Catalytic Process Technology [1 ed.] 9780309576291
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Copyright © 2000. National Academies Press. All rights reserved.
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CATALYTIC PROCESS TECHNOLOGY
Committee on Catalytic Process Technology for Manufacturing Applications Board on Manufacturing and Engineering Design Commission on Engineering and Technical Systems National Research Council
NATIONAL ACADEMY PRESS Washington, D.C.
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NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competencies and with regard for appropriate balance. This report by the Board on Manufacturing and Engineering Design was conducted with the support of the U.S. Department of Energy, Grant No. DP-FG41-95R110859. Any opinions, findings, conclusions, or recommendations expressed herein are those of the authors and do not necessarily reflect the view of the Department of Energy. Available in limited supply from: Board on Manufacturing and Engineering Design 2101 Constitution Avenue, N.W. Washington, DC 20418 202-334-3124 [email protected] Copyright 2000 by the National Academy of Sciences. All rights reserved. Printed in the United States of America.
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The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the charter granted to it by the Congress in 1863, the Acade my has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Bruce Alberts is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. William Wulf is president of the National Academy of Engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Kenneth I. Shine is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy’s purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Bruce Alberts and Dr. William Wulf are chairman and vice chairman, respectively, of the National Research Council. www.national-academies.org
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Copyright © 2000. National Academies Press. All rights reserved.
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COMMITTEE ON CATALYTIC PROCESS TECHNOLOGY FOR MANUFACTURING APPLICATIONS STANLEY A. GEMBICKI (chair), UOP Corporation, Des Plaines, Illinois RALPH A. DALLA BETTA, Catalytica, Inc., Mountain View, California FRANCIS G. DWYER, Mobil Research and Development Corporation (retired), West Chester, Pennsylvania ROBERT J. FARRAUTO, Engelhard Corporation, Iselin, New Jersey RANDOLPH L. GREASHAM, Merck and Company, Inc., Rahway, New Jersey JAMES F. ROTH, Air Products and Chemicals, Inc. (retired), Sarasota, Florida MARTIN B. SHERWIN, ChemVen Group, Boca Raton, Florida FRANCIS A. VIA, GE Corporate Research and Development Center, Schenectady, New York BARBARA K. WARREN, Union Carbide Corporation, South Charleston, West Virginia JOSEPH R. ZOELLER, Eastman Chemical Company, Kingsport, Tennessee NRC Staff CUNG VU, Study Director TERI G. THOROWGOOD, Research Associate AIDA C. NEEL, Senior Project Assistant JUDITH L. ESTEP, Senior Project Assistant Government Liaison PAUL SCHEIHING, U.S. Department of Energy, Washington, D.C.
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BOARD ON MANUFACTURING AND ENGINEERING DESIGN JOSEPH WIRTH, (chair), Raychem Corporation (retired), Mount Shasta, California F. PETER BOER, Tiger Scientific, Inc., Boynton Beach, Florida JOHN BOLLINGER, University of Wisconsin, Madison HARRY COOK, University of Illinois, Urbana PAMELA DREW, The Boeing Company, Seattle, Washington ROBERT EAGAN, Sandia National Laboratories, Albuquerque, New Mexico EDITH FLANIGEN, UOP Corporation (retired), White Plains, New York JOHN GILLESPIE, JR., University of Delaware, Newark JAMIE HSU, General Motors Corporation, Warren, Michigan RICHARD KEGG, Milacron, Inc. (retired), Cincinnati, Ohio JAY LEE, United Technologies Corporation, East Hartford, Connecticut JAMES MATTICE, Universal Technology Corporation, Dayton, Ohio CAROLYN MEYERS, North Carolina Agricultural and Technical State University, Greensboro JOSEPH MIZE, Oklahoma State University, Stillwater FRIEDRICH PRINZ, Stanford University, Palo Alto, California JAMES RICE, Massachusetts Institute of Technology, Cambridge JOHN STENBIT, TRW, Inc., Fairfax, Virginia DALIBOR F. VRSALOVIC, Intel Corporation, Santa Clara, California JOEL SAMUEL YUDKEN, AFL-CIO, Washington, D.C. NRC Staff ARUL MOZHI, Acting Director PATRICK J. DOYLE, Staff Officer TERI G. THOROWGOOD, Research Associate JUDITH L. ESTEP, Senior Administrative Assistant
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PREFACE
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Preface
The chemical industry has a long history of combining theory (science) and practice (engineering) to create new and useful products. Catalysis has been, and continues to be, a key to the development and growth of this large, diverse industry. This report builds on previous studies, especially Technology Vision 2020, prepared in 1996 by a group of chemical industry organizations, as well as the collective industrial experience of committee members and presentations by representatives of industry and the national laboratories. The report provides an overview of current research on catalysis and identifies areas for future research and development with the potential for significant industrial impact. I wish to thank the members of the committee for their hard work, enthusiasm, and diversity of thought. Innovation in this important area will depend on creative interchanges of ideas in the scientific community. The combined efforts of the entire catalysis community will be necessary to meet future technological challenges. Stanley A. Gembicki, chair Committee on Catalytic Process Technology for Manufacturing Applications
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PREFACE viii
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ACKNOWLEDGMENTS
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Acknowledgments
The Committee on Catalytic Process Technology for Manufacturing Applications would like to thank the following individuals for their presentations: James Quinn, Office of Industrial Technologies; Brian Valentine, Office of Industrial Technologies; James Stevens, Dow Chemical Company; Robert Dorsch, E.I. du Pont de Nemours and Company; Thomas Baker, Los Alamos Laboratory; Tom Verhoeven, Merck and Company, Inc.; and Ronald Heck, Engelhard Corporation. This report has been reviewed by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the NRC’s Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the authors and the NRC in making the published report as sound as possible and to ensure that the report meets the institutional standards for objectivity, evidence, and responsiveness to the study charge. The content of the review comments and draft manuscript remains confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their participation in the review of this report: Thomas Baker, Los Alamos National Laboratory; Norman Blank, Sika Corporation; Scott Han, Rohm and Haas; Lanny Schmidt, University of Minnesota; Jeffrey Siirola, Eastman Chemical Company; Gabor Somorjai, University of California, Berkeley; Gregory Whited, Genencor International, Inc.; and Ronald Yates, Dow Chemical Company. Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recommendations nor did they see the final draft of the report before its release. The review of this report was overseen by George Keller, appointed by the Commission on Engineering and Technical Systems, who was responsible for making certain that an independent examination of this report was carried out in accordance with institutional procedures and that all review comments were carefully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution. Finally, the committee gratefully acknowledges the support of the staff of the Board on Manufacturing and Engineering Design, including Cung Vu, study
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ACKNOWLEDGMENTS x
director; Teri G. Thorowgood, research associate; Judith L. Estep, and Aida C. Neel, senior project assistants. The report was edited by Carol R. Arenberg, Commission on Engineering and Technical Systems.
