation in which methane is separated from the higher boiling components. Demex process is a solvent extraction demetallizing process that separates high metal vacuum residuum into demetallized oil of relatively low metal content and asphaltene of high metal content. The density of active centers ‒ this term refers to solid phase catalysts and denotes the surface concentration of the active centers (i.e., the number of active centers per unit surface). Depentanizer is a fractionating column used to remove pentane and lighter fractions from hydrocarbon streams. The deposited catalyst is a heterogeneous catalyst in which the finely divided particles of the active component are located on the surface of the carrier. Example: in the Pt/Al2O3 hydrogenation catalyst, dispersed particles of metallic platinum (the active component) are deposited on the surface of alumina (carrier). The deposition is a step of preparing the supported (put) catalysts, as a result of which the precursor of the active component passes from the solution or from the gas phase to the surface of the solid support. Different methods of application have their own names (for example, impregnation, deposition-precipitation, etc.). Deposition-precipitation is a method of producing deposited catalysts that combines methods of impregnation and precipitation. The active component is applied to the surface from the solution in the form of a suspension, which is formed by the gradual addition of a precipitant to the impregnating solution, the surface of

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the carrier acts as the crystallization centers. The method is used in cases where the compound, which is a precursor of the active component, is poorly adsorbed on the surface of the carrier. Depentanizer is a fractionating column for the removal of pentane and lighter fractions from a mixture of hydrocarbons. Depropanization is distillation in which lighter components are separated from butanes and higher boiling material; also called depropanation. Depropanizer is a fractionating column for removing propane and lighter components from liquid streams. Desalting is removal of mineral salts (most chlorides, e.g., magnesium chloride and sodium chloride) from crude oil. Desorption is the reverse of adsorption process. As a result of desorption, the adsorbed material passes from the interface to the volume of the adjacent homogeneous phase. Desulfurization is a chemical treatment to remove sulfur or sulfur compounds from hydrocarbons. Detergent oil is a lubricating oil possessing special sludge-dispersing properties. Devolatilized fuel is the smokeless fuel; coke that has been reheated to remove all of the volatile material. Dewaxing is the removal of wax from petroleum products (usually lubricating oils and distillate fuels) by solvent absorption, chilling, and filtering. Diagenesis is the concurrent and consecutive chemical reactions which commence the alteration of organic matter (at temperatures up to 50°C (120°F) and ultimately result in the formation of petroleum from the marine sediment. Diesel fuel is fuel used for internal combustion in diesel engines; usually that fraction which distills after kerosene. Diesel cycle is a repeated succession of operations representing the idealized working behavior of the fluids in a diesel engine. Diesel index is an approximation of the cetane number of diesel fuel calculated from the density and aniline point. Diesel knock is the result of a delayed period of ignition and accumulated diesel fuel in the engine. Diethanolamine is a chemical (C4H11O2N) used to remove H2S from gas streams. Differential selectivity is the ratio of the rate of formation of the target product to the total rate of consumption of the reagent due to all reactions. Unlike integral selectivity, differential selectivity depends only on the temperature and composition of the reaction mixture, and does not depend on the type of reactor. Differential heat of adsorption is the thermal effect of adsorption, which is measured during a calorimetric experiment when a small portion of a substance is fed. A significant change in the differential heat of adsorption with increasing surface filling is usually attributed to the inhomogeneity of adsorption centers and/or to intermolecular interactions in adsorbed molecules. Differential mode of the reactor is the mode of operation of the ideal displacement reactor, in which the conversion of the initial reactants at the outlet from

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the reactor remains low. Under such conditions, it can be assumed that the entire volume of the catalyst interacts with the reaction mixture in which the concentration of the reactants is the same. Diffusion impregnation is an impregnation method in which the putting of a substance is carried out by diffusion from the solution into the pores of the carrier, previously filled with a pure solvent. Diffusion inhibition is a decrease in the rate of the catalytic process due to the low diffusion rate of the reagents. In the case of a heterogeneous catalyst, external diffusion inhibition is distinguished (diffusion of the substance from the volume to the surface of the catalyst) and intra-diffusion inhibition (diffusion of the substance inside the catalyst granules). The dispersed phase is a finely divided substance in the composition of a dispersed system. Dispersing is the crushing or grinding of macroscopic particles of matter. Dispersion is a quantity that is equal to the ratio of the number of surface atoms to the total number of atoms in the particle. Dispersion is inversely proportional to the particle size. The higher the dispersion of the particles, the smaller their size and, consequently, the higher the fraction of surface atoms. The dispersion medium is a part of the disperse system, in the volume of which the disperse phase is distributed. The dispersion system is a heterogeneous system containing a finely divided substance (dispersed phase), which is distributed in the volume of some other substance and does not mix with it (dispersion medium). Dissociative adsorption is chemisorption, during which the adsorbed molecule breaks up into two or more fragments. Example: dissociative adsorption of hydrogen H2 on metals leads to the formation of two Н⋅ radicals on the metal surface. Distillate are the products of distillation formed by condensing vapors. Distillation is the physical and technological process of separation of mixtures of liquids based on differences in the boiling points of the components. Doctor solution is a solution of sodium plumbite used to treat gasoline or other light petroleum distillates to remove mercaptan sulfur; see also Doctor test. Doctor sweetening is a process for sweetening gasoline, solvents, and kerosene by converting mercaptans to disulfides using sodium plumbite and sulfur. Doctor test is a test used for the detection of compounds in light petroleum distillates that react with sodium plumbite; see also Doctor solution. Doping is the formation of a solid solution when small amounts of foreign atoms are added to the crystal lattice of a nonmetallic catalyst. The term is generally applied to catalysts that are semiconductors. Doping changes the electronic properties of the catalyst, which can affect the rate of catalytic conversion. Downflow is a process in which the hydrocarbon stream flows from top to bottom. Downflow reactor is a reactor in which the feedstock flows in a downward direction over the catalyst bed. Drying is a removal of a solvent or water from a chemical substance; also referred to as the removal of solvent from a liquid or suspension.

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Dropping point is the temperature at which grease passes from a semi-solid to a liquid state under prescribed conditions. Dry gas is natural gas with so little natural gas liquids that it is nearly all methane with some ethane. Drying is the stage of preparation of catalysts, as a result of which excess solvent is removed from the catalyst. Typically, drying takes place at elevated temperatures, but without any chemical transformation in the catalyst structure. Dry stripped gas (DSG) is a product of processing associated petroleum or natural gas. It is a methane with minor impurities of other hydrocarbons. It is used mainly as a fuel. Dualayer distillate process is a process for removing mercaptans and oxygenated compounds from distillate fuel oils and similar products, using a combination of treatment with concentrated caustic solution and electrical precipitation of the impurities. Dualayer gasoline process is a process for extracting mercaptans and other objectionable acidic compounds from petroleum distillates; see also Dualayer solution. Dualayer solution is a solution that consists of concentrated potassium or sodium hydroxide containing a solubilizer; see also Dualayer gasoline process. Dubbs cracking is an older continuous, liquid-phase thermal cracking process formerly used. E The effective (apparent) activation energy is the value of the activation energy of a complex chemical process, determined experimentally from the tangent of the slope of the graph constructed in Arrhenius coordinates (coordinates log (k) -1/T, where k is the rate constant, and T is the temperature). Effective density is the density of solid phase catalysts, determined on the basis of the volume of liquid that is displaced by the sample when it is placed in this liquid. The effective density values can differ significantly for different liquids due to the fact that a different degree of penetration of liquids into the pores of the catalyst is observed. The effective diffusion coefficient is the average diffusion coefficient in solid porous particles, taking into account molecular and Knudsen diffusion. The effective pore size is the diameter of the maximum circumference, which can be inscribed in a flat pore cross section. In this case, the plane section of the pore can have an arbitrary geometric shape. Efficiency of the catalyst is the number of mol of the formed products referred to one mol of the active centers of the catalyst. It is the cumulative characteristic of catalytic properties considering activity, selectivity and period of operation of the catalyst without loss of catalytic activity. Elastomers are polymers characterized by highly elastic properties under normal conditions, that is, they can be reversibly deformed. Electrocatalysis is a change in the rate or direction of an electrochemical reaction, depending on the electrode material. The electrode material has a catalytic

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effect on the reaction rate through the chemisorption steps of various particles on the electrode surface. For example, the speed of electrode allocation of H2 increases by 1,010 times when replacing an electrode from lead by an electrode from platinum. In electrochemical oxidation of alkanes to CO2 which represents a complex chain of intermediate stages with a rupture of C-C and S-N links the electrode can participate in dehydrogenation of chemisorbed fragments and influence the selectivity of some stages. Electrocatalysis is not possible if the electrode material is included in the general electrochemical equation of the process. Example: for anodic copper dissolution Cu0 → Cu2+ + 2e-), or the electrochemical process proceeds without the chemisorption stage at the electrode. The electronic theory of a catalysis is the theory of a catalysis which connects catalytic action to features of electronic (zonal) structure of catalytic agents (metals, semiconductors, dielectrics). Transfer of charges between the reacting molecule and the catalytic agent influences chemisorption strength of reagents. Electrophilic catalysis is a catalytic reaction in which the catalyst is a Lewis acid. Example: Friedel-Crafts alkylation in the presence of aluminum chloride AlCl3. Emission control is the use gas cleaning processes to reduce emissions. Emission standard is the maximum amount of a specific pollutant permitted to be discharged from a particular source in a given environment. Emulsion breaking is the settling or aggregation of colloidal-sized emulsions from suspension in a liquid medium. Emulsion polymerization is the polymerization of an emulsion of monomer (droplets of monomer or its solution, immiscible with medium, usually water) stabilized by the surfactants (S) with formation of polymeric suspension, that is a suspension of solid substance in the liquid medium. The initiator of the monomer is soluble in water. Process of growth of a chain of polymer goes in micelles surfactant. Enzymes are protein macromolecules that are catalysts in living organisms. Enzymes have unique catalytic properties ‒ they have high activity, are highly specific to reagents, are capable of performing stereo- and regioselective processes with 100% yield. Enzymatic catalysis means catalytic reactions, carried out under the influence of specific biological catalysts ‒ enzymes. Catalytic reactions involving enzymes ensure the vital activity of biological organisms. Also, enzymatic catalysis is widely used in the chemical industry, for example, in the production of glucose from starch, in the synthesis of amino acids, vitamins and other substances. Ethane is a naturally gaseous straight-chain hydrocarbon (C2H6) extracted from natural gas and refinery gas streams. Ethyl alcohol (ethanol or grain alcohol) is an inflammable organic compound (C2H5OH) formed during fermentation of sugars; used as an intoxicant and as a fuel. The excited state is a state with the energy exceeding energy of the main condition of a chemical object. In photochemistry it can be the electronic excited state. The photogenerated free electrons in a zone of conductivity and the free photogenerated holes in a valent zone are the excited condition of the photocatalyst. Free and

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bound excitons also represent an excited state of the photocatalyst. The active state of the photocatalytic (photoadsorption) center is the excited state of the photocatalyst. At the same time, this state is in its lowest energy state with respect to the set of possible electronic states in the solid subsystem (for example, empty defects and carriers). Exciton is the electronic excitement considered as quasi-particles which are capable to migration. For the description of organic materials use two models: zonal or wave (low temperature, high crystal order) and hopping (higher temperature, low crystal order or amorphous state). In the hopping model, the energy transfer coincides with the migration energy. In semiconductors and insulators, a free electronhole pair (neutral quasi-particle) is a free exciton, capable of migrating and transferring its energy to the lattice of a solid. The exciton localized is the exciton taken by defect or self-taken by the center in a regular lattice because of its polarization that leads to the electronic excited condition of defect or the localized excitement of a regular lattice respectively. In the latter case, the decay of the exciton can lead to the formation of new defects. The decay of a self-trapped exciton on a surface can lead to the formation of surface active centers with catalytic activity. Expanding clays are clays that expand or swell on contact with water, e.g., montmorillonite. Explosive limits are the limits of percentage composition of mixtures of gases and air within which an explosion takes place when the mixture is ignited. External diffusion regime is a mode of catalytic reaction, in which the rate of the process is limited by the diffusion of matter from the volume of the reaction mixture to the surface of the heterogeneous catalyst. The concentration of reagents on the surface of the catalyst can approach zero. The apparent activation energy of the entire process is determined by the activation energy of diffusion in the volume and is usually ~ 10 kJ/mol. The external diffusion regime is used for a small number of industrial processes, for example, in the oxidation of methanol to formaldehyde on a silver catalyst. External surface is an external surface of particles of catalysts and adsorbents without their internal porous structure (an internal surface). Usually, superficial pores and cavities are also referred to the external surface if their width exceeds the depth. Extrudate is a product obtained by extrusion. Extrusion is a forming method in which a paste is extruded through a spinneret. The size of the holes in the spinneret determines the size and shape of the resulting particles. The quality of the product (extrudate) depends to a large degree on the water content and rheological properties in the initial paste, which are regulated by special additives. F Faujasite is a naturally occurring silica-alumina (SiO2-A12O3) mineral. FCC is a fluid catalytic cracking. Feedstock is petroleum as it is fed to the refinery; a refinery product that is used as the raw material for another process; the term is also generally applied to

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raw materials used in other industrial processes. So, it stock from which material is taken to be fed (charged) into a processing unit. The Fermi level is the level associated with the energy of the electrons that are least firmly held in the solid body. The value of the Fermi level at a temperature of 0 K is Fermi energy and is constant for each solid. The Fermi level changes when the solid is heated and when electrons are added or removed. At nonzero temperatures, as the Fermi level, one can select a level that is filled exactly by half in the statistical distribution of the Fermi-Dirac probabilities. Doping of the initial substance leads to a shift in the Fermi level and, consequently, to a change in its energy. Fire point is the lowest temperature at which, under specified conditions in standardized apparatus, a petroleum product rapidly vaporizes sufficiently to form above its surface an air-vapor mixture which burns continuously when ignited by a small flame. The Fischer-Tropsch process is a catalytic process for the production of liquid hydrocarbons from synthesis gas. Metal catalysts containing iron and cobalt are generally used. Due to exhaustion of world reserves of hydrocarbonic raw materials this process was of particular importance for production of synthetic fuels and lubricant coal oils. Fixed bed is a stationary bed (of catalyst) to accomplish a process. The fixed catalyst is an immobilized catalyst in which the active site is attached to the carrier by a covalent chemical bond. Typically, this term refers to systems in which the surface functional group of a carrier is covalently bound to one of the ligands in the organometallic complex. Such a system retains the properties inherent in free metal complexes in solution, including, for example, the mechanism of catalytic conversion. The advantage of fixed catalysts compared with metal complexes in solution is the possibility to separate the catalyst from the reaction mixture by filtration. Flashing is the process in which a heated oil under pressure is suddenly vaporized in a tower by reducing pressure. Flash point is the lowest temperature at which a petroleum product will give off sufficient vapor so that the vapor-air mixture above the surface of the liquid will propagate a flame away from the source of ignition. Flue gas is gas from the combustion of fuel, the heating value of which has been substantially spent and which is, therefore, discarded to the flue or stack. The flowing and circulating reactor is the reactor used in laboratory researches in which the catalyst is in a circulating contour with rapid circulation of reactionary mixture through the catalyst. Reagents with a constant speed are entered into a contour, and products with a constant speed are taken away from a contour. Due to rapid circulation of mixture on a contour a number of advantages is reached (constant temperature is established, influence of external diffusion, etc. is eliminated). The flowing reactor is the reactor of continuous action having a constant stream of reagents on an entrance to the reactor and a constant stream of products at the exit from the reactor. Fluid bed is use of an agitated bed of inert granular material to accomplish a process in which the agitated bed resembles the motion of a fluid.