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CONTENTS
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Contents
EXECUTIVE SUMMARY
1
1
INTRODUCTION U.S. Chemical Industry Industrial Catalysis Policy Background Office of Industrial Technologies Current Study
7 7 7 8 11 11
2
AREAS FOR APPLIED RESEARCH Alkane Activation and Selective Oxidation Synthesis of Fine Chemicals Alternative and Renewable Resources Olefin Polymerization Alkylation Technology Environmental Applications
13 16 20 24 28 29 31
3
POLICY-RELATED ISSUES Innovation Computational Technology Combinatorial Chemistry and Data Management Funding for Catalysis Research Proposal Review Process Program Metrics Research Centers
37 38 38 39 40 41 41
REFERENCES
43
APPENDIXES A
Invited Speakers
45
B
Biographical Sketches of Committee Members
47
GLOSSARY
51
ACRONYMS
55
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CONTENTS xii
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EXECUTIVE SUMMARY
1
Executive Summary
Catalysis is critical to the U.S. chemical industry. Sixty percent of today’s chemical products and 90 percent of current chemical processes are based on catalytic chemical synthesis. Therefore, general advances in the field of catalysis could potentially have many applications, as well as a major impact on the entire $500-billion industry. In December 1996, a group of chemical industry organizations, including the American Chemical Society, the American Institute of Chemical Engineers, the Chemical Manufacturers Association, the Council for Chemical Research, and the Synthetic Organic Chemical Manufacturers Association, produced a report entitled Technology Vision 2020. The report outlined the current state of the chemical industry, proposed a vision for the future, and identified the technical advances that would be necessary to make this vision a reality. The report noted that continued advances in chemical synthesis would be necessary to maintain the competitiveness of the U.S. chemical industry. The report recommended that the industry work toward the following goals: • the development of new synthesis techniques incorporating the disciplines and approaches of biology, physics, and computational methods • increased collaborations in research and development (R&D) on surface and catalytic science relevant to commercial products and processes • improved understanding of the fundamentals in synthesis, processing, and fabrication for structural control of complex molecular architectures • increased support for fundamental studies to advance the development of chemistry in alternative reaction media In March 1997, the Council for Chemical Research sponsored a follow-up study to Technology Vision 2020. The results of that study and a subsequent workshop were summarized in The Catalyst Technology
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EXECUTIVE SUMMARY
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Roadmap Report, which also emphasized that advances in catalysis would be a fundamental factor in the economic viability of the chemical industry. The report also identified and ranked areas in which improvements in catalytic technologies could significantly contribute to meeting the goals of Technology Vision 2020. These two reports provide a framework for the present study. This study, sponsored by the U.S. Department of Energy (DOE) Office of Industrial Technologies (OIT), was designed to bring together a panel of industrial experts with diverse areas of interest and points of view to identify high-impact opportunities for OIT’s applied research programs. The committee was charged with addressing the following tasks: • Identify opportunities for the use of catalytic process technologies in manufacturing applications with an emphasis on the Industries of the Future (IOF) and a focus on opportunities for chemical and petrochemical synthesis and processing, including biocatalysis of fossil or petroleum-based materials. • Recommend applied research areas in catalytic processing that are consistent with OIT’s program strategy and objectives. • Suggest means by which industry can leverage research results in federal programs, including those at other federal agencies, national laboratories, and other DOE offices. Although this report is focused on identifying opportunities for applied research, the committee wishes to express its strong reservations about government funding for applied research at the expense of projects that would not otherwise be pursued by individual corporations, such as long-term, high-risk, but potentially high payoff, theoretical research in catalysis or the development of tools that would accelerate advances in catalysis. RECOMMENDATIONS The committee reviewed the previous studies primarily to ascertain industry’s point of view. Data from this review, additional source material, and input from a cross section of technology leaders were then collected. The committee identified the six areas that would have the greatest impact on the industry: alkane activation and selective oxidation; synthesis of fine chemicals; alternative and renewable resources; olefin polymerization; alkylation technology; and environmental applications. Research areas were considered for their direct impact on technology advances, their timeliness, their probability of success, the cost of investment relative to the potential benefit, and their appropriateness for government support.
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EXECUTIVE SUMMARY
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Because of the breadth and diversity of the field of catalysis, the committee was unable to prioritize these six areas. The committee strongly believes that they are all important and that they all have potentially high payoffs. In addition, they are all applicable to OIT’s strategies for reducing energy requirements and minimizing waste and pollution. OIT’s decision to fund a project, however, also depends on the technical and economic merit and impact of each proposal. Based on the experience and expertise of committee members, the two most important and appropriate opportunities for catalytic research in each area (or crosscutting research, such as sintering) are recommended for funding by OIT. All proposals submitted to OIT for research projects should include both metrics for measuring progress and estimates of the potential impact on the industry as a whole. Recommendations for Applied Research Alkane Activation and Selective Oxidation Recommendation. The Office of Industrial Technologies should support the development of catalysts and processes for the low-temperature, oxidative dehydrogenation of alkanes to alkenes. Recommendation. The Office of Industrial Technologies should support the development of mixed-metal oxide catalysts for alkane activation using predictive computing methods. Synthesis of Fine Chemicals Recommendation. The Office of Industrial Technologies should support the development of catalysts with substantially improved synthetic versatility and atom economy. Recommendation. The Office of Industrial Technologies should support the development of enzymes with substrate specificity and stereoselectivity for chiral synthesis in fine chemicals. Alternative and Renewable Resources Recommendation. The Office of Industrial Technologies should support a study of alternative, lower cost means of producing synthesis gas from alternative resources.