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The fluidized bed reactor is a reactor in which solid catalyst particles (0.010.1 mm in size) are suspended in an upward flow of gaseous reactants. The advantages of this type of reactor are the intensive heat exchange between the catalyst particles, the absence of external diffusion inhibition, and the ease of catalyst loading. The lack of a fluidized bed is an increased abrasion of the catalyst particles. Reactors of this type are suitable for reactions with very high heat release, or in cases where the catalyst needs frequent replacement. The fluidized bed reactor is a fluidized bed reactor containing a gas, liquid, and a solid phase. Flux is lighter petroleum used to fluidize heavier residual so that it can be pumped. Forming is a stage of preparation of catalysts which is responsible for the external sizes and a form of particles of the ready catalyst. Forming can be carried out by various methods (spray drying, extrusion, tabletting, granulation, etc.). Fouling is an accumulation of deposits in condensers, exchangers, etc. Fraction is one of the portions of fractional distillation having a restricted boiling range. Fraction С2+ is a mixture of hydrocarbons with the number of carbon atoms from 2 and above. Most often, this term means light hydrocarbons with a carbon number of up to 5. Fractionating column is a process unit that separates various fractions of petroleum by simple distillation, with the column tapped at various levels to separate and remove fractions according to their boiling ranges. FTC process is a heavy oil and residuum upgrading process in which the feedstock is thermally cracked to produce distillate and coke, which is gasified to fuel gas. Free sulfur is sulfur that exists in the elemental state associated with petroleum; sulfur that is not bound organically within the petroleum constituents. Fuel Gas is refinery gas used for heating. Fuel oil is also called heating oil, it is a distillate product that covers a wide range of properties Functional group is the portion of a molecule that is characteristic of a family of compounds and determines the properties of these compounds. Fundamental absorption (internal absorption) is absorption of ultraviolet, visible or infrared radiation in semiconductors and insulators, which causes optical transitions of electrons, which occur solely because of transitions from the valence band to the conduction band, with the formation of free electron-hole pairs and/or exciton absorption bands. Furnace oil is a distillate fuel primarily intended for use in domestic heating equipment. G Gas is a natural mixture of hydrocarbon, non-hydrocarbon compounds and elements that are in formation conditions in the gaseous phase, or dissolved in oil or water conditions, and under standard conditions ‒ only in the gaseous phase.

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The gas cap is the accumulation of free oil gas in the most elevated part of the oil reservoir above the oil deposit. It will produce only gas. Gas condensate ‒ this term means liquid hydrocarbons of various structures, which are in situ in a gaseous state and are mixed with the natural gas condensate fields. When extracted, they condense and become liquid. During processing, the gas condensate must be stabilized, that is, the dissolved light hydrocarbons-propane, butane, etc., must be removed from it. Gas/diesel oil (distillate fuel oil) is primarily a medium distillate distilling between 180°C and 380°C. Examples: transport diesel (on road diesel oil for diesel compression ignition cars, trucks, etc., usually of low sulphur content); heating and other gas oil: light heating oil for industrial and commercial uses, marine diesel and diesel used in rail traffic, other gas oil including heavy gas oils which distil between 380°C and 540°C and which are used as petrochemical feedstocks. The gas field ‒ one or several gas deposits, confined territorially to one area, or associated with a favorable tectonic structure (anticlinal fold, dome, etc.) or other type of trap. Gas factor is the amount of natural gas (in cubic meters) per 1t or 1m3 of oil. Gas flow is the amount of gas in volume or weight terms, released from a well or from any source per unit of time (per hour, per day, etc.). Gas fractionation is a process for separating gas mixtures (for example, BFLH) into their individual hydrocarbons or narrower mixtures to produce liquefied hydrocarbon gases. A gas fractionation unit (GFU) is used to separate mixtures of light hydrocarbons into individual components or narrower mixtures ‒ liquefied hydrocarbon gases. Gas-condensate deposit is a deposit in which hydrocarbons in the conditions of the existing reservoir pressure and temperature are in gaseous state. At pressure decrease and temperatures the phenomenon of the so-called "return condensation" at which hydrocarbons partially pass into a liquid phase takes place and remain in pore channels of layer from which it is difficult to extract. The operation of the gas condensate deposit in order to avoid these losses must be done with maintaining the pressure above the reverse condensation point, for which the injection of extracted gas back into the formation after its topping is organized. Gas mode (dissolved gas mode) is the mode of operation of the oil deposit in which oil is entrained to the bottom of the wells by the more mobile masses of the expanding gas that has passed when the pressure in the reservoir decreases below the saturation pressure from the dissolved state to the free state. Gas oil is middle-distillate petroleum fraction with a boiling range of about 175 – 400ºC, usually includes diesel fuel, kerosene, heating oil, and light fuel oil. It is a petroleum distillate with a viscosity and boiling range between those of kerosine and lubricating oil. Gas-oil ratio is a ratio of the number of cubic feet of gas measured at atmospheric (standard) conditions to barrels of produced oil measured at stocktank conditions. Gaseous pollutants are gases released into the atmosphere that act as primary or secondary pollutants.

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Gasoline is a blend of naphthas and other refinery products with sufficiently high octane and other desirable characteristics to be suitable for use as fuel in internal combustion engines. It is fuel for the internal combustion engine that is commonly, but improperly, referred to simply as gas. Gasoline type jet fuel (naphtha type jet fuel) includes all light hydrocarbon oils for use in aviation turbine power units, distilling between 100°C and 250°C. It is obtained by blending kerosenes and gasoline or naphthas by method at which the aromatic content does not exceed 25% in volume, and the vapour pressure is between 13.7kPa and 20.6kPa. Gas processing plant (GPP) is an enterprise where drying, desulfurization (removal of sulfur compounds) and separation of associated oil or natural gas into components ‒ methane and other hydrocarbons takes place. The gas-oil reservoir is a reservoir in which free gas occupies the entire higher part of the structure and is directly in contact with oil occupying a reduced part of the structure in the form of a rim, and the volume of the oil part of the deposit is much smaller than the volume of the gas cap. At a large depth of bedding, the gas cap, regardless of its size, may contain petroleum hydrocarbons in the gascondensate state. The gas saturation pressure is a pressure at which a certain volume of gas is in a dissolved state in the oil. General acid-base catalysis is a catalytic reaction which speed is proportional to concentration of acid or the basis in undissociated form. Such regularity is observed in case the limiting stage is transfer of a proton of H + or OH- hydroxide ion to a reagent molecule. Granules are the substances in the form of unbound particles with a size of more than 1 mm. Granulation is a method for forming granules from powders. Usually, this procedure is performed when the powder is moistened in a rotating drum. Grafting is the formation of a covalent chemical bond between a metal center and a functional group on the surface of a carrier. Usually this term refers to fixed metal complexes in which the functional group of the carrier enters the internal coordination sphere of the metal. This leads to a change in such properties as the symmetry, coordination number, degree of oxidation of the central atom in comparison with the free metal complex in solution. Greenhouse effect is warming of the earth due to entrapment of the sun’s energy by the atmosphere. Greenhouse gases are gases that contribute to the greenhouse effect. H The heat of adsorption is the thermal effect observed during adsorption. The magnitude of the thermal effect gives information on the binding energy of the adsorbent-adsorbate. In some cases, the heat of adsorption strongly depends on the degree of filling of the surface, which is explained by the presence of intermolecular interactions and inhomogeneity of adsorption centers. The thermal adsorption effect can be directly measured with a calorimeter, or calculated from the adsorption iso-

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therms measured at different temperatures. There are isosteric, integral and differential heat of adsorption. Heat exchanger is the equipment to transfer heat between two flowing streams of different temperatures. Heat is transferred between liquids or liquids and gases through a tubular wall. Heteroatom compounds are chemical compounds that contain nitrogen and/or oxygen and/or sulfur and/or metals bound within their molecular structure(s). The heterogeneity of the centers is the presence of adsorption centers or active centers in the structure of the catalyst with different properties. For example, there is often a different heat of adsorption, a different strength of acid sites, etc. Heterogeneous catalysis is a phenomenon of the change in the rates of chemical reactions under the influence of catalysts, which form a separate phase, while the reagents are in a different phase. The reactants are contacted with the catalyst at the interface. The most widespread systems are those in which reactants from a liquid or gaseous phase interact with a solid catalyst. The heterogeneous catalyst is a catalyst existing in the reaction mixture as a separate phase. A catalytic reaction involving a heterogeneous catalyst necessarily takes place at the phase boundary. Unlike a homogeneous catalyst, the advantage of a heterogeneous catalyst is the ease of separating the reaction products from the catalyst. Heterolytic adsorption ‒ the term applied to the dissociative chemical adsorption means heterolytic bond cleavage in the original molecule adsorbed to form the anion and cation. HF alkylation is an alkylation process whereby olefins (C3, C4, C5) are combined with iso-butane in the presence of hydrofluoric acid catalyst. High-boiling distillates are fractions of petroleum that cannot be distilled at atmospheric pressure without decomposition, e.g., gas oils. High-line or high-pressure gas is high-pressure (100 psi) gas from cracking unit distillate drums that is compressed and combined with low-line gas as gas absorption feedstock. Highly elastic state is a physical state into which passes solid polymer when heating. It is characterized by ability of polymer in such state reversibly to be deformed when imposing small loading. High-sulfur petroleum is a general expression for petroleum having more than 1 wt % sulfur; this is a very approximate definition and should not be construed as having a high degree of accuracy because it does not take into consideration the molecular locale of the sulfur. All else being equal, there is little difference between petroleum having 0.99 wt% sulfur and petroleum having 1.01 wt% sulfur. Homogeneous heterogeneous catalysis is a special type of catalytic processes in which a solid catalyst is capable of initiating a chemical reaction in the bulk phase (in a liquid or in a gas). Examples of processes: oxidation of methane on oxide catalysts at not too high temperatures. Homogeneous catalysis is a phenomenon of changes in the rates of chemical reactions under the influence of catalyst substances that are present in one phase with reagents and are dispersed in this phase at the molecular level. Homogeneous catalysis is possible in the gas phase or in the liquid phase, however, only liquid-

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phase catalytic reactions are of practical use. Therefore, the term homogeneous catalysis is often used in a narrower sense to refer to reactions in liquid solutions involving soluble catalysts. A homogeneous catalyst is a catalyst that is present in a single phase with reagents and is dispersed in this phase at the molecular level. For example, the catalytically active substance can be dissolved in the liquid phase together with the reagents, or it can be present as a gaseous compound in the gas mixture with the reagents. Advantage of the homogeneous catalyst in comparison with the heterogeneous catalyst is the one-type interaction with reagent molecules throughout the volume of reactionary mixture, and the main shortcoming – difficulty of separation of products of reaction from the catalyst. Homolytic adsorption ‒ the term is applied to dissociative chemical adsorption, means homolytic breaking of the bond in the initial molecule with the formation of two adsorbed (surface) radicals. Example: the adsorption of hydrogen to form two radicals H⋅ on the surface of metals. Homogeneous photocatalysis is photocatalysis occurring in homogeneous systems. HOT process is a catalytic cracking process for upgrading heavy feedstocks using a fluidized bed of iron ore particles. Houdriflow catalytic cracking is a continuous moving-bed catalytic cracking process employing an integrated single vessel for the reactor and regenerator kiln. Houdriforming is a continuous catalytic reforming process for producing aromatic concentrates and high-octane gasoline from low-octane straight naphthas. Houdry butane dehydrogenation is a catalytic process for dehydrogenating light hydrocarbons to their corresponding mono- or diolefins. Houdry fixed-bed catalytic cracking is a cyclic regenerable process for cracking of distillates. Houdry hydrocracking is a catalytic process combining cracking and desulfurization in the presence of hydrogen. Hydrocarbon compounds are chemical compounds containing only carbon and hydrogen. Hydrocarbon gasification process is a continuous, noncatalytic process in which hydrocarbons are gasified to produce hydrogen by air or oxygen. Hydrocarbon resources are resources such as petroleum and natural gas that can produce naturally occurring hydrocarbons without the application of conversion processes. Hydrocarbon-producing resource is a resource such as coal and oil shale (kerogen) which produce derived hydrocarbons by the application of conversion processes; the hydrocarbons so-produced are not naturally-occurring materials. Hydroconversion is a term often applied to hydrocracking. Hydrocracking is a catalytic process, the cracking of heavy hydrocarbons in the presence of hydrogen H2. A process used to convert heavier feedstock into lower-boiling, higher-value products. The process employs high pressure, high temperature, a catalyst, and hydrogen. In addition to cracking reactions, hydrogenolysis, hydrogenation of aromatic hydrocarbons, the opening of cycles in naphthenes, hydrodealkylation of alkylaromatic compounds and naphthenes occur. Hydrocracking catalysts can be oxides and sulphides of Ni, Co and Mo.