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EXECUTIVE SUMMARY
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Recommendation. The Office of Industrial Technologies should support the development of processes for converting biomass to feedstocks and polymers. Research should focus on microorganisms, biological catalysts (enzymes), and traditional catalysis. Olefin Polymerization Recommendation. The Office of Industrial Technologies should support the development of catalysts that can copolymerize olefins with a diverse class of polar unsaturated monomers. Recommendation. The Office of Industrial Technologies should support the development of catalysts that are tolerant of common impurities, such as water and amines. Alkylation Technology Recommendation. The Office of Industrial Technologies should support the development of catalysts with ultrahigh selectivity. Recommendation. The Office of Industrial Technologies should support the development of catalysts with tolerance to functional groups. Environmental Applications Recommendation. The Office of Industrial Technologies should support a study to evaluate “step-out” innovative catalyst strategies for controlling nitrogen oxide emissions in lean environments. Recommendation. The Office of Industrial Technologies should support the development of a basic understanding of the sintering of supported metals. Policy-Related Recommendations In addition to technical recommendations, the committee was asked to suggest means by which OIT could help industry leverage research resources and federal programs, including programs at other federal agencies, national laboratories, and other DOE offices. In keeping with OIT’s program strategy
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EXECUTIVE SUMMARY
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and objectives, the committee recommends that government support only precompetitive, high-risk, innovative research. Short-term, applied research should be supported by industry. Innovation Recommendation. The Office of Industrial Technologies should support precompetitive, high-risk, innovative research that has a high potential of addressing targeted industry needs. Computational Technology Recommendation. The Office of Industrial Technologies should assist industry in supporting the development of high-throughput screening and computational technologies that would benefit the entire chemical industry. Funding for Catalyst Research Recommendation. The Office of Industrial Technologies should consider reducing the number of projects it funds and coordinating its projects with those of other federal agencies to provide enough critical mass to support innovative research in many areas. Proposal Review Process Recommendation. The Office of Industrial Technologies should promote industry involvement in the proposal review process and also streamline this review process. Program Metrics Recommendation. The Office of Industrial Technologies (OIT) should establish aggressive objectives and procedures for assessing the progress of each program. Programs should be formally reviewed annually by OIT and semiannually by industry participants.
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EXECUTIVE SUMMARY 6
Research Centers
Recommendation. The Office of Industrial Technologies should encourage and facilitate the formation of “virtual catalyst research centers” based on the unique capabilities of the national laboratories.
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INTRODUCTION
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1 Introduction
U.S. CHEMICAL INDUSTRY The U.S. chemical industry (excluding the petroleum and pharmaceutical industries) includes 9,000 businesses that develop, manufacture, and market more than 70,000 products. The United States is the world’s largest producer of chemicals; $367 billion in products was shipped in 1995. The chemical industry, the third largest manufacturing sector in the United States, employs one million people and represents approximately 10 percent of all U.S. manufacturing (ACS, 1996). This research-intensive industry spends approximately $17.6 billion annually on research and development (R&D)(DOC, 1996). The success of the U.S. chemical industry is largely attributable to breakthroughs in science and technology. INDUSTRIAL CATALYSIS Catalysis has been defined as the process by which chemical reaction rates are altered by the addition of a substance (the catalyst) that is not itself changed during the chemical reaction (ACS, 1996). Catalysts are usually used so that chemical reactions can occur at temperatures and pressures low enough for producers to use economically priced equipment or to ensure that the rate of production of a desired product is greater than the rates of production of undesirable by-products. Catalysis-based chemical synthesis accounts for 60 percent of today’s chemical products and is a factor in 90 percent of current chemical processes (ACS, 1996). Catalysis is a broad technical field rather than a product. Setting targets for the development of catalytic designs or production is, therefore, different from setting targets for particular products. The chemical industry is so large that general advances in the field, rather than advances in specific
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INTRODUCTION
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catalysts/processes, could have a large impact in terms of economics, the environment, and energy use. 1 POLICY BACKGROUND Traditionally, the chemical industry has funded most of its own R&D. In the last decade or so, because of increased competition and environmental constraints, the industry has shifted its research away from basic research and toward the development of near-term processes and products (ACS, 1996). Although recent improvements in computer-based modeling and instrumentation have revitalized R&D, because of global competition and the long time scale for breakthroughs, and hence the high risk, industry has attempted to leverage its investment in R&D through industry-government partnerships. Technology Vision 2020: The U.S. Chemical Industry, produced by a group of chemical industry trade associations, including the American Chemical Society, the American Institute of Chemical Engineers, the Chemical Manufacturers Association, the Council for Chemical Research, and the Synthetic Organic Chemical Manufacturers Association, is a study of factors that affect the competitiveness of the chemical industry in a rapidly changing business environment (ACS, 1996). Vision 2020 was undertaken in response to a request from the White House Office of Science and Technology Policy for industry advice on how the government could allocate R&D funding to advance the U.S. manufacturing base. More than 200 technical and business leaders participated in the study, which concluded that the growth and competitive advantage of the chemical industry is dependent on both R&D by individual companies and collaborative efforts by industry, government, and academe. Vision 2020 outlines the current state of the chemical industry, provides a vision for the industry in 2020, and identifies the technical advances necessary to make this vision a reality. The report notes that continued advances in chemical synthesis (including catalysis) will be necessary for the U.S. chemical industry to maintain its competitiveness and encourages the industry to develop new synthesis techniques, enhance R&D collaborations in surface and catalytic science, promote the understanding of structure-property relationships in complex molecular architectures, and support fundamental research to advance the use of alternative reaction media (to reduce the use of organic solvents).
1 Catalysis is also a vital component of a number of national critical technologies and an important factor in energy security (Jackson, 2000; Phillips, 1991). This report focuses only on the chemical industry.
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INTRODUCTION
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Several specific needs and challenges were identified in Vision 2020, including catalysts and reaction systems for economical and environmentally safe processes with the lowest life-cycle costs; and catalysts to replace toxic and corrosive mineral acids and bases for organic synthesis. The following challenges were also identified: • methods of synthesis and catalysis to convert product molecules and polymers back into useful starting materials • catalysts with long life and self-repairing capabilities • new catalysts for the efficient conversion of biomass and unused by-products into useful raw materials • new catalysts for customizing polymer properties (composition, stereochemistry) during synthesis • catalysts for reaction pathways focused on ultrahigh selectivity, higher molecularity, higher regiospecificity and stereospecificity, and asymmetric and chiral synthesis Vision 2020 also noted significant changes in the “supply side” of the chemical industry, including reduced time-to-market for new products, shorter production schedules, shorter delivery time, and improved logistics for delivery. Many of these changes are the direct result of new technologies, such as new computer hardware and software, and are expected to lead to lower production costs, faster introduction of new products, and improved environmental performance. However, these changes will also lead to significant changes in R&D on catalysis. The chemical industry, especially the producers of high-profit fine chemicals and specialty chemicals faced with increasing global competition, are under great pressure to accelerate the identification of new catalysts and catalyst compositions for specific transformations. As a consequence, catalytic scientists are increasingly becoming dependent on high-throughput catalyst screening and the use of predeveloped catalysts, as well as a well established understanding of the nature of catalytic processes at the molecular level. Computational processes are increasingly being used to assist in the evaluation and improvement of catalysts identified from high-throughput screening processes and of new catalysts. Tools for faster methods of catalyst discovery and development are not yet fully developed, but they will be critical to the rapid advancement of the chemical industry and are implicit in the Vision 2020 report. As a result of the Vision 2020 report, the Council for Chemical Research created a Chemical Synthesis Team to identify crosscutting and critical needs in catalytic technology. In addition, a catalysis workshop was held on March 20 and 21, 1997, with experts from industry, academia, and government. All participants considered catalysis fundamental to the
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INTRODUCTION
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economic and environmental viability of the chemical industry and concluded that advances in catalytic science and technology will be crucial for the chemical industry. The Catalyst Technology Roadmap Report was produced as a result of the workshop (Jackson, 1997). Two major goals emerged from the work of the Chemical Synthesis Team and the workshop: • acceleration of the catalyst development process • the development of catalysts with selectivity approaching 100 percent Achieving these goals will require high-throughput and diversity in the synthesis and screening of catalysts; faster characterization systems; rational catalyst design using both empirical and fundamental computational techniques; and a better fundamental understanding of intermediate pathways, transition states, and in-situ monitoring. The workshop also identified and ranked areas in which improvement of catalytic processes could have a significant impact. The rankings were based on the following criteria: impact of technology advances, timeliness of the impact, probability of successful development, cost of investment relative to the potential benefits, and appropriateness of government support. The areas for improvement were: selective oxidation, hydrocarbon activation, by-product and waste minimization, stereoselective synthesis, functional olefin polymerization, alkylation, living polymerization, and alternative renewable feedstocks. The following primary needs in catalysis were identified: •
catalyst design through combined experimental and mechanistic understanding and improved computational chemistry • techniques for high-throughput synthesis of catalysts and use of new assays for rapid-throughput catalyst testing, potential combinatorial techniques, and reduction of analytical cycle time by parallel operation and automation • better techniques for in-situ catalyst characterization • synthesis of catalysts with specific-site architectures A Vision 2020 Catalyst Implementation Team, under the auspices of the Council for Chemical Research, was formed to develop a preliminary list of crosscutting needs and targets and produce a road map of technical targets for achieving the Vision 2020 goals in the area of catalysis. This Catalyst Implementation Team, which included academic and industrial scientists, worked out a consensus on the important areas for future catalysis research. An interim report, issued in March 1998, outlines the future technology
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INTRODUCTION
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needs of the chemical industry in the area of catalysis (Haynes, 1998). No timeline for achieving milestones was included. OFFICE OF INDUSTRIAL TECHNOLOGIES The Office of Industrial Technologies (OIT) is part of the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy. OIT develops advanced energy-efficient technologies, including renewable energy and pollution prevention for U.S. industry. OIT works with industry and other government and nongovernmental organizations to improve the resource efficiency and competitiveness of materials and process industries. It also helps industries identify and pursue technology needs through public/private partnerships. OIT has initiated the Industries of the Future (IOF) Program, a customer-driven program that encourages energyintensive and resource-intensive industries to work together toward the following objectives: • the creation of broad, industry-wide goals for the future • identification of specific needs and priorities through industry-developed road maps • formation of cooperative alliances to help attain those goals CURRENT STUDY The current study to identify high-impact opportunities for OIT-funded applied research programs was conducted by the National Research Council Committee on Catalytic Process Technology for Manufacturing Applications. The study was sponsored by OIT. The committee was asked to address the following tasks: •
Identify opportunities for the use of catalytic process technologies in manufacturing applications, emphasizing the IOF and focusing on opportunities for chemical and petrochemical synthesis and processing, including biocatalysis of fossil or petroleum-based materials. • Recommend areas for applied R&D in catalytic processing that are consistent with OIT’s program strategy and objectives (i.e. reducing energy and resource consumption and reducing waste generation). • Suggest means by which industry can leverage research resources, work by federal programs, including programs at other federal agencies, national laboratories, and other DOE offices.
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INTRODUCTION 12
The committee reviewed previous studies and was briefed by experts in various catalysis areas. Based on this information and the knowledge and experience of committee members, the committee identified high-impact areas and recommended specific areas for research.
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2 Areas for Applied Research
The committee reviewed previous studies for their applicability to industry, consulted a variety of other printed sources, and met with a cross section of leaders in industry and academia to generate a list of potential research areas (see Table 2-1 ). Members of the committee included industry representatives with diverse backgrounds: catalysis, including Fischer-Tropsch catalyst systems; catalytic sensor systems for monitoring combustion systems; catalytic processes for the manufacture of pharmaceutical intermediates and other specialty chemicals; catalyst characterization; noble metal catalysts; catalytic combustion catalysts and combustion system components; zeolite catalysts; catalysts for environmental applications for stationary and mobile sources; biological catalysis, including fermentation biochemistry, and microbial genetics; heterogeneous catalysis; homogeneous catalysis; catalysts and processes for the generation of acetic acid, acetic anhydride, methyl acetate, propionic acid, and propionic anhydride from synthetic gas; chemical engineering research; development of new applications for catalysts; and commercialization and scale-up of new catalytic processes. For biographical information about the committee members see Appendix B . After the initial list was generated, each research area was debated and evaluated against five criteria: impact of the technology advance; timeliness of the impact; probability of successful development; cost of investment relative to the potential benefit; and appropriateness of government involvement. After several iterations, the committee reached a consensus. The final list was then categorized into six areas: • • • • • •