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Hydrocracking catalyst is a catalyst used for hydrocracking which typically contains separate hydrogenation and cracking functions. Hydrodenitrogenation is the removal of nitrogen by hydrotreating. Hydrodemetallization is the removal of metallic constituents by hydrotreating. Hydrodesulfurization is a catalytic process of the removal of sulfur from oil or its fractions by hydrogenation of sulfur-containing compounds to form hydrogen sulfide and convert to hydrocarbons and H2S. The process is carried out in the presence of hydrogen H2. The catalysts are supported oxides of Co and Mo, which under the process conditions become sulfides. Hydrogenation is the chemical addition of hydrogen to a material in the presence of a catalyst. Hydrogenolysis is a catalytic process of rupture of C-C or C-X bonds (X = N, S, O, etc.) in hydrocarbons under the action of hydrogen H2. It is carried out on catalysts of hydrogenation and dehydrogenation (for example, metal catalysts). Often, the hydrogenolysis reaction requires high temperatures and a strong binding of the reactants to the catalyst and is therefore difficult to implement. Hydrofinishing is a catalytic treating process carried out in the presence of hydrogen to improve the properties of low viscosity-index naphthenic and medium viscosity-index naphthenic oils. It is also applied to paraffin waxes and microcrystalline waxes for the removal of undesirable components. This process consumes hydrogen and is used in lieu of acid treating. Hydroforming is a catalytic reforming of naphtha at elevated temperatures and moderate pressures in the presence of hydrogen to form high-octane aromatics for motor fuel or chemical manufacture. This process results in a net production of hydrogen and has rendered thermal reforming somewhat obsolete. It represents the total effect of numerous simultaneous reactions such as cracking, polymerization, dehydrogenation, and isomerization. Hydroformylation is a catalytic process, the reaction of an olefin with carbon monoxide CO and hydrogen H2 to form aldehydes of a branched and unbranched structure. Cobalt carbonyl Co2(CO)8, as well as phosphine complexes of cobalt and rhodium, are used as catalysts. Hydrothermal synthesis is a method of obtaining carriers and catalysts in aqueous solutions at temperatures above 100°C and pressures above 1 atm. Under such conditions, water can dissolve many substances (oxides, silicates, sulfides), which under normal conditions are practically insoluble. Advantages of the method are the ability to synthesize large crystals of high quality, as well as the possibility of obtaining crystals of substances that are unstable near the melting point. The main parameters of hydrothermal synthesis are the initial pH of the medium, the duration and temperature of the synthesis, the amount of pressure in the system. Hydrotreating is the removal of heteroatomic (nitrogen, oxygen, and sulfur) species by treatment of a feedstock or product at relatively low temperatures in the presence of hydrogen. Hydrovisbreaking is a noncatalytic process, conducted under similar conditions to visbreaking, which involves treatment with hydrogen to reduce the viscosity of the feedstock and produce more stable products than is possible with visbreaking.

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The ideal displacement reactor is a fixed-bed flow reactor in which there is no diffusion stirring of the reaction mixture when passing all length of the reactor. The ideal displacement condition means that in the cross section of the reactor all particles of the reaction mixture move with the same velocity, directed along the flow axis. Thus, all of the reagent molecules have the same contact time with the catalyst. The ideal mixing reactor is a reactor in which the reaction mixture is stirred intensively, and as a result, it can be assumed that the temperature and concentration of the substances in the entire reaction volume remain constant. Conditions close to ideal mixing can be realized both in flowing reactors, and in reactors of periodic action. The Ili-Ridil mechanism is a mechanism of a heterogeneous catalytic reaction, in which the compound adsorbed on the surface of a solid catalyst reacts with a molecule from the gas or liquid phase. The immobilized catalyst is a heterogeneous catalyst obtained by applying (putting) a homogeneous catalyst (often a metal-complex compound or enzyme) onto the surface of a solid-phase carrier. The immobilized catalysts have high activity and selectivity characteristic of homogeneous catalysts, and at the same time can be easily separated from the reaction medium, which is an advantage of heterogeneous catalysts. The fixing of homogeneous catalysts on a carrier can be achieved in various ways: through adsorption, non-covalent interactions (ionic or hydrogen bonds), the formation of a covalent bond with a carrier (fixed catalyst), grafting. Impregnation is a method of producing supported (deposited) catalysts, which consists in converting the predecessor of the active component from the solution to the carrier surface. When the substance is applied from the solution, adsorption on the carrier surface, ion exchange or chemical interaction with surface functional groups is possible. It is also possible that there is no specific interaction between the substance from the solution and the carrier, and in this case the deposited material is deposited in the pores of the carrier during the drying of the catalyst. Impregnation on a moisture capacity is an impregnation method in which the volume of impregnating solution is equal to the free volume of the carrier pores (a carrier moisture capacity). Thus, all entered predecessor of an active component appears in the carrier pores. The free volume of the carrier pores can be known in advance, or it is determined in the empirical way or by appearance of granules of the carrier during impregnation. Impurities are substances that are present in small (trace) amounts in the feed, or in the catalyst. Usually this term implies that within the developed chemical technology it is difficult to control the composition of these substances and their quantity. The inhibitor is a substance that slows down the chemical reaction. This term is applied to any reactions (catalytic, non-catalytic, chain). Sometimes for such substances the term negative catalyst is used, which is not recommended by IUPAC rules. The effect of inhibitors can be due to a variety of mechanisms. For example, some inhibitors are irreversibly consumed during the reaction. In case of enzymatic

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reactions chemical linkng of inhibitor with enzyme is the frequent reason of delay of reaction. This term also means an additive used to prevent or retard undesirable changes in the quality of the product, or in the condition of the equipment in which the product is used. Index group is a part of atoms of the reacting molecule which directly interacts with the surface of the catalyst at adsorption. The induction period is the initial stage of the chemical transformation, during which an increase in the reaction rate is observed (self-acceleration of the reaction). The induction period can be observed in catalytic processes due to various factors (for example, autocatalysis, heating of the system in the case of highly exothermic reactions, adsorption of interfering impurities from the reaction mixture onto the catalyst, etc.). The initiator of polymerization is a substance that excites polymerization and is irreversibly consumed. Irreversible consumption at the initiation stage distinguishes the initiator from the polymerization catalyst. Example: a peroxide that is readily cleavable to form radicals is used as a radical polymerization initiator. The resulting radicals are embedded in the monomer and thus initiate a chain radical process. Integral selectivity is the ratio of the amount of the target product to the amount of all products obtained during the reaction. The integral heat of adsorption is determined by integrating the differential heat of adsorption for a certain range of values of the degree of filling of the surface. The integrated mode of the reactor is an operating mode of the reactor of ideal replacement at which considerable conversion of initial reagents at the outlet from the reactor is reached. The interface of the phases is the boundary separating the two neighboring phases. Sometimes this term refers to a surface layer thickness of a few atoms, which are different in energy from atoms in the bulk of each phase. For solid particles, this is an external monolayer consisting of a regular matrix of surface atoms (or ions), as well as internal and external surface defects of various types. Internal diffusion is the molecular or Knudsen diffusion of a substance occurring inside granules of a solid porous catalyst. Internal surface is a part of an interface of phases which belongs to pores in particles of the catalyst or adsorbent. Other part of a surface belongs to an external (geometrical) surface of particles. At high porosity the internal surface can considerably (to 106 times) to surpass an external surface in the area. Interphase catalysis is an acceleration of chemical reactions in heterophase systems at addition of a small amount of substance which is called the catalyst of phase transfer. The effect is reached due to acceleration of transfer of molecules between various phases in heterophase systems. The greatest distribution was gained by heterophase systems of type water solution – organic solution or a solid phase – organic solution. The interphase catalysis allows to increase significantly the yield and purity of target products, and also to raise regio-and stereoselectivity of chemical reactions between molecules from different phases. The interphase catalysis is widely used for implementation of nucleophilic and radical-anionic reactions in thin organic synthesis.

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Intradiffusion area is the range of parameters within which the intra-diffusion regime of the reaction proceeds. Intradiffusion mode is the mode of reaction in which the diffusion of reactants in the pores of a heterogeneous catalyst has a significant effect on the rate of the catalytic reaction. Diffusion difficulties lead to a significant concentration gradient within the catalyst granule. At intradiffusion mode, the apparent activation energy is the arithmetic mean value of the true activation energy and the activation energy of the diffusion. Intrakinetic area is the range of parameters within which the intrakinetic mode of course of reaction is carried out. The intra kinetic mode is an implementation of catalytic reaction in conditions when the speed of reaction is small in comparison with the speed of diffusion of reagents in the pores of the solid catalyst. In particles of the heterogeneous catalyst there are no gradients on concentration. At the intrakinetic mode the true kinetic regularities characteristic of this chemical reaction are observed. Intramolecular catalysis is a special type of catalytic reactions when acceleration of chemical reaction in some functional group of a molecule results from catalytic action of other functional group which is in structure of the same molecule. The intrinsic inhomogeneity is the inhomogeneity of the adsorption centers, due solely to the properties of the adsorbent. For example, the strength of chemisorption may depend on the type of crystalline faces present on the surface of the adsorbent. Introduction is a type of reaction in metal complex compounds, when one ligand is built in by the bond between the metal and another ligand. Example: introduction of a CO ligand on a metal-alkyl bond to form an acyl group. Isomerization is a catalytic process for obtaining high-octane components of commercial gasoline from low-octane oil fractions. The reaction rearranges the carbon skeleton of a molecule without adding or removing anything from the original material. As a result of the process, linear hydrocarbons are isomerized into branched hydrocarbons. Heterogeneous acid catalysts of various types are used: aluminoplatinum fluorinated catalysts (high-temperature isomerization, 360-440°C), zeolite catalysts (mediumtemperature isomerization, 250-300°C); alumina promoted by chlorine, or sulfated zirconium oxide (low-temperature isomerization, 120-180°C). Isomerism is the phenomenon of the existence of compounds that have the same composition (the same molecular formula), but a different structure. Iso-octane is a hydrocarbon molecule (2,2,4-trimethylpentane) with exccellent antiknock characteristics on which the octane number of 100 is based. Isostere of adsorption is the dependence of equilibrium pressure of an adsorbtive in a gas phase from temperature measured at an adsorption constant. K Kerogen is a complex carbonaceous (organic) material that occurs in sedimentary rocks and shales; generally insoluble in common organic solvents. Kerosene (kerosine) is a fraction of petroleum that was initially sought as an illuminant in lamps; a precursor to diesel fuel.

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Kerosene type jet fuel is a distillate used for aviation turbine power units. It has the same distillation characteristics between 150°C and 300°C (generally not above 250°C) and flash point as kerosene. The kinetic mode is implementation of catalytic reaction in conditions when the kinetics of process isn't complicated by diffusion processes (for example, the intra kinetic mode for the heterogeneous catalyst). L Laminar flow is the flow of a liquid or gas, in which particles of matter move in the direction of flow in an orderly and constant linear velocity. An increase in the flow rate or a decrease in the viscosity of the medium can lead to transition of a laminar flow into the turbulent flow. The Langmuir-Hinshelwood mechanism is the mechanism of a heterogeneous catalytic reaction, in which the slowest stage is the reaction between chemisorbed particles. In this case, the adsorption (chemisorption) of the reagents and the desorption of the products are considered as fast equilibrium processes. Leaching is the transition into a solution of one or more components of a solid substance when it interacts with a solvent. The selectivity of the leaching of a particular component is determined by the solubility of the compounds, the chemical properties of the solvent, and the structure of the solid. Leaded gasoline is gasoline containing tetraethyl lead or other organometallic lead antiknock compounds. Lean gas is the residual gas from the absorber after the condensable gasoline has been removed from the wet gas. Lean oil is the absorption oil fed to absorption towers in which gas is to be stripped. After absorbing the heavy ends from the gas, it becomes fat oil. When the heavy ends are subsequently stripped, the solvent again becomes lean oil. Lewis acid is a substance capable of attaching an electronic pair. Lewis Acid Center (LAC) is a group of atoms in a substance that can attach an electron pair. For example, a coordinatively unsaturated aluminum atom on the surface of Al2O3. Lewis base is the substance capable to give (to donate) electronic pair. The lifetime, τ, is the lifetime of the molecule, which is destroyed by the firstorder kinetics, the time of the molecule concentration decrease by 1/e from its initial value. The lifetime is equal to the reciprocal of the rate constants of the first-order reactions leading to the death of the molecule. Time of life of particles in reactions not of the first order depends on initial concentration of substance. In this case it is called "observed time of life" or “death time”. In some cases use the half-decay time which is time of reduction of concentration of substance half from initial. The lifetime of adsorption is the average time during which the molecule is in the adsorbed state and corresponds to the time interval between the collision of the molecule with the surface of the adsorbent and desorption. Light hydrocarbons are hydrocarbons with molecular weights less than that of heptane (C7H16). Light oil are the products distilled or processed from crude oil up to, but not including, the first lubricating-oil distillate.