alkane activation and selective oxidation synthesis of fine chemicals alternative and renewable resources olefin polymerization alkylation technology environmental applications
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AREAS FOR APPLIED RESEARCH
TABLE 2-1 Potential Research Areas Novel pathways for the selective conversion of methane/ethane to higher molecular-weight products: • methane to methanol • methane to ethylene • ethane to ethylene • methane to higher molecular-weight molecules • alkane alkylation with carbon monoxide Characterization of the types of oxygen present on oxide surfaces and their role in alkane activation and subsequent oxidation Identification of factors controlling selectivity in selective oxidation and oxidative dehydrogenation of alkanes and selective oxidation of olefins and aromatics Identification of novel methods of activating oxygen Development of novel catalysts for the selective oxidation of alkanes, olefins, and aromatics: • sulfur dioxide to sulfur trioxide at low temperature • catalysis with nonprecious metals (ammonia to nitric oxide for nitric acid) • direct production of hydrogen peroxide • benzene to phenol • low-temperature oxidative dehydrogenation of alkanes • low-temperature dehydrogenation of alkanes • alkene epoxidation (ethylene to ethylene oxide, propylene to propylene oxide) • propane to acrolein/acrylic acid • primary oxidation of alkanes to alcohols and diols • direct amination Production of motor-fuel alkylate Production of aliphatic amines (ethylamine, propylamine, ethylamine) Replacement of aluminum trichloride as an alkylation/isomerization catalyst for pharmaceutical production Benign manufacturing to eliminate chloride, cyanide, hydrogen cyanide, phosgene, halogen alternatives
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Development of high-activity catalysts for the direct decomposition of nitric oxide to nitrogen and oxygen in the presence of oxygen and water in the feed components that act as poisons or inhibitors (auto/lean burn; stationary power) Development of active, low-temperature (lower than 250° C) catalysts for control of volatile organic compounds and combustion of methane Development of catalysts for the efficient hydrogenolysis of chlorinated hydrocarbons to hydrochloric acid Development of catalysts for the selective deep removal of sulfur from feed streams and the conversion of sulfur oxide to products of value Discovery and development of catalysts for the production of commercially significant products at lower temperatures and pressures than those required for current processes Development of catalysts for depolymerizing polymers Stereoselective synthesis to conserve source materials and use more complex materials effectively Enantioselective synthesis to meet the growing needs of the life sciences, including medicine, nutrition, animal health, and plant control Development of more active catalysts for hydrogen production for fuel cells Development of catalysts for the conversion of biological feedstocks to chemicals Improvements in existing processes by reductions in the levels of carbon dioxide produced as a by-product Identification of methods of controlling polymer architecture and composition Development of catalysts for the incorporation of a variety of functional groups during olefin polymerization Development of catalysts for the synthesis of chiral polymers
Because of the breadth and diversity of the field of catalysis, the committee was not able to prioritize these six areas. The committee strongly believes that all of them are important and that all of them offer opportunities for high-payoff research in catalysis. Within each area, the two most important opportunities for catalytic research were selected and recommended to OIT for funding.
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ALKANE ACTIVATION AND SELECTIVE OXIDATION Using current commercial processes, yields of many common organic chemicals (e.g., propylene oxide, formaldehyde, and 1,4-butanediol) are low. The economics of production of acrolein, acrylic acid, methanol, acetic acid, phthalic anhydride, and linear alcohols could be considerably improved if they could be produced from simpler feedstocks (e.g., propane instead of propylene, ethane instead of ethylene). In some cases, significant amounts of coproducts are produced (e.g., acetone is produced in phenol production from cumene, and t-butanol is produced in propylene oxide production from propylene and isobutane) so that the economics are more complicated than those of a process for producing a single product. Other reactions (e.g., methane to ethylene, methanol, or formaldehyde; ethane to ethylene, ethylene glycol, acetic acid, or acetaldehyde; propane to propylene, acrolein, acrylic acid, or 1,3-propane diol; butane to butene, 1,4-butane diol, or maleic anhydride; isobutane to methacrylic acid, linear long-chain alkanes to the alpha olefins or linear alcohols, and benzene to phenol) could be used if they were highly selective and high yield and required low investment and low operational costs. Not only are yields of common organic chemicals low, but some reactions require more complex oxidants (e.g., hydrogen peroxide, ozone, chlorine, nitric acid, manganese oxide or potassium manganese oxide, and peroxyacids), which are more expensive than oxygen or air. Highly selective, active, stable catalysts that activate molecular oxygen could be used for alkane activation processes instead of current energy-intensive processes. New processes that could coproduce energy would be more environmentally appealing than current processes. The development of a viable process to convert alkanes into cost-efficient commodity products will require a good deal of R&D focused on the synthesis of desired materials and computational and modeling studies of catalysts and reactions. The primary building blocks for the production of chemical intermediates and polymers are olefins and aromatics, both of which are produced from petroleum and natural-gas liquids using high-temperature, endothermic processes (e.g., cracking, dehydrogenation, and reforming). There are significant economic incentives for using alkanes rather than olefins and aromatics as starting materials because low molecularweight alkanes, especially methane, are readily available and are less expensive than olefins or aromatics. Alkanes have not been used because they are highly stable compared to the products and require highenergy pathways to react compared with olefins. High- energy pathways can lead to the further conversion of desired products to less useful, but more thermodynamically stable, products (e.g., hydrogen-deficient products for nonoxidative reactions and carbon oxides
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for oxidation). Although both alkane and alkene prices are coupled to the price of crude oil, alkenes have substantial value as chemical feedstocks, whereas alkanes primarily have fuel value. Novel catalysts and reactions will be necessary for the selective conversion of methane, ethane, propane, and other inexpensive, readily available hydrocarbons to more valuable products. The single greatest challenge in using hydrocarbon as raw material is the selective, economical, partial oxidation of a light hydrocarbon to produce a single, more valuable product. The primary problem is converting a low-energy material into a high-energy material by oxidation. If this process could be used, selective catalytic oxidation of organic compounds could reduce the environmental impact of a broad range of industrial processes. Low-Temperature, Oxidative Dehydrogenation of Alkanes to Alkenes Low-temperature oxydehydrogenation of alkanes is a logical area for exploration if alkanes are used as the primary starting materials in the petrochemical industry. Alkane oxydehydrogenation is exothermic and has been demonstrated without complete combustion in a number of reactions One of the earliest low-temperature examples of selective, low-temperature alkane oxidation is the conversion of ethane to ethylene using a molybdenum-vanadium based catalyst with promoters (Thorsteinson, 1981) Selectivities of 90 to 95 percent to ethylene at yields of 50 to 80 percent were achieved at temperatures between 250°C and 400°C. Propane oxydehydrogenation to propylene has been far less successful. Under different conditions (e.g., higher pressure, added water, and recycled ethane), acetic acid could be the major product (Arne, 1986) Conversion of methane to ethylene is also appealing, and a variety of mixed-metal oxides have been shown to accomplish this reaction, both in a redox mode and in a cooxidation mode (Keller and Bhasin,1982). Catalysts containing vanadium have demonstrated selective partial alkane activation at unusually low temperatures. Iridium complexes with “pincer” ligands has also been reported for low-temperature alkane dehydrogenation (Gupta et al., 1997). New ideas for novel catalysts based on appropriate precedents and the principles of molecular chemistry at the active site could also be investigated. Other interesting mixed-metal oxides reported to oxidize alkanes without complete combustion include oxides of nickel, molybdenum, and iron. In addition, attempts have been made to modify Group VIII metals, hopcalite, and other materials that oxidize alkanes at
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very low temperatures to carbon dioxide to make them more selective towards partial oxidation products. Recommendation. The Office of Industrial Technologies should support the development of catalysts and processes for the low-temperature, oxidative dehydrogenation of alkanes to alkenes. Molecularly Designed Metal Oxides A major challenge for successful alkane activation is to predict, design, and make effective new catalytic materials (particularly mixed-metal oxide materials). Specifically defined bulk materials containing only two or three metal oxides will require novel approaches (Rulkens and Tilley, 1998) Synthesis of targeted new materials with defined structures, both on the molecular scale at the active site and on a larger scale requiring specific catalyst morphology, is beyond current capabilities. To design better catalysts, one must first understand precisely how catalysts work and how alkanes can be activated at low temperatures. Improved characterization and computational capabilities will be necessary to define the factors responsible for selective and unselective pathways. Once the dynamics, kinetics, and transition states of individual reactions are understood, reaction selectivity (ratio of the desired to undesired products) can be predicted and/or used as a conceptual model that might lead to the development of an entirely new class of catalysts. Capital investment and operating costs must also be kept in mind. For a selective-oxidation catalyst, one must consider not only the molecular design on the catalytically active site, but also catalyst morphology and bulk physical characteristics, such as crush strength or acidity, which might be very important for selectivity. Uniform large pores might result in significantly higher selectivities for partial-oxidation reactions. New methods of catalyst synthesis will be neccessary to control both active-site composition and the larger structure and physical properties of the catalyst. Successful discoveries could be used in the conversion of ethane to ethylene or acetic acid or of propane to propylene, acrolein, or acrylic acid, or the oxidation of isobutane to methacrylic acid. Anything that accelerates the discovery and testing of catalysts, especially ingenious ways of testing new catalyst compositions or processes, will decrease the time for, and increase the probability of, discovering a new, useful catalyst for alkane activation.
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Recommendation. The Office of Industrial Technologies should support the development of mixed-metal oxide catalysts for alkane activation using predictive computing methods. .
Direct Epoxidation of Higher Alkenes with Molecular Oxygen Propylene oxide is a high-volume commodity chemical produced by the chlorohydrin method and by two variants of the coproduct approach (propylene oxide/styrene monomer and propylene oxide/MTBE), which is energy intensive and has a significant adverse environmental impact. An efficient, direct-oxidation process using oxygen as the oxidant would significantly change the economics of the production of propylene oxide and other higher olefins. The highly reactive allylic positions of higher olefins have presented a significant challenge to the development of a selective epoxidation process. Homogeneous routes to epoxides that work on a simple olefin (without functional groups for complexation) have not been developed, although direct heterogeneous oxidation of propylene with high selectivity has been accomplished (Haruta, 1997). Carefully designed heterogeneous materials have shown some promise of achieving this cooxidation reaction with high selectivity and is an appropriate area for research by academia. Primary Oxidation of Alkanes to Alcohols and Diols Economical processes for converting methane to methanol, ethane to ethanol or ethylene glycol, propane to 1,3-propane diol, butane to butanol or 1,4-butane diol, and other transformations of alkanes to primary alcohols and diols could have major benefits for the chemical industry. Precedents in biological systems have demonstrated that it is possible for transition metals to selectively oxidize an alkane to a primary alcohol under mild conditions (low temperatures and pressures). However, this enzymatic process cannot yet compete with robust, heterogeneous, inorganic alternatives in terms of production rate and costs. R&D could focus on the development of ingenious heterogeneous catalyst designs that allow oxygen transfer to carbon to produce an alcohol and simultaneously prevent the further oxidation of alcohols to carbon monoxide and carbon dioxide. Homogeneous complexes have been shown to activate alkanes noncatalytically under mild conditions, or catalytically with only limited activity (Barton, 1993). Shilov (1984) reported mild conditions for catalytic reaction of alkanes with platinum metal complexes. Electrophilic alkane activation by certain transition metals (e.g., platinum, palladium, and rhodium) has been used to convert methane to methyl sulfate with high
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selectivity (Periana et al., 1998). However, rates, catalyst life, and the cost of the oxidant have not been determined. Although biomimetic catalysts were catalytic under mild conditions for hydroxylation of certain alkanes, their potential commercial use is limited. None has been robust enough to merit continued research, and rates per volume of catalyst in the most optimistic extrapolation of possibilities are still orders of magnitude below commercial requirements. Stable, heterogeneous, mixed-metal oxide analogs might provide the same advantages as biomimetic catalysts without their limitations. They could be designed with stable inorganic “ligands” to hold a metal oxide in an active redox or coordination state, analogous to how biomimetic catalysts function. For example, single-site, metal-oxide ligated zirconium and tantalum hydrides which affect alkane deoligomerization and metathesis, respectively, at very low temperatures (< 200°C) (Basset, 1999). Additional novel nonbiomimetic-catalytic approaches to primary oxidation of alkanes to alcohols should be investigated by academia. SYNTHESIS OF FINE CHEMICALS The recent increase in the production of fine chemicals has been driven by the increasing number of new pharmaceuticals, many of which are being synthesized as single enantiomers. The fine chemical industry is actively pursuing the use of catalysis in chiral syntheses. Given the high value and strict purity control necessary for manufacturing fine chemicals, product yield and selectivity are important criteria in the design of catalytic processes. The functional complexity of the reaction substrates and products present significant challenges to chemoselectivity, regioselectivity, and stereoselectivity. Catalysis, which has always been an important step in the synthesis of fine chemicals, has become even more important with the advent of rational catalyst/ligand design, the use of high-throughput catalyst screening tools, and the discovery of novel catalytic reactions that provide synthetic versatility and atom economy (i.e., the simplification of substrate structure and minimization of protecting-group techniques). In addition to metallic and organometallic catalysts, enzymes and microorganisms (both biocatalysts) are rapidly becoming attractive for chiral synthesis, especially for specific reaction steps that are difficult to achieve by other chemical methods. Biocatalysis (or biotransformation) is also proving to be valuable in the chemical modification of naturally synthesized compounds (e.g., antibiotics and enzyme inhibitors) that yield high-value fine chemicals.