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Light petroleum is petroleum having an API gravity greater than 20º. Ligroine (Ligroin) is a saturated petroleum naphtha boiling in the range of 20 to 135°C (68 to 275°F) and suitable for general use as a solvent; also called benzine or petroleum ether. The limiting stage is the elementary stage in the complex process (consisting of several consecutive stages) which is characterized by the difference of chemical potentials, maximum for process, between the interacting reactionary groups. For simple and quite often for complex chemical processes the limiting stage can coincide with the speed ‒ defining (speed ‒ controlling) stage. The Liquefied Hydrocarbon Gases (LHG) are the hydrocarbonic gases or their mixtures with temperatures of boiling from -50 to 0°C compressed under pressure. The major LHG are propane, butane, isobutane, butylene of various structure and their mixture of different structure. They are made generally from associated petroleum gas, and also at oil refineries. Liquefied natural gas (LNG) is natural gas cooled to approximately –160°C under atmospheric pressure condenses to its liquid form called LNG. LNG is odourless, colourless, non-corrosive and non-toxic. Liquefied petroleum gases (LPG) are light paraffinic hydrocarbons derived from the refinery processes, crude oil stabilisation and natural gas processing units. They consist mainly of propane (C3H8) and butane (C4Hl0) or a combination of the two. They could also include propylene, butylene, isobutene and isobutylene. LPG are normally liquefied under pressure for transportation and storage. Localized adsorption is an adsorption in which the surface diffusion of adsorbed particles is impossible, or unlikely. This is due to the presence of a high energy barrier for the transition between neighboring adsorption centers. In some cases, localized adsorption leads to the ordering of adsorbate molecules in a twodimensional lattice. Low-Line/Low-Pressure Gas is a low-pressure (5 psi) gas from atmospheric and vacuum distillation recovery systems that is collected in the gas plant for compression to higher pressures. Low-temperature condensation is a technological process for processing associated petroleum gas to separate BFLH from a dry stripped gas. The technology is based on the separation of raw materials components with their gradual cooling and condensation: when cooling below -42°C, BFLH components become liquid, and the components of dry gas (methane and ethane) are separated in a gaseous state. Lubricants are hydrocarbons produced from distillate by-products; they are mainly used to reduce friction between bearing surfaces. They include all finished grades of lubricating oil, from spindle oil to cylinder oil, and those used in greases, including motor oils and all grades of lubricating oil base stocks. M Macrokinetics is the study of kinetic regularities of chemical reactions, under conditions when they are accompanied by heat transfer and mass transfer phenomena. Macropores are the pores with an effective size of more than 50 nm. A massive catalyst is a heterogeneous catalyst, consisting entirely of an active component, for example Raney nickel.

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Mass transfer is the diffusion of substance or convection resulting from distinction of concentration or electric potentials in the considered initial and final states. The mechanism of the chemical process is the set of all intermediates and transition states of the chemical process, which explains the transformation of the initial reagents into final products. Mercaptans are organic compounds having the general formula R-SH. Metagenesis is the alteration of organic matter during the formation of petroleum that may involve temperatures above 200°C (390°F). Mercury porometry is a method of porosimetry based on the property of liquid mercury not moisten (wet) the majority of solid bodies. The volume of mercury entering the pores is measured, depending on the applied pressure. The method can be used to determine the pore size in a wide range (from 3 nm to 400 μm). Mesopores are pores with an effective size of 2 nm to 50 nm. Methanation is a catalytic process of removing small amounts of carbon monoxide from a gas stream. It leads to the production of methane by the reaction CO + 3H2 → CH4 + H2O. Nickel supported on alumina is used as the catalyst. The process can be carried out at any pressure, typical process temperatures are 200-370°C. Methyl alcohol (methanol; wood alcohol) is a colorless, volatile, inflammable, and poisonous alcohol (CH3OH) traditionally formed by destructive distillation of wood or, more recently, as a result of synthetic distillation in chemical plants. Micellar catalysis is an increase in the rate of chemical reactions in the presence of micelles. This term is used even in cases where the acceleration of the reaction is caused by a simple change in the concentration of substances during the transition from solution to micelles. If the structure of micelles contains catalytically active functional groups, acceleration of reaction can be caused by true catalytic process, i.e. intermediate chemical interaction of reagents with the catalyst. Micelles are associates consisting of diphilic molecules (surface-active substances). The diphilic molecule contains a hydrophobic radical and a polar functional group, which determines the characteristic structure of the associates in the aqueous medium (direct micelles) or in a non-aqueous medium (reverse micelles). Micropores are pores with effective size less than 2 nm. The microspherical catalyst is the catalyst in the form of microspheres with a diameter from 20 to 200 microns used in a fluidized bed reactor. The moisture capacity of the carrier is the amount of solvent that is absorbed when the porous system is filled in a pre-dried carrier. Mineralization is the process of complete conversion of organic matter to carbon dioxide, water and other simple inorganic substances, depending on the heteroatom in the starting material. Mineral oil is the older term for petroleum; the term was introduced in the nineteenth century as a means of differentiating petroleum (rock oil) from whale oil which, at the time, was the predominant illuminant for oil. Minerals are naturally occurring inorganic solids with well-defined crystalline. Mineral seal oil is a distillate fraction boiling between kerosine and gas oil. Mineral wax ‒ from yellow to dark brown, solid substances that occur naturally and are composed largely of paraffins; usually found associated with considerable

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mineral matter, as a filling in veins and fissures or as an interstitial material in porous rocks. A mixed catalyst is a catalyst consisting of two or more components, each of which is catalytically active with respect to the reaction. Usually, in mixed catalysts, the components are in commensurate amounts. An increase in the activity of such catalysts can be achieved through the interaction of the components with the formation of a new more active phase. Example: iron-molybdenum catalyst for the oxidation of methanol to formaldehyde has the highest activity at a ratio of iron and molybdenum oxides of 1.5: 1 (the phase of iron molybdate is formed). Modifier ‒ this term is used in asymmetric catalysis and means a chiral substance, without which the catalyst can not produce an optically active product. For example, the Raney nickel catalyst is capable of performing asymmetric hydrogenation reactions if an optically active isomer of tartaric acid is present on its surface. The modifying additive – see the promoter. Molecular diffusion is a spontaneous process of transfer of substance of area with high concentration to the area with low concentration. Molecular diffusion takes place in gases, liquids, and also when filling of pores of solid substance with gas or liquid if the pore sizes are larger than the length of a free run of a molecule. If the last condition isn't satisfied, so-called Knudsen diffusion is realized. Molecular sieve effect is the effect of the effect of the pore size in the catalyst structure on the selectivity of the catalytic reaction, based on the different availability of the internal space of porous materials for molecules differing in size. A typical example is the catalysis on zeolites and other microporous materials, when the pore sizes are comparable to the dimensions of the molecules. The selectivity of the process may depend on the size of the reagents, products or transition state of the reaction. Example: the cracking process on some zeolites is possible only in normal alkanes. Molecules of a larger size, for example, isoalkanes, are not cracked, as they cannot diffuse to active centers located in narrow pores of the zeolite. Monodisperse ‒ this term is applied to dispersed systems if particles of the same size are present in the dispersed phase. Monolayer adsorption is adsorption, in which all adsorbed molecules directly contact the surface of the adsorbent. Based on the limiting value of monolayer adsorption, the degree of filling of the surface is determined. A monomer is a component of a polymer, its structural unit, a molecule capable of polymerization or polycondensation. Usually contains one (olefins) or two (dienes) double bonds involved in the polymerization. Monomolecular adsorption is an adsorption in which one adsorption center can occupy only one molecule of adsorbate. Monomolecular adsorption reaches a limit when the monolayer is filled and can be described by the Langmuir adsorption theory. The morphology is geometrical features of a structure of solid substances, including a geometrical form and degree of crystallinity of particles of substance, and also a geometrical form of the agglomerates formed of primary particles and the presence in them of porous structure. Motor gasoline consists of a mixture of light hydrocarbons distilling between 35°C and 215°C. It is used as a fuel for land-based spark ignition engines. Motor gasoline may include additives, oxygenates and octane enhancers.

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Motor gasoline can be divided into two groups: ‒ unleaded motor gasoline: motor gasoline where lead compounds have not been added to enhance octane rating. It may contain traces of organic lead. ‒ motor gasoline with Pb added to enhance octane rating. They include motor gasoline blending components (excluding additives/oxygenates), e.g. alkylates, isomerate, reformate, cracked gasoline destined for use as finished motor gasoline. Motor octane method is a test for determining the knock rating of fuels for use in spark-ignition engines. Moving-bed catalytic cracking is a cracking process in which the catalyst is continuously cycled between the reactor and the regenerator. Multifunctional (polyfunctional) catalysis is a complex difficult multistage catalytic reaction with participation of the multifunctional (polyfunctional) catalyst. Multifunctional (polyfunctional) catalyst is a catalyst containing active centers with different functions. Such catalysts are effective in reactions with several intermediate stages, each of which requires catalytic centers of its own type. Multilayer adsorption is the adsorption, in which several layers of adsorbed molecules are formed. Only molecules from the first adsorption layer interact directly with the surface of the adsorbent, the remaining molecules are adsorbed above the previous layer. N Naphtha is a generic term used for low boiling hydrocarbon fractions that are a major component of gasoline. Aliphatic naphtha refers to those naphthas containing less than 0.1% benzene and with carbon numbers from C3 through C16. Aromatic naphthas have carbon numbers from C6 through C16 and contain significant quantities of aromatic hydrocarbons such as benzene (>0.1%), toluene, and xylene. Naphtha is a feedstock destined for petrochemical industry (e.g. ethylene manufacture or aromatics production). Naphtha comprises material in the 30°C and 210°C distillation range or part of this range. This term is also applied to refined, partly refined, or unrefined petroleum products and liquid products of natural gas, the majority of which distills below 240°C (464°F). Naphthenes are hydrocarbons (cycloalkanes, cycloparaffins) with the general formula CnH2n, in which the carbon atoms are arranged to form a ring. Natural gas comprises gases, occurring in underground deposits, whether liquefied or gaseous, consisting mainly of methane. It includes both “nonassociated” gas originating from fields producing hydrocarbons only in gaseous form, and “associated” gas produced in association with crude oil as well as methane recovered from coal mines (colliery gas). Natural gas liquids (NGL) are the hydrocarbon liquids that condense during the processing of hydrocarbon gases that are produced from oil or gas reservoir; see also natural gasoline. Natural gasoline is a mixture of liquid hydrocarbons extracted from natural gas suitable for blending with refinery gasoline. Natural gasoline plant is a plant for the extraction of fluid hydrocarbon, such as gasoline and liquefied petroleum gas, from natural gas.

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Negative catalyst ‒ see inhibitor. Non-activated adsorption ‒ the term emphasizes that adsorption (or chemisorption) is carried out without an activation barrier, in contrast to activated adsorption. Nondissociative adsorption is a variant of chemisorption, in which the adsorbed molecule does not undergo dissociation into fragments, in contrast to dissociative adsorption. An example of nondissociative adsorption is the adsorption of CO on metals and oxides. Non-localized adsorption is an adsorption in which adsorbed molecules are able to migrate along the surface of the adsorbent. Unlike localized adsorption, the energy barrier separating neighboring adsorption centers is either absent or insignificant in magnitude. Normal hydrocarbons are hydrocarbons of unbranched, linear structure of the chain. Nucleophilic catalysis is a catalytic reaction in which the catalyst is the Lewis base. Example: hydrolysis of acetic anhydride in an aqueous solution in the presence of pyridine. O Octane number is a measure of the detonation resistance of fuel, that is, the ability of the fuel to withstand self-ignition when compressed in the combustion chamber of a gasoline engine. A number indicating the relative antiknock characteristics of gasoline. The name comes from the fact that in the conventional scale of detonation resistance the number 100 is assigned to a normal octane. Oil (petroleum) is an oily liquid, usually brown to almost black, less often brownish-red to light orange, with a specific odor. It is a mixture of hydrocarbons of methane, naphthenic and aromatic series with an admixture of (usually minor) sulfur, nitrogen and oxygen compounds. The specific gravity is seldom below 0.7 and above 1, fluctuating usually in the range 0.82-0.89. The low specific gravity of oils (light oils) can be due to both their chemical character ‒ the predominant content of methane hydrocarbons and the fractional composition ‒ high content of gasoline. Heavy oils have a high specific gravity due to the high content of asphalt-resinous substances, the predominance of cyclic structures in the structure of hydrocarbons and the low content of easily boiling fractions (the initial boiling point sometimes exceeds 200ºC). The sulfur content of the oils is usually lower than 1%, but sometimes reaches 5 ‒ 5.5%. The amount of paraffins varies from trace amounts to 10% or more. Oil with the high content of paraffin differ in the increased freezing temperatures (it is higher than 0ºC also to + 20ºC), oil with the low content of paraffin stiffen at temperatures sometimes below ‒ 20 ºC. The maintenance of asphalt and resinous components and viscosity of heavy oil, as a rule, above, than that of light oil. Oil-absorption unit is a technological unit intended for the processing of associated petroleum gas ‒ separation of a wide fraction of light hydrocarbons and dry stripped gas. The principle of operation is the difference in the ability of hydrocar-

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bon gases to dissolve in oil media. Components of dry gas (mainly methane, as well as ethane) are not soluble, and components with more than 2 carbon atoms are dissolved. Oil-bearing characteristics – 1) the direct separation of liquid oil, 2) the impregnation of rocks with oil; 3) deposits of solid bitumens (asphalt, ozocerite); 4) release of combustible gas; 5) the presence of mud volcanoes; 6) an oil or bituminous smell emitted by the rock, sometimes only after a strong heating of it; 7) coloring of the gasoline or benzene extract of the determined rock. Oilbearing characteristics indicate the possible presence of oil in the rocks in the considered rocks of this area. Oil-bearing rocks are rocks impregnated with oil. Typically, oil impregnates well-porous rocks ‒ sands, sandstones, fossilized limestones, etc., creating from such rocks the industrial-oil-bearing horizons to be developed. Oil-bearing rocks are also clays, etc., dense rocks, but the oil in them is dispersed and slightly concentrated only in bends and crushed parts. The oil-bearing region is a set of several adjacent genetically linked structures with signs of oil or a set of similar oil deposits with similar oil-bearing suites. Oil recovery is a degree of completeness of oil recovery. Oil reservoir is a layer of rock, more or less impregnated with oil. Oil saturation of layer is the amount of the oil which is available in layer in relation to the total volume of pores, cavities and cracks in oil-containing rock. In natural conditions, oil saturates a small part of the pores, and larger ones. Small pores, due to the action of surface tension forces, are occupied by water. The more small pores, the more “buried” water in the layer. In some layers, the amount of this water is quite significant ‒ up to 40%. “Buried” water in the process of exploitation of the reservoir does not usually manifest itself, and the wells give waterless oil. Olefins ‒ it is a family of unsaturated hydrocarbons with one carbon-carbon double bond and the general formula CnH2n. Also see alkenes. Open pores are channels or cavities that communicate with the outer surface of the particle. Molecules from the surrounding space can freely penetrate into the open pores by diffusion. Ostwald's maturation is the process of increasing the particle size due to the transfer of matter from small particles to larger particles. Such mechanism is implemented in many processes, for example, at coarsening of sols, crystallization of soluble precipitates, increase in the sizes of deposited metal particles. Oxidative addition is a type of ligand binding reaction to a metal complex compound when a metal atom provides electrons to form a bond with a ligand. The initial complex should have two vacant positions in the coordination sphere, and the state of the central metal atom should be stable in oxidation states that differ by two units. In the oxidative addition reaction, many substances (H 2, HI, CH3I, etc.) enter. Oxidative dissociative adsorption ‒ this term indicates the direction of transfer of electrons from the adsorbent to the adsorbate during dissociative adsorption.

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Example: oxidative dissociative adsorption of Cl2 on metals leads to the formation of two surface Cl- ions. Oxygenate is an oxygen-containing compound that is blended into gasoline to improve its octane number and to decrease gaseous emissions. P Paraffins – it is a family of saturated aliphatic hydrocarbons (alkanes) with the general formula CnH2n+2. Paraffin waxes are saturated aliphatic hydrocarbons. These waxes are residues extracted when dewaxing lubricant oils. They have a crystalline structure which is more or less fine according to the grade. Their main characteristics are: they are colourless, odourless and translucent, with a melting point above 45°C. Particle density is the density of solid particles. Passivation is a method of protecting metal catalysts by means of a small controlled oxidation of the surface in an oxygen medium. The resulting oxide layer on the surface of metal particles prevents further oxidation of the metal. Penex process is a continuous, nonregenerative process for isomerization of C5 and/or C6 fractions in the presence of hydrogen (from reforming) and a platinum catalyst. Pentafining is a pentane isomerization process using a regenerable platinum catalyst on a silica-alumina support and requiring outside hydrogen. Peptization is a process that reverses coagulation, the destruction of aggregates in a dispersed system, for example, the destruction of the gel structure with the formation of sol. Petrol is a term commonly used in some countries for gasoline. Petroleum (crude oil) is a naturally occurring mixture of gaseous, liquid, and solid hydrocarbon compounds usually found trapped deep underground beneath impermeable cap rock and above a lower dome of sedimentary rock such as shale; most petroleum reservoirs occur in sedimentary rocks of marine, deltaic, or estuarine origin. Petroleum coke is a black solid by-product, obtained mainly by cracking and carbonising petroleum-derived feedstock, vacuum bottoms, tar and pitches in processes such as delayed coking or fluid coking. It consists mainly of carbon (90% to 95%) and has a low ash content. It is used as a feedstock in coke ovens for the steel industry, for heating purposes, for electrode manufacture and for production of chemicals. Petroleum natural gases are gases consisting of a mixture of gaseous hydrocarbons of the paraffin series (СnН2n+2): methane CH4 (sometimes up to 99%), ethane C2H6, propane C3H8, butane C4H10, with an admixture of nitrogen, carbon dioxide, hydrogen sulfide and gasoline vapors. Distinguish dry gas ‒ with a predominance of methane ‒ and fatty gas ‒ with a high content of heavy hydrocarbons. The phase transfer catalyst is a substance that facilitates the acceleration of reactions in heterophase systems by accelerating the transport of molecules between different phases in heterophase systems. For example, ammonium and phosphonium salts (or their organic analogues), as well as crown ethers, aliphatic ethers and other compounds serve as phase transfer catalysts for the most common systems of the

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type of water-organic solutions. The mechanism of action of the phase transfer catalysts depends on the phase in which the reaction takes place. Example: the process of nucleophilic substitution in alkyl halides proceeding in the organic phase is accelerated in the presence of ammonium cations NH4+, which are capable of transferring the inorganic anion from the aqueous phase to the organic phase. In some cases, the interfacial catalyst increases the solubility of the organic matter in the aqueous phase due to the effect of salting, for example, such an action has NH 4+X- salts during benzoin condensation. Phosphoric acid polymerization is a process using a phosphoric acid catalyst to convert propene, butene, or both, to gasoline or petrochemical polymers. Photoadsorption is adsorption, usually chemisorption initiated by ultraviolet, visible or infrared radiation absorbed by adsorbate or adsorbent. Photoadsorption often is considered as primary stage of heterogeneous photocatalytic reaction. However in some cases photocatalytic reaction is initiated not by adsorption on the surface of the photocatalyst. Example: photocatalytic oxidation of the chlorinated hydrocarbons. Photodesorption is a desorption caused by absorption of ultraviolet, visible or infrared radiation by an adsorbate or adsorbent. Photodesorption can be a step in the general mechanism of heterogeneous photocatalysis. Photodesorption is the reverse process of photoadsorption. For a specific system, both processes (or reactions) are caused by ultraviolet, visible or infrared radiation of the same wavelength range. A photoinitiator is an agent that initiates a corresponding chemical transformation under the influence of ultraviolet, visible or infrared radiation, and is spent in this transformation. The photocatalyst can also act as a photoinitiator, but it is not consumed in the chemical transformation. Photoinitiation is photo origination of the free radical, electron-hole pair or the ion capable to initiate chain reaction, for example polymerization, halogenation, and nitrosylation. Photocatalysis is the phenomenon of change of speed of chemical reaction or its initiation under the influence of ultra-violet, visible or infrared radiation in the presence of substance − the photocatalyst which absorbs light and participates in chemical transformations. Physical adsorption is adsorption, which is provided by weak physical interactions (usually due to van der Waals forces, dipole interactions, etc.) between adsorbent and adsorbate. Physical adsorption, in contrast to chemical adsorption, is completely reversible and is characterized by low values of Gibbs energy and heat of adsorption. For example, in the physical adsorption of gas molecules, the heat of adsorption often corresponds to the heat of condensation of the vapor into the liquid. Pitch is the nonvolatile, brown to black, semi-solid to solid viscous product from the destructive distillation of many bituminous or other organic materials, especially coal; has also been incorrectly applied to residua from petroleum processes where thermal decomposition may not have occurred. Platforming is a reforming process using a platinum-containing catalyst on an alumina base. The plasticizer is a substance that is introduced into the material to give it plastic properties.

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Poisoning is a decrease in the activity of the catalyst, which is caused by the interaction of the active sites of the catalyst with the catalytic poison present in the reaction mixture. There are reversible poisoning and irreversible poisoning. In reversible poisoning, the catalytic activity is restored to its original level after removal of the poison from the reaction mixture. In case of irreversible poisoning, for example due to strong adsorption of the poison on the active centers of the catalyst, the catalytic activity remains low even after removal of the poison from the reaction mixture. In this case, the catalytic activity can be recovered by regenerating the catalyst, or by complete chemical processing of the poisoned catalyst. Pollution is the introduction into the land water and air systems of a chemical or chemicals that are not indigenous to these systems or the introduction into the land water and air systems of indigenous chemicals in greater-thannatural amounts. Pollution of the catalyst is blocking of the active centers of the catalyst by the mechanical impurity which is contained in raw materials. In case of the heterogeneous catalyst mechanical impurity can also block porous system in granules of the catalyst and, thus, reduce degree of use of a surface. Polydisperse ‒ this term is applied to dispersed systems, if in a dispersed phase there are particles of unequal size. Polyforming is the thermal conversion of naphtha and gas oils into highquality gasoline at high temperatures and pressure in the presence of recirculated hydrocarbon gases. Polymerization is a chemical reaction (and also a corresponding technological process) for the formation of polymers from constituent parts ‒ monomers. The process of combining two or more unsaturated organic molecules to form a single (heavier) molecule with the same elements (monomers) in the same proportions as in the original molecule. The polymerization catalyst is a substance which excites ionic or coordination and ion polymerization. The role of the catalyst of polymerization consists in creation of the active centers on which growth of molecules of polymer is carried out. The nature of active centers determines the mechanism of the process, the kinetics of the elementary stages of the process, the molecular weight distribution of polymer molecules, and the spatial structure of the polymer formed. Thus, the polymerization catalyst, in contrast to the polymerization initiator, takes part not only in the polymerization excitation stage but also in all subsequent polymer chain growth stages. Polymers are organic substances that are long molecular chains composed of identical fragments ‒ monomers. Polymolecular adsorption is adsorption, in which several adsorbate molecules can be adsorbed on a single adsorption center. For example, the theory of BET adsorption is based on the assumption of polymolecular adsorption. Polynuclear hydroxocomplexes (PGA) are polymer multinucleated complex metal compounds containing bridging bonds of OH-hydroxide-ions. Polynuclear hydroxocomplexes are formed from amorphous and difficult-to-crystallize hydroxides in the process of hydrolysis of metal salts. Pores are cavities (emptiness) or channels in solid particles. It is commonly believed that the depth of the pores exceeds their width. There are open pores and closed pores.

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Pore size distribution is the statistical distribution of pore volume, depending on their size in the material under study. It is determined experimentally by the results of porosimetry or by calculation methods (by the adsorption isotherm). The pore size distribution affects the diffusion of the reactants and products in the solidphase catalyst particles. The pore volume is the total volume of all pores present in the solid material. Porometry is the determination of the pore size in a solid. Porometry provides information on the minimum and maximum pore size, the distribution of pores by size, and the average pore size in the sample. The main porometry methods are the adsorption method (pore size from 0.35 to 100 nm) and mercury porosimetry (pore size from 3 nm to 400 μm). Porosity is a share of the free volume which isn't occupied with catalyst granules in a layer from such granules. Porosity is the presence of pores or cavities in the material. Numerically, the porosity is expressed as the ratio of the pore volume in the particle of the substance to the total volume of this particle. Thus, the porosity can vary from 0 (total absence of pores) to ~ 1, and a strict value of 1 is unattainable. In industrial catalysts, the porosity is 0.2-0.8. Porous structure of substance is structure of porous space, i.e. a spatial arrangement and the sizes of pores in substance particles. Possible reserves are reserves where there is an even greater degree of uncertainty but about which there is some information. Post-adsorption is adsorption after preliminary irradiation of the photocatalyst in a vacuum. Potential reserves are reserves based upon geological information about the types of sediments where such resources are likely to occur and they are considered to represent an educated guess. Pour point is the lowest temperature at which oil will pour or flow when it is chilled without disturbance under definite conditions. Precipitation is the process of formation of a solid precipitate in a solution. The precipitation of the solution can be caused by evaporation of the solution, a decrease in the solubility of the substance when the solvent is replaced, a chemical reaction with the transfer of the substance to a less soluble compound. Precipitation is widely used as a sufficiently universal method in the synthesis of various catalysts. For the technology of catalyst preparation, the rate of deposition, temperature and the presence of impurity ions, which may be a catalytic poison, are of great importance. Precipitator is a substance which addition to solution causes formation of a deposit. The added substance can interact with the dissolved substance with formation of insoluble compounds, or change acidity of the medium or polarity of solvent. A precursor is a weak adsorption complex or a special nonequilibrium state of the molecule, preceding the strong chemisorption of this molecule. The predecessor is an initial or intermediate chemical compound which at the subsequent stages of synthesis passes into target substance. Preheater is the exchanger used to heat hydrocarbons before they are fed to a unit.