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Catalysis The identification and exploitation of new catalysts in the synthesis of fine chemicals will require continuing development of enabling technologies. Rapid preparation and screening of candidates by high-speed automation and analytical detection systems will greatly accelerate the identification of novel catalysts, as well as provide efficient optimization within catalyst families. These preparation/screening systems parallel the use of combinatorial techniques in the fields of synthetic and medicinal chemistry. The rational design of metal ligands (the basis for many stereoselective catalysts) will be assisted by advances in computational chemistry towards predicting optimal transition-state behaviors. For heterogeneous catalysts, computational chemistry and the analysis of surface-bound intermediates will improve our understanding of catalytic mechanisms and lead to improved catalysts. And finally, the use of in-situ analytical probes to uncover catalytic reaction mechanisms will lead to better optimization of their yield and selectivity. Synthetic Versatility and Atom Economy Catalytic processes could enable the use of simpler, cheaper substrates while minimizing prefunctionalization or the need for protecting groups. Thus, synthetic versatility would be enhanced without requiring more complex substrates. The development of selective catalytic oxidations using simple oxidants, and catalytic activation of carbon-hydrogen bonds and schemes to generate carbon-carbon bonds would all be of great benefit to the fine-chemical industry. Recommendation. The Office of Industrial Technologies should support the development of catalysts with substantially improved synthetic versatility and atom economy. Selectivity Catalytic selectivity is essential to the synthesis of fine chemicals, where yields of products from high-value substrates are paramount and the minimization of difficult-to-remove impurities can determine the choice of synthetic options. To control regioselectivity and enantioselectivity, R&D should focus on metal ligand design and optimization, by both experimental and computational techniques, especially the secondary and tertiary orientation effects of the metal ligand complexes to optimize the active-site
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effect and, therefore, their effectiveness and selectivity. In particular, the asymmetric hydrogenation of carboncarbon, carbon-oxygen, and carbonnitrogen bonds by organometallic complexes, which is used extensively in fine-chemical processing, could be improved by the development of novel chiral ligands. Selectivity in heterogeneously catalyzed, fine-chemical reactions is also important, and the development by the commercial pharmaceutical industry of novel catalysts, chiral surface modifiers, and fundamental knowledge of reaction mechanisms will lead to improvements in selectivities. Reaction Conditions Successful processing of a catalytic reaction step often involves optimizing of reaction conditions to increase yield and selectivity, as well as careful control of catalyst deactivation and recovery to allow for the recycling and reuse of expensive catalysts. R&D on optimizing reactions might focus on in-situ analytical probes to reveal reaction mechanisms and kinetics, both of which can be used to control selectivity. R&D on novel catalysts, catalytic ligands, and catalyst support substrates to improve the activity and performance of reactions, as well as to improve the retention of catalyst activity and increase catalyst recovery, should be supported by industry. Biocatalysis The efficient development of a biocatalyst for the synthesis of both fine chemicals and bulk chemicals will require the parallel development of three enabling technologies. The first key technology is efficient biocatalyst screening, which will require rapid “analytical” detection methods, particularly as they relate to chirality (e.g., chromatographic separation of race mates). Screening, miniaturization, and automation will also be required to evaluate available and potential biocatalysts. Second, the development of microchip technology for the rapid study of enzyme kinetics under a variety of chemical and physical conditions is very important for rapid process scale-up. Microchips can also enable molecular biologists to identify genes responsible for specific biocatalysts of interest. Finally, data management systems must be developed to ensure that the enormous amount of data being generated from enzyme screening and characterization can be easily retrieved and reviewed in a way that leads to a better understanding of trends in biocatalyst performance.
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A number of separate steps should be investigated in the biocatalyst (enzymatic) process. The first step, and the most critical, is to design enzymes with specific characteristics (e.g., substrate specificity and stereoselectivity in chiral synthesis) to optimize the conversion rate. The second step is to stabilize this enzyme long enough to produce the desired product. The third step is to maintain the enzymatic activity in a nonaqueous environment because the organic synthetic product is often nonaqueous. The fourth step is to maintain the level of reactivity of the enzyme throughout the production period, which can be done by a cofactor generation process. Substrate Specificity and Stereoselectivity Enzymes are well known catalysts that accept not only their specific native substrates but also closely related ones. However, to increase their yield or conversion rate, the fine-chemical industry must learn how to alter their substrate specificity (e.g., their preference for a specific molecular structure as its raw material) to “construct” industrially useful enzymes with perfect stereoselectivity. Fundamental studies of enzyme structures coupled with molecular biology studies will be important for achieving this goal. The committee believes that designing enzymes with specific characteristics (e.g., substrate specificity and stereoselectivity in chiral synthesis) to optimize the conversion rate is the most critical step in biocatalysis. Recommendation. The Office of Industrial Technologies should support the development of enzymes with substrate specificity and stereoselectivity for chiral synthesis in fine chemicals. Enzyme Stability Currently, R&D on improving stability is focused on immobilization through covalent coupling of an enzyme to a polymer, noncovalent gel entrapment, and cross-linked enzyme crystals. Continued research in this area will have a high probability of improving enzyme stability. A fundamental knowledge base will be necessary to achieve stability at the molecular level when a biocatalyst is exposed to various environments. In addition to chemical and physical studies, methods of improving intrinsic enzyme stability through molecular biological approaches, such as directed evolution, should be investigated. The ultimate goal of this R&D is to develop enzymes/microorganisms that will remain stable in altered environments. This R&D is, and should continue to be, supported by universities and industry.
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Enzyme Activity Many chemical intermediates that become enzyme substrates are insoluble in aqueous solutions, requiring that the enzyme system function in a nonaqueous environment. Frequently, this causes a considerable decrease in enzyme activity. Additional studies should be conducted to achieve equal performance in both aqueous and organic solvents, but also to enhance performance in the organic solvents. A number of specific chemical reactions (e.g., transaminations, carbon-carbon bond formation, reductive amination) that are performed with enzymes should be investigated. In the opinion of the committee, enzyme stability in nonaqueous environments is an important subject for further industry and university research. Cofactor Regeneration To ensure that certain important enzymes remain active throughout the reaction, the presence of another component, called a cofactor, is necessary. As the enzymatic reaction takes place, the cofactor component is reduced and must be regenerated to maintain the same level of enzymatic activity throughout the reaction. Although in-situ regeneration with isolated NADH-dependent (nicotinamide adenine dinucleotide based) enzymes has been used, alternatives should be investigated by industry or academia, including molecular biology to modify or eliminate the need for a cofactor. ALTERNATIVE AND RENEWABLE RESOURCES Currently, crude petroleum is the primary source of petrochemicals. As domestic reserves of crude petroleum are reduced, U.S. industries are becoming increasingly dependent on foreign sources, which has greatly compromised the competitiveness of the U.S. chemical manufacturing sector. Foreign oil-producing regions are trying to attract higher value products and higher value manufacturing jobs for their own populations, and the production of petrochemicals in proximity to the sources of crude petroleum gives them a significant cost advantage. In addition, although there is no shortage of crude petroleum today, long-term availability is a concern. In the near term, the U.S. chemical industry is likely to remain competitive because of its technological, infrastructural, and workforce advantages. In the longer term, however, the U.S. will have to find ways to reduce its reliance on foreign oil to remain competitive. The United States still has plentiful reserves of coal and natural gas. Indeed, natural gas, which is plentiful worldwide, is increasingly being used
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in fuels and chemicals. Increasing the use of these domestic resources would somewhat negate the logistical advantages of other oil-producing regions. The large capacity of the U.S. agricultural sector is the source of a large carbon reserve and a source of specialty chemicals that has gone largely untapped by the chemical industry. In the terms of this discussion, alternative resources refers to noncrude-oil-based resources. Renewable resources refers to carbon resources available from biological, especially agricultural, sources. Catalysis will be crucial to using both alternative and renewable resources. Alternative Resources R&D on alternative resources should be focused on the conversion of alternative materials to synthesis gas (a mixture of hydrogen and carbon monoxide) and subsequent conversions. Natural gas and, to a much lesser extent, coal are already being used to make synthesis gas used by the chemical industry: (1) to generate methanol and, in further reactions, with carbon monoxide to generate downstream products (e.g., acetic acid, acetic anhydride, formaldehyde, formic acid); and (2) to functionalize olefins (e.g., via hydroformylation) to generate aldehydes, alcohols, carboxylic acids, and esters. Synthesis gas has several additional, smaller scale uses in the functionalization of various chemicals. However, this potential has not been completely realized. A large number of other potential products (e.g., ethylene glycol, vinyl acetate, acetaldehyde, acrylic acid, ethanol, and isobutanol) have been conceived, demonstrated in the laboratory, and, in some cases, demonstrated on the pilot-plant scale. In many cases, the biggest hurdle to the commercialization of these chemicals is the high capital cost of generating and separating synthesis gas components. Therefore, the highest priority for the chemical industry is to increase the availability and reduce the cost of synthesis gas. Low-Cost Production of Synthesis Gas A large number of processes for the generation of chemicals based on synthesis gas are competitive or nearly competitive with existing technology. Examples include, but are not limited to, the production of ethylene glycol, ethanol, ethyl acetate, acetaldehyde, isobutanol, linear alcohols, and vinyl acetate. The high capital expenditures related to the generation and separation of synthesis gas components are the limiting factor in the implementation of these technologies. Therefore, the development of lower cost processes for generating, separating, and
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delivering the components of synthesis gas, especially synthesis gas from coal, would accelerate the commercialization of these processes, as well as the development of new synthesis gas-based processes for chemicals and fuels. R&D could also focus on using waste products and biomass as feedstocks for synthesis gas. Recommendation. The Office of Industrial Technologies should support a study of alternative, lower cost means of producing synthesis gas from alternative resources. Available Chemicals The chemical industry would greatly benefit from new technologies for the conversion of synthesis gas to chemicals. Most research is currently focused on the generation of oxygenates. R&D should also focus on innovative approaches to increasing the number of materials and their functionality produced from synthesis gas. The committee has strong reservations about using carbon dioxide as a carbon source in the chemical industry because a substantial amount of energy will probably be required to reduce it to an oxidation state useful for organic synthesis. Therefore, it is not likely that carbon dioxide will be a cost-effective source of carbon, except as a means of increasing the carbon content of synthesis gas through the shift reaction or as a reaction solvent. The transportation-fuel industry may provide a strong impetus for shifting toward alternative resources. The transportation industry is now anticipating a need to reformulate transportation fuels to reduce their environmental impact, which could require fuels with a significant oxygen content. It is widely believed that the most likely source of the oxygenated component will be a synthesis gas-derived material. If so, the availability of synthesis-gas will have to be greatly increased, which could provide the infrastructure for bringing these synthetic gas technologies to fruition. Although fuel technology is beyond the scope of this study, the committee encourages the use of these alternative resources in fuels, which will certainly involve catalysis. Opportunities for developing a range of chemicals from alternative resources, especially single-carbon molecules, should be evaluated by commercial industry and academia. Renewable Resources The U.S. agricultural sector has the potential to provide a large volume, as well as a wide variety, of carbon resources that can be continually renewed and may represent the only viable means of
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sequestering carbon dioxide. In addition, the United States has a distinct advantage over other countries in the development of biological and genetic technologies, which should be translatable to an advantage in the development of technologies for the conversion of renewable agricultural resources to chemicals and fuels. The feasibility of biotechnology to deliver economically viable products for the chemical industry from renewable resources was recently demonstrated for 1,3-propanediol (DuPont/Genencor), ascorbic acid (Eastman/Genencor), and NatureWorks R (a biopolymer from DOW/Cargill). The problems facing the development of technologies for the generation of raw materials from renewable resources and their downstream conversion to chemical products on a large scale are similar to those associated with the use of biocatalysis for the generation of fine chemicals. Converting Biomass to Feedstocks and Polymers R&D should focus on more efficient means of converting and purifying biomass components, including (but not limited to) cellulose, sugars, amino acids, and natural polymers (e.g., polylactic acid), both for direct use and for use as feedstocks in biological and chemical conversion processes. Their industrial use will require development in several areas, including microorganisms, biological catalysts (enzymes), and traditional catalysis. Tests on biological systems have shown that transition metals can selectively oxidize an alkane to a primary alcohol under mild conditions (e.g., low temperatures and pressures). However, this enzymatic process cannot yet compete with robust, heterogeneous, inorganic alternatives in terms of production rate and costs. Recommendation. The Office of Industrial Technologies should support the development of processes for converting biomass to feedstocks and polymers. Research should focus on microorganisms, biological catalysts (enzymes), and traditional catalysis. Efficient Use of Carbon Currently, biological techniques require that a large portion of the feedstock be converted to carbon dioxide to drive the chemical processes. It would be useful if alternative means of providing energy, such as through the activation