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Pressure-regulating valve is a valve that releases or holds process-system pressure (that is, opens or closes) either by preset spring tension or by actuation by a valve controller to assume any desired position between fully open and fully closed. Primary particles are particles of the smallest size, which can be identified as independent discrete constituents of the substance. Since the resolution of methods can depend strongly on a particular sample, usually when specifying the primary particles, it is also necessary to indicate the identification method (for example, transmission or scanning electron microscopy). Probability of sticking is probability that the molecule is adsorbed after collision with the surface of adsorbent. The probability of sticking average on all possible impacts happening to different angles and speeds corresponds to sticking coefficient. The production rate of a well is the amount of production that is obtained from a well in a unit of time. Oil always has as its companion the oil gas released from the oil when it leaves the surface. Therefore, distinguish oil production and gas production. Some wells produce oil with water, sometimes in the form of an emulsion. For these wells, the water production rate and the emulsion discharge are distinguished in addition to the oil and gas production rate. In oil field practice, oil, emulsion and water flow rates are usually measured in tons per day, and gas production in cubic meters per day. Sometimes the water flow rate is expressed as a percentage of all the liquid produced by the well. Product yield is the relation of amount of the reagent which has turned into this product to the total of reagent given on a reactor entrance. The amount of reagent can be measured in various units (mol number, weight, etc.). A promoter is a substance added in small amounts to a catalyst in order to improve its activity, selectivity or stability. At the same time, the improvement in the properties of the catalyst is much greater than that which could be obtained as a result of the independent action of the promoter itself. Promoters can be a variety of substances. Distinguish textural promoters (have a physical effect on the catalyst) and structural promoters (change the chemical properties of the catalyst). Propane-propylene fraction is a mixture of gaseous hydrocarbons with the number of carbon atoms 3, formed in the course of catalytic cracking during oil processing. Proved reserves are mineral reserves that have been positively identified as recoverable with current technology. The pulse reactor is a flow reactor operating in a pulsed mode. It is used in laboratory studies to study fast processes. In a pulsed reactor, a carrier gas stream is continuously fed through the catalyst, into which a stream of reagents is periodically added in the form of a short pulse. After each pulse, the reaction products can be analyzed, or the changes that have occurred to the catalyst are studied. Pyrolysis is a thermal process of decomposition of hydrocarbon feedstock to produce ethylene, propylene, benzene, butadiene, hydrogen and a number of other products. Pyrolysis gasoline is a by-product from the manufacture of ethylene by steam cracking of hydrocarbon fractions such as naphtha or gas oil. Pyrophoric Iron Sulfide is a substance typically formed inside tanks and processing units by the corrosive interaction of sulfur compounds in the hydrocarbons

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and the iron and steel in the equipment. On exposure to air (oxygen) it ignites spontaneously. Q Quench oil is oil injected into a product leaving a cracking or reforming heater to lower the temperature and stop the cracking process. R Radiation catalysis is a change in the rate of a chemical reaction under the action of ionizing radiation in the presence of a radiation catalyst. When using ionizing radiation, from vacuum ultraviolet to higher energies, the phenomenon of photocatalysis does not differ from the phenomenon of radiation catalysis. In connection with non-selective absorption of ionizing radiation, it is possible to excite all participants in the reaction (both reagents and catalysts). Thus, the phenomenon designated as "radiation catalysis" includes both direct radiation and catalytic processes. Raffinate is the product resulting from a solvent extraction process and consisting mainly of those components that are least soluble in the solvents. The product recovered from an extraction process is relatively free of aromatics, naphthenes, and other constituents that adversely affect physical parameters. Reaction speed is the number of acts of chemical transformation for a unit of time carried to unit of volume of reactionary mixture (in case of homogeneous reaction) or to surface unit of area (in case of heterogeneous reaction). Reactor is the vessel in which chemical reactions take place during a chemical conversion type of process, usually defined by the nature of the catalyst bed, e.g., fixed-bed reactor, fluid-bed reactor and by the direction of the flow of feedstock, e.g., upflow, downflow. Reactive adsorption is dissociative adsorption, in which one molecule fragment is attached to the adsorbent, and the second ‒ to another adsorbed molecule. Reactive desorption is an associative desorption, the reverse process to reactive adsorption. The reactor of periodic action is a hermetically closed capacity where reactionary mixture and the catalyst are placed. After certain time process is stopped for extraction of products. As during process the reactor remains hermetically closed, partial pressure of substances in the reactor can change considerably at course of reactions. The reactor productivity is the quantity of the obtained product in unit of time referred to volume (sometimes to weight) of the reactor. The reactor with the ascending stream of particles of the catalyst is the reactor representing a vertical strut in which from below the two-phase stream from gaseous reagents and solid particles of the catalyst moves up. Usually use a stream with the increased relation of solid substance to gas as gas rises up quicker, than catalyst particles. Reactors of this kind apply, for example, in processes of cracking of hydrocarbons on the zeolite catalysts, while the time of contact of reagents with the catalyst makes 5-7 sec.

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Reboiler is an auxiliary unit of a fractionating column designed to supply additional heat to the lower portion of the column. Recombination ‒ in the case of photocatalysis, the term means the disappearance of free electrons and holes due to the transition of electrons from the conduction band to the valence band. Recombination can also occur as a result of the interaction of trapped electrons and holes or electrons and holes inside the forbidden band or because of the influence of impurities or defects in the crystal structure. The rate of recombination determines the steady-state concentration of nonequilibrium photocarriers in continuously irradiated solid photocatalysts. Thus, recombination determines the rates and quantum yields of most heterogeneous photocatalytic reactions. Rectification is the process and technology of separation of substances based on gradual evaporation and condensation of vapors. Recycle gas is a high hydrogen-content gas returned to a unit for reprocessing. Recycle stock is the portion of a feedstock that has passed through a refining process and is recirculated through the process. Recycling is the use or reuse of chemical waste as an effective substitute for commercial products or as an ingredient or feedstock in an industrial process. Reduced crude is a residual product remaining after the removal by distillation of an appreciable quantity of the more volatile components of crude oil. Reductive dissociative adsorption is the direction of electron transfer from adsorbate to adsorbent under dissociative adsorption. The refinery is an oil refinery. Refines oil into fuels, oils, and also produces petrochemical raw materials ‒ straight-run gasoline, liquefied gases, propylene, butane-butylene fraction, aromatic compounds, etc. Refinery feedstocks are the processed oil destined for further processing (e.g. straight run fuel oil or vacuum gas oil) excluding blending. With further processing, it will be transformed into one or more components and/or finished products. This definition also covers returns from the petrochemical industry to the refining industry (e.g. pyrolysis gasoline, C4 fractions, gasoil and fuel oil fractions). Refinery gas (not liquefied) includes a mixture of non-condensable gases mainly consisting of hydrogen, methane, ethane and olefins obtained during distillation of crude oil or treatment of oil products (e.g. cracking) in refineries. It also includes gases which are returned from the petrochemical industry. Refining is the process(es) by which petroleum is distilled and/or converted by application of a physical and chemical process to form a variety of products. Reflux is the portion of the distillate returned to the fractionating column to assist in attaining better separation into desired fractions. Reformate is an upgraded naphtha resulting from catalytic or thermal reforming. Reformed gasoline is gasoline made by a reforming process. Reforming of gasoline oil fractions is the thermal or catalytic conversion of petroleum naphtha into more volatile products of higher octane number. I.e. it is a process which is carried out to increase the octane number in gasoline fractions with a boiling point of 80-180°C (naphtha). In the process of reforming, alkane molecules undergo rearrangement without changing the number of carbon atoms in the mole-

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cule (isomerization, dehydrogenation and dehydrocyclization reactions). So it represents the total effect of numerous simultaneous reactions such as cracking, polymerization, dehydrogenation, and isomerization. Bifunctional catalysts containing active centers of acidic and dehydrogenating type, for example, Pt/Al 2O3, are used. Reformulated gasoline (RFG) is gasoline designed to mitigate smog production and to improve air quality by limiting the emission levels of certain chemical compounds such as benzene and other aromatic derivatives; often contains oxygenates. Regeneration is the treatment of the deactivated catalyst under conditions other than the reaction one. Regeneration is carried out in order to completely or partially restore the catalytic activity. In a catalytic process it is the reactivation of the catalyst, sometimes done by burning off the coke deposits under carefully controlled conditions of temperature and oxygen content of the regeneration gas stream. Relative catalytic activity is a value determined to compare the activity of several catalysts when they interact with a reaction mixture of the same composition. Usually compare time demanded for achievement of the same degree of transformation of reactionary mixture on different catalysts. An alternative way is comparison of temperature at which various catalysts give identical conversion at the same time of reaction. The method of relative catalytic activity is applicable for a number of similar catalysts when the mechanism of catalytic reaction doesn't change. Renewable energy sources are solar, wind, and other nonfossil fuel energy sources. Research octane method is a test for determining the knock rating, in terms of octane numbers, of fuels for use in spark-ignition engines. The reverse spillover is the transfer of adsorbed particles from the carrier to the active component in the supported (deposited) catalyst as a result of surface diffusion. Reserves are well-identified resources that can be profitably extracted and utilized with existing technology. Residuum (resid; pl. residua) is the residue obtained from petroleum after nondestructive distillation has removed all the volatile materials from crude oil, e.g., an atmospheric (345ºC, 650°F) residuum. Resins are that portion of the maltenes that is adsorbed by a surface-active material such as clay or alumina; the fraction of deasphaltened oil that is insoluble in liquid propane but soluble in n-heptane. Resource is the total amount of a commodity (usually a mineral but can include nonminerals such as water and petroleum) that has been estimated to be ultimately available. A rock is a mineral mass of more or less constant composition and structure, usually consisting of several minerals, sometimes from one mineral (for example, gypsum), and is involved in the structure of the earth's crust. The rocks are divided into three large groups according to their origin: magmatic, sedimentary and metamorphic. S Scrubbing is purification of a gas or liquid by washing it in a column. Sedimentary rocks are rocks that are the products of the destruction of any rocks, the vital activity of organisms and the loss of mineral particles from the aquat-

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ic or air environment and their subsequent compaction and change ‒ in all cases at the pressure and temperature peculiar to the surface parts of the earth's crust. Self-poisoning is a deactivation of the catalyst in case the product of catalytic reaction is an inhibitor or catalytic poison. Selective chemisorption is a method for determining the surface area of an active component in supported metallic catalysts. The method is based on the selective chemisorption of probe molecules (H2, CO, etc.) on the metal surface. In this case, the conditions are selected so that the probe molecules are not adsorbed on the surface of the carrier. Selective poisoning is a method of increasing the selectivity of a catalyst in the presence of a catalytic poison that has a selective effect on the active centers of the catalyst. Example: selective poisoning of a silver catalyst with halogens results in the complete oxidation reaction of ethylene being suppressed to a greater degree than the formation of ethylene epoxide. Selectivity of the catalyst is the reagent share (in %) which has turned into a target product, to a share of the reacted reagent. It shows degree in which the catalyst is capable to accelerate reaction with formation of a target product instead of the side (undesirable) reaction. Depending on a way of calculation distinguish integrated and differential selectivity. The semiconductor is a material which conductance increases exponentially in case of increase in temperature owing to thermal generation of the free charge carriers under the Van Hoff law. Energy of the forbidden band of the intrinsic semiconductor can be about 2 eV. The intrinsic semiconductor represents material with insignificant defect concentrations and impurity in which thermal excitation leads to interzonal generation both electrons, and holes with identical concentration of both types of carriers. This condition requires small energy of the forbidden band of the semiconductor. In process of growth of crystals these materials are doped by trace quantities of other elements for creation of the areas of n-or p-types. The n-type semiconductor is a material in which electrons are the main carriers because of presence of small donor intrinsic defects and/or impurity in a lattice. The p-type semiconductor is a material in which holes are the main carriers due to the presence of small acceptor intrinsic defects and/or impurities in the lattice. The presence of defects and impurities (doping) in n- or p-type semiconductors leads to the appearance of semiconductor properties for materials having a wider forbidden band than for intrinsic semiconductors. For example, ZnO and TiO2 having the forbidden band 3 eV behave as n-type semiconductors. In case of contiguity of the n-areas and p-types there is a transition sending current to one side and prevents a reverse current forming the diode. Sibunit is the carbon ‒ carboneous composite material obtained by oxidizing processing of the system consisting of pyrolitic carbon and soot. The variation of the sizes of pores and specific surface area over a wide range is possible. Sibunit finds broad application, including it is used as the carrier for preparation of catalysts. Sintering is an accretion (fusion) of small crystals with formation of agglomerates of various size. At the same time there is a disorder consolidation of structure. At sintering, unlike crystallization, the unstable and disorder structure is formed.

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Sintering is always followed by simultaneous decrease in specific surface area and volume of pores that leads to irreversible deactivation of the catalyst. Accelerated sintering of catalysts can be caused by overheating in industrial devices. Coked sections on the surface of heterogeneous catalysts also tend to be sintered due to overheating. The size of the pore is the distance between the opposite walls of the pore. The skeleton catalyst is a highly disperse metal catalyst obtained by leaching from alloys. The first step in the preparation of the skeletal catalyst is the preparation of an alloy of the active component with aluminum (or other reactive metal). In the second stage, the aluminum is removed from the alloy by the action of an alkali. This results in the formation of a highly disperse metal phase of the active component. Advantages of skeletal catalysts are high mechanical strength and high thermal conductivity. The most frequently used skeletal catalyst is Raney nickel. Solvent extraction is the separation of materials of different chemical types and solubilities by selective solvent action. Sour gas is natural gas that contains corrosive, sulfur-bearing compounds such as hydrogen sulfide and mercaptans. Sour crude oil is crude oil containing an abnormally large amount of sulfur compounds; see also Sweet crude oil. Specific acid-base catalysis is a catalytic reaction which velocity is proportional to the concentration of protons H+ or hydroxide ions OH-. Such regularity is observed in case transfer of H+ or OH- to a molecule of reagent is carried out quickly and precedes the limiting stage. At the same time the speed of catalytic reaction doesn't depend on nature the catalyst (at constant pH). Specific catalytic activity (SCA) is the catalytic activity per unit surface of a solid phase catalyst. In some cases, the specific catalytic activity is determined per unit surface area of the active component. Specific productivity of the reactor is the amount of product formed per unit time in a unit of reactor volume. This value is often used to compare the efficiency of industrial reactors. The specific surface area (specific surface) is the surface area related to the mass of the corresponding phase. As adsorbents and catalysts substances with specific surface area from ~ 10 m2/g to ~ 1,000 m2/g are applied. Specific volume of pores is the volume of pores in a solid, per unit mass. Spent catalyst is the catalyst that has lost much of its activity due to the deposition. Spillover is a transfer of adsorbed particles from the active component to the carrier. It occurs as a result of surface diffusion of particles formed as a result of dissociative adsorption on the active component. The speed-defining stage is a stage which parameters are included into expression for resultant speed gross ‒ reactions. Sol is a dispersed system formed by particles of a liquid or solid, which are distributed in a liquid or gaseous dispersion medium. The particle size of the dispersed phase is from 1 to 100 nm. The sol-gel method is a method for synthesizing catalysts and adsorbents. Includes a number of consecutive stages: hydrolysis of the starting material in the

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solution, the formation of low molecular weight complexes and their further conversion to sol, the formation of a gel-like structure of the sol particles, the aging of the gel, the drying of the gel. The advantage of the sol-gel method is the ability to control the composition and microstructure of the porous body at the molecular level, which ensures homogeneity of chemical, physical and morphological properties in the resulting material. Speed (TON) is the number of acts of catalytic transformation at one active center of the catalyst during the catalytic reaction. The number of transformations characterizes the total activity of the catalyst during its entire service life. In photocatalysis, this is the ratio of the number of acts of photoinduced transformations over a certain period of time to the number of active centers or photocatalytic centers in the main state. Spray drying is a method for formation of particles by dispersion of suspension or solution in hot air. Such way allows to replace with one operation stages of filtering, drying and formation, however demands big expenses of energy. Spray drying is used, for example, in the manufacture of a microsphere catalyst. Stabilization is a process for separating the gaseous and more volatile liquid hydrocarbons from crude petroleum or gasoline and leaving a stable (less-volatile) liquid so that it can be handled or stored with less change in composition. Stabilization of condensate is a technological process for the processing of gas condensate, consisting in the isolation of light gases (methane, ethane and a wide fraction of light hydrocarbons) from it to obtain a stable condensate and a number of other products. Stable natural gasoline is a product of gas condensate stabilization. A mixture of liquid hydrocarbons of different structures, which are gasoline-kerosene fractions of petroleum. The stationary mode of catalysis is a method for carrying out a catalytic reaction, in which the properties of the system remain constant in time at each point of the reaction space. Such unchanged properties can be, for example, the composition of the reaction mixture, the reaction rate, the surface state of the catalyst. Typically, in a stationary mode, flow reactors operate. In contrast, the pulsed and static reactors operate in a non-stationary mode. Steam conversion of carbon monoxide is the CO reaction with steam, which products are hydrogen and carbon dioxide are used for increase in amount of hydrogen in synthesis ‒ gas. The reaction is thermodynamically reversible, so the final stage of the reaction is attempted at a minimum temperature to increase the yield of hydrogen. In a number of cases, the reverse reaction of the reduction of CO 2 by hydrogen is used to reduce the H2/CO ratio in the synthesis gas. Steam conversion of hydrocarbons is a catalytic process of synthesis gas production from hydrocarbons (methane, propane-butane fraction, etc.) and water vapor. The process is carried out on the modified nickel catalysts at temperatures of 600 ‒ 800°C and characterized by a strong endothermic effect. Steam conversion of hydrocarbons is the main way to produce hydrogen for ammonia production. Steam cracking is a conversion process in which the feedstock is treated with superheated steam. Stereoregular polymers are polymers with a clearly structured position of the links in space and relative to each other.

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Straight-run gasoline (naphtha) is a product of primary distillation of oil, fraction of hydrocarbons of a normal structure with number of atoms of carbon usually from 5 to 9 and temperatures of boiling to 180°C. It is gasoline produced by the primary distillation of crude oil. It contains no cracked, polymerized, alkylated, reformed, or visbroken stock. It is important raw materials for the petrochemical industry. Straight-run products are products obtained from a distillation unit and used without further treatment. Stripping is the removal (by steam-induced vaporization or flash evaporation) of the more volatile components from a cut or fraction. The structure of the catalyst is the chemical structure of the substances constituting the catalyst. For solid phase catalysts, this term implies, in particular, the features of the chemical structure of the surface of a solid. Structurally insensitive reactions are reactions for which the specific catalytic activity does not depend on the size of the catalytically active phase. For example, the majority of reactions of hydrogenation with participation of metal catalysts are structurally insensitive. Structurally sensitive reactions are reactions for which the specific catalytic activity depends on the size of the catalytically active phase. Typical examples are hydrogenolysis and isomerization reactions of hydrocarbons on metal catalysts. Reactions proceed at multicenter adsorption of hydrocarbons on a surface of an active component that demands presence of a certain geometry of an arrangement of atoms of metal on the surface of the catalyst. Reducing the size of the particles of the active component (usually less than 2-3 nm) or the formation of alloys disrupts the arrangement of atoms on the surface, which leads to a sharp decrease in the rate of structurally sensitive reactions. Structural promoter is a substance added in small amounts to the catalyst in order to modify the chemical properties of the active component. The effect of the structural promoter can be associated, for example, with the creation of defects in the crystal lattice or a change in the electronic structure of the catalyst, which affects the strength of chemisorption. Unlike the texture promoter, the structural promoter changes the activation energy of the process or the isotherm of adsorption of any substance involved in the process. The structural promoter is, for example, potassium oxide as part of an iron catalyst for the synthesis of ammonia (affects the chemisorption of hydrogen). Substitute natural gas is a high calorific value gas, manufactured by chemical conversion of a hydrocarbon fossil fuel. It is chemically and physically interchangeable with natural gas and is usually distributed through the natural gas grid. The main raw materials for manufacture of substitute natural gas are: coal, oil and oil shales. Substitute natural gas is distinguished from other manufactured gases by its high heat value (above 8,000 kcal/m3) and by its high methane content (above 85%). Substitute natural gas produced by synthesis from fuels other than coal-based should also come from other sources. Sulfuric acid alkylation is an alkylation process in which olefins (C3, C4, C5) combine with iso-butane in the presence of a catalyst (sulfuric acid) to form branched chain hydrocarbons used especially in gasoline blending stock.

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Sulfuric acid treating is a refining process in which unfinished petroleum products such as gasoline, kerosene, and lubricating oil stocks are treated with sulfuric acid to improve their color, odor, and other characteristics. Synthesis gas generation process: a noncatalytic process for producing synthesis gas (hydrogen and carbon monoxide) from gaseous or liquid hydrocarbons Sulfurization is combining sulfur compounds with petroleum lubricants. Suspension is a system with the liquid dispersive medium and a solid disperse phase with a size of particles of a disperse phase more than 10 μm. Suspension polymerization is the polymerization of an emulsion of a liquid monomer (its droplets immiscible with the medium, usually water) stabilized with water-soluble organic substances or inorganic salts to form a polymer slurry, i.e., a slurry of a solid in a liquid medium. The polymerization initiator is soluble in the monomer. The growth of the polymer chain itself occurs in the drops of the monomer. Suspensoid catalytic cracking is a nonregenerative cracking process in which cracking stock is mixed with slurry of catalyst (usually clay) and cycle oil and passed through the coils of a heater. Sweated wax is a crude wax freed from oil by having been passed through a sweater. Sweating is the separation of paraffin oil and low-melting wax from paraffin wax. Sweetening ‒ this term refers to the processes that either remove obnoxious sulfur compounds (primarily hydrogen sulfide, mercaptans, and thiophens) from petroleum fractions or streams, or convert them, as in the case of mercaptans, to odorless disulfides to improve odor, color, and oxidation stability. It is the process by which petroleum products are improved in odor and color by oxidizing or removing the sulfur-containing and unsaturated compounds. Sweet crude oil is a crude oil containing little sulfur; see also Sour crude oil. Switch loading is the loading of a high static-charge retaining hydrocarbon (i.e., diesel fuel) into a tank truck, tank car, or other vessel that has previously contained a low-flash hydrocarbon (gasoline) and may contain a flammable mixture of vapor and air. Syndiotactic polymer is a polymer in which the orientation of the side fragments of the molecular chain relative to the axis of the chain is strictly alternated: each subsequent fragment is oriented in the opposite direction from the previous one. Synthetic crude oil (syncrude) is a hydrocarbon product produced by the conversion of coal, oil shale, or tar sand bitumen that resembles conventional crude oil; can be refined in a petroleum refinery. T Tableting is a method of forming powders by squeezing them under a press to form particles of the desired shape (tablets, rings, etc.). In many cases, the addition of plasticizers to the initial powder is required. Tail gas is the lightest hydrocarbon gas released from a refining process.

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Tar is the volatile, brown to black, oily, viscous product from the destructive distillation of many bituminous or other organic materials, especially coal; a name used for petroleum in ancient texts. Tertiary structure is the three-dimensional structure of a molecule. Tetraethyl lead (TEL) is an organic compound of lead, Pb(CH3)4 which, when added in small amounts, increases the antiknock quality of gasoline. The texture of the catalyst is the geometry of the porous space in the particles of solid-phase catalyst. The texture promoter is an inert substance that is present in the heterogeneous catalyst in the form of fine particles and prevents the sintering microcrystals of active phase. The texture promoter physically separates the catalyst particles, as a result of which their fusion slows down during the operation of the catalyst. As texture promoters, substances with a very high melting point (Al 2O3, SiO2, ZrO2, Cr2O3, TiO2) are used. Unlike the structural promoter, the texture promoter does not affect the activation energy of the catalytic reaction. The texture promoter is, for example, alumina in the iron catalyst for ammonia synthesis. Thermal cracking is a non-catalytic cracking of hydrocarbons. It flows in the absence of a catalyst at high temperature through a free-radical mechanism. It is a process of decomposition of hydrocarbons of heavy fractions of oil under treating of high temperatures. The predominant process is the cleavage of the C-C bond at the β-position with respect to the carbon atom having an unpaired electron. This causes high yields of ethylene during thermal cracking. Process of thermal cracking of vacuum gasoil, black oil or tar has received the name viscosity breaking. Thermal polymerization is a thermal process to convert light hydrocarbon gases into liquid fuels. Thermal process is any refining process that utilizes heat, without the aid of a catalyst. Thermal reforming is a process using heat (but no catalyst) to effect molecular rearrangement of low-octane naphtha into gasoline of higher antiknock quality. Thermal stability (thermal instability) is the ability (inability) of a liquid to withstand relatively high temperatures for short periods of time without the formation of carbonaceous deposits (sediment or coke). Thermofor catalytic cracking is a continuous, moving-bed catalytic cracking process. Thermofor catalytic reforming is a reforming process in which the synthetic, bead-type catalyst of coprecipitated chromia (Cr2O3) and alumina (A12O3) flows down through the reactor concurrent with the feedstock. Thermal decomposition is the chemical decomposition of substances at elevated temperatures without the participation of gaseous compounds from the surrounding atmosphere. Thermochemical activation is a thermal treatment of solid substance in nonequilibrium conditions with formation of the metastable structures having the increased energy and considerable reactionary ability. As a result of thermochemical activation some elements of structure in a steady crystal lattice are removed, or are replaced with foreign structures which aren't peculiar to initial substance. Time of contact is time during which reactionary mixture contacts to the catalyst. For flowing reactors time of contact is determined by division of free volume of the reactor into the volumetric flow rate of initial reactionary mixture.

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Topped crude is petroleum that has had volatile constituents removed up to a certain temperature, e.g., 250°C (480ºF) topped crude; not always the same as a residuum. Topping is the distillation of crude oil to remove light fractions only; differs from distillation in the manner in which the heat is applied. Tower is an equipment for increasing the degree of separation obtained during the distillation of oil in a still. Trace element are those elements that occur at very low levels in a given system. The transition diffusion region is an intermediate range of parameters in which molecular diffusion and Knudsen diffusion have approximately equal effects on the catalytic reaction. The majority of reactions with participation of the catalysts possessing a large specific surface in transitional diffusive area. The position of the boundary of the transition region is affected by a number of parameters, for example, the composition of the reaction mixture, the pressure in the gas phase, the pore size distribution, etc. Traps are sediments in which oil and gas accumulate from which further migration is prevented. Treatment is any method, technique, or process that changes the physical and/or chemical character of petroleum. Trickle hydrodesulfurization is a fixed-bed process for desulfurizing middle distillates. Turbulent flow is the flow of a liquid or gas, in which particles of matter make the diverse casual chaotic movements in different directions. At the same time the average speed of particles coincides in the direction with the flow velocity. The tubular reactor is a flow type reactor in which the catalyst is located inside a metal tube. Heating or cooling of the tubular reactor is carried out from the outside by means of an external coolant (liquid or gas). In the industry, apparatuses consisting of a large number of tubes (multi-tubular reactors) are used. Tubular reactors are commonly used for reactions that occur at high rates and are accompanied by significant heat release. Turnaround is a planned complete shutdown of an entire process or section of a refinery, or of an entire refinery to perform major maintenance, overhaul, and repair operations and to inspect, test, and replace process materials and equipment. Turnover frequency (TOF) is a number of acts of catalytic transformation on one active center of the catalytic agent for a unit of time. The term is used to refer to the turnover per unit time, as in enzymology. For most relevant industrial applications, the turnover frequency is in the range of 10 −2 ‒ 102 s−1 (enzymes 103 ‒ 107 s−1). Turnover number of catalase is maximum i.e. 4·10 7 s−1. TOF represents the most accurate measure of catalytic activity, allows to compare activity of different catalytic agents. In some cases the number of the active centers is unknown, for example, in heterogeneous photocatalysis. Then use the surface frequency of turns, i.e. number of acts of catalytic transformation for a unit of time on unit of the surface measured on nitrogen adsorption by the BET method. U Unisol process is a chemical process for extracting mercaptan sulfur and certain nitrogen compounds from sour gasoline or distillates using regenerable aqueous solutions of sodium or potassium hydroxide containing methanol.

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Unstable – this term usually refers to a petroleum product that has more volatile constituents present or refers to the presence of olefin and other unsaturated constituents. UOP alkylation is a process using hydrofluoric acid (which can be regenerated) as a catalyst to unite olefins with iso-butane. UOP copper sweetening is a fixed-bed process for sweetening gasoline by converting mercaptans to disulfides by contact with ammonium chloride and copper sulfate in a bed. UOP fluid catalytic cracking is a fluid process of using a reactor-overregenerator design. Upflow reactor is a reactor in which the feedstock flows in an upward direction through the catalyst bed. Upgrading is the conversion of petroleum to value-added salable products. Urea dewaxing is a continuous dew axing process for producing low-pour-point oils, and using urea which forms a solid complex (adduct) with the straightchain wax paraffins in the stock; the complex is readily separated by filtration. V Vacuum distillation is a process of separating petroleum hydrocarbon mixtures into components under reduced pressure, based on the difference in their boiling points. The use of a reduced pressure allows reducing the boiling point of the components, since at atmospheric pressure the heavy components decompose earlier than they boil out. It is the distillation of petroleum under vacuum which reduces the boiling temperature sufficiently to prevent cracking or decomposition of the feedstock. Vacuum distillation is used for a finer separation of residual atmospheric distillation (mazut, fuel oil). Its products are gas oils and residues (for example, tar). Vacuum gas oils are used as components of diesel fuel, and also as raw materials for the process of catalytic cracking and a number of others. Vacuum residuum is a residuum obtained by distillation of a crude oil under vacuum (reduced pressure); that portion of petroleum which boils above a selected temperature such as 510°C (950°F) or 565°C (1050°F). The valence band is the highest energy of the continuum of energy levels in the solid, which are completely occupied by electrons at 0 K. The valence band is lower in energy than the conduction band and in semiconductors is usually completely filled. When heated, the electrons jump through the forbidden zone from the valence band to the conduction band, which makes the material conductive. The Fermi level at an energy EF separates the valence band from the conduction band. In metals, the valence band is a conduction band. Vapor is the gaseous phase of a substance that is a liquid at normal temperature and pressure. Vapor-phase cracking is a high-temperature, low-pressure conversion process. Vapor-phase hydrodesulfurization is a fixed-bed process for desulfurization and hydrogenation of naphtha. Visbreaking is viscosity breaking i.e. a low-temperature cracking process used to reduce the viscosity or pour point of straight-run residuum.

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Viscous flow is a physical condition in which a highly elastic polymer passes when heated. Polymers can flow in this state. The volumetric rate is the ratio of the volume of the reaction mixture supplied per hour to the inlet of the reactor to the bulk volume of the catalyst in this reactor. This term is used for both liquid and gaseous reaction mixtures, the conditions for determining the volume of the mixture can be reduced to standard and differ from the conditions of the process. W Wet gas is a gas containing a relatively high proportion of hydrocarbons that are recoverable as liquids. Wet impregnation ‒ see diffusion impregnation. Wet scrubbers are devices in which a counter-current spray liquid is used to remove impurities and particulate matter from a gas stream. White oil is a generic term applied to highly refined, colorless hydrocarbon oils of low volatility, and covering a wide range of viscosity. Width of the forbidden band is a difference of energy of a conduction band and energy of the forbidden band of substance. In semiconductors and insulators (dielectrics) it is a difference of energies between a bottom (lower level) of a conduction band and a ceiling (upper level) of the valence band. The Wilkinson catalyst is chloride tris(triphenylphosphine) of rhodium [(Ph3P)3Rh]Cl, a homogeneous catalyst for the hydrogenation of a double or triple bond in hydrocarbons. White spirit and specific boiling point (SBP) spirits are defined as refined distillate intermediates with a distillation in the naphtha/kerosene range. X Xerogel is a structure obtained by removing a liquid dispersion medium from a gel. Z Zeolites are natural or synthetic aluminosilicates which crystal structure contains regular system of cavities and channels with sizes of 0.2-1.5 nm. The structure of zeolites represents a three-dimensional framework from tetrahedral fragments [SiO4] and [AlO4] at which there are counterion (cations of metals, H+, NH4+, etc.) compensating a negative charge. Zeolites are used in catalysis as solid acids, in particular, as an active component of catalysts of cracking. Ziegler-Natta process is a catalytic reaction of polymerization of α-olefins with formation of stereoregular polymers. In the industry the catalysts prepared from α-TiCl3 and alkyls of metals like Al(C2H5)2Cl are used.

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INTRODUCTION ..................................................................................... 3 1. PETROLEUM REFINING. OIL REFINING FACTORIES ................. 5 1.1. The general concepts about oil and oil processing ............................. 5 1.2. Refinery: general information, refinery types ..................................... 14 1.3. Oil refining in Kazakhstan. Kazakhstan refineries .............................. 21 2. THE CONCEPT OF CATALYSIS ....................................................... 26 2.1. Catalysis as phenomena. Catalysis preconditions. Catalytic activity .. 26 2.2. Classification of catalysis and catalytic reactions ............................... 31 2.3. Stages of heterogeneous catalysis ....................................................... 35 2.4. A role and features of a catalysis in industry and oil processing......... 37 3. FUNDAMENTALS OF CATALYTIC HETEROLYTIC PROCESSES OF OIL AND GASES REFINING ..................................... 46 3.1. Cracking of crude oil. Catalytic cracking ............................................ 46 3.1.1. General information. Types of cracking. Thermal cracking............. 46 3.1.2. Catalytic cracking ............................................................................ 49 3.1.2.1. Preparation of raw materials for catalytic cracking ....................... 50 3.1.2.2. Catalysts ........................................................................................ 53 3.1.2.3. Chemistry of the process .............................................................. 62 3.1.2.4. Transformations of alkanes during catalytic cracking .................. 63 3.1.2.5. Transformations of alkenes during catalytic cracking ................... 69 3.1.2.6. Transformations of naphthenes during catalytic cracking ............. 72 3.1.2.7. Transformations of aromatic hydrocarbons during catalytic cracking ..................................................................................................... 75 3.1.2.8. Catalytic cracking installations ..................................................... 76 3.2. Synthesis of high-octane gasoline components from catalytic cracking gases.............................................................................. 82 3.2.1. Alkylation: general information ...................................................... 82 3.2.2. Theoretical and technological bases of alkylation of isobutene by alkenes .................................................................................................. 83 3.2.2.1. Raw materials, chemistry and process catalysts ........................... 83 3.2.2.2. Types of alkylation reactors .......................................................... 88 3.2.3. Theoretical and technological bases of the catalytic esterification of methanol with isobutylene ............................................... 92

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3.2.3.1. Raw materials, process catalysts ................................................... 92 3.2.3.2. Theoretical basis of reaction ......................................................... 94 3.2.3.3. O-alkylation catalysts .................................................................... 95 3.2.3.4. Raw materials. Fundamentals of process control of O-alkylation ........................................................................................... 96 4. BASICS OF CATALYTIC HOMOLYTIC PROCESSES OF OIL REFINING ................................................................................... 102 4.1. General information. Catalytic homolytic processes in oil refining. Catalysis by metals and oxides ............................................... 102 4.2. Processes of catalytic oxidation .......................................................... 104 4.2.1. Classification of reactions ................................................................ 104 4.2.2. Heterogeneous catalysts of oxidization ............................................ 106 4.3. Theoretical bases and technology of steam catalytic conversion of hydrocarbons for the hydrogen manufacturing ...................................... 107 4.4. Oxidative conversion of hydrogen sulphide to elemental sulphur. The Claus process ........................................................................ 113 4.4.1. General information. The Claus process unit ................................... 113 4.4.2. Influence of the main technological parameters on the Claus process ............................................................................................. 117 4.4.3. Thermal stage technology ............................................................... 119 4.4.4. Catalytic stage technology ............................................................... 121 4.4.5. Catalysts of Claus process................................................................ 124 4.5. Technology of oxidative demercaptanization of liquefied gases and gasoline-kerosene fractions. Processes “Merox” and “Bender” ............................................................................................. 126 5. FUNDAMENTALS OF PROCESS OF HYDROCATALYTIC OIL-REFINING PROCESSES .................................................................. 132 5.1. Classification of processes. The purpose and significance of hydrocatalytic processes ........................................................................ 132 5.2. Theoretical bases and technology of catalytic reforming processes .... 134 5.2.1. General information. Process chemistry .......................................... 134 5.2.2. Catalysts of reforming ..................................................................... 136 5.2.3. Installations of catalytic reforming ................................................. 138 5.3. Technological bases and technology of catalytic isomerization of pentane-hexane fraction ......................................................................... 144 5.3.1. General information ......................................................................... 144 5.3.2. Catalysts. Installations ..................................................................... 146 5.4. Fundamentals of catalytic hydrogenation processes of processing of oil raw materials .............................................................. 154 5.4.1. General information. Purpose and main parameters of the process ............................................................................................. 154 5.4.2. Catalysts of hydrogenation processes .............................................. 158 5.4.3. Installations. Processes examples ..................................................... 162 5.4.3.1. Installation of hydrotreating of diesel fuel ................................... 163

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5.4.3.2. Hydrotreating of vacuum distillates ............................................. 165 5.4.3.3. Processes of hydrotreating oil residues. Hydrodesulfurization of oil residues by the method of the French Institute of Oil ............................................................................................ 165 5.5. Bases of hydrocracking of oil raw materials ...................................... 169 6. ECOLOGICAL PROBLEMS OF OIL REFINING AND PETROCHEMISTRY ...................................................................... 176 7. MODERN PROBLEMS OF OIL AND GASES REFINING. PROBLEMS OF PETROCHEMICAL SYNTHESIS ................................ 186 GLOSSARY .............................................................................................. 197 BIBLIOGRAPHY...................................................................................... 254

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Еducational issue

Sassykova Larissa Ravil’evna TECHNOLOGY OF HETEROLYTIC AND HOMOLYTIC OIL REFINING PROCESSES Educational manual

Typesetting and cover design G. Кaliyeva Cover design used photos from sites www.global_images-chemicals-abstract-ssk_92683132.com

IB №12112 Signed for publishing 21.06.2018. Format 70x100 1/12. Offset paper. Digital printing. Volume 16,81 printer’s sheet. 80 copies. Order №3918. Publishing house «Qazaq University» Al-Farabi Kazakh National University KazNU, 71 Al-Farabi, 050040, Almaty Printed in the printing office of the «Kazakh University» publishing house.

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«ҚАЗАҚ УНИВЕРСИТЕТІ» баспа үйінің жаңа кітаптары Seilkhanova G.A. Chemical technology of glass: educational manual / G.A. Seilkhanova. – Almaty: Qazaq university, 2017. – 64 p. ISBN 978-601-04-2997-0 The educational manual presents the theoretical foundations of glass production, its physico-chemical properties, discusses in detail the basic technological stages of obtaining glassware. The textbook contains laboratory works for determining some characteristics of the glass. In order to improve the learning of theoretical material, and also for the control of the students’ knowledge, there are test questions in the textbook. The textbook can be used during the study of the subjects «Chemical technology of silicate materials», «Chemical technology of glass and ceramics». The educational manual is designed for the students enrolled in the chemi-caltechnological specialties, and can also be used by the lecturers and staff working in the field of producing silicate materials. Қоқaнбaев Ә.Қ. Коллоидтық химияның есептері мен жaттығулaры: оқу-әдістемелік құрaлы / Ә.Қ. Қоқaнбaев, Д.М-К. Aртыковa, М.Ж. Керімқұловa. – Aлмaты: Қaзaқ университеті, 2017. – 192 б. ISBN 978-601-04-3053-2 Оқу-әдістемелік құралда коллоидтық химияның есептері мен жаттығулары осы пәннің жеті негізгі тараулары: «Беттік керілу, беттік құбылыстар және коллоидтық бетті-активтік заттар», «Әртүрлі фазалардың жанасу беттеріндегі адсорбциялар», «Коллоидтық жүйелердегі электр­ кинетикалық құбылыстар», «Дисперстік жүйелердің молекулалықкинетикалық қасиеттері», «Дисперстік жүйелердің оптикалық қа­сиеттері», «Коллоидтық жүйелердің тұрақтылығы және коагуля­ циясы», «Дисперстік жүйелердің құрылымдық-механикалық (реоло­ гиялық) қасиеттері» бойынша түзілген. Әр тараудың басында тип­тік есептердің шығару жолдары және студенттердің өз бетімен орындауға арналған есептері берілген. Оқу-әдістемелік құрал коллоидтық химия пәнін оқитын ЖОО-ның «Химия», «Бейорганикалық заттардың химиялық технологиясы», «Орга­ никалық заттардың химиялық технологиясы» мамандықтарының студенттеріне арналған. Ospanova A.K. Chemical technology of glass: еducational manual / A.K. Ospa­ nova, G.A. Seilkhanova. – Almaty: Qazaq university, 2017. – 136 p. ISBN 978-601-04-3046-4 In the еducational manual presents the theoretical and practical aspects of chemical kinetics and electrochemistry. Much attention is paid to the important section on the problems of catalysis. Modern views on the nature of homogeneous and heterogeneous catalysis are considered. And the features of the influence of the catalyst on the rate of chemical reactions are given. The problems of the theory of solutions of strong and weak electrolytes, the thermodynamics of electrochemical processes are considered. The еducational manual is intended for students studying in chemical and chemical-technical specialties, and can also be used by undergraduates, doctorants, teachers of higher educational institutions of the Republic of Kazakhstan. Кітаптарды сатып алу үшін «Қазақ университеті» баспа үйінің маркетинг және сату бөліміне хабарласу керек. Байланыс тел: 8(727) 377-34-11. E-mail: [email protected], cайт: www.read.kz, www.magkaznu.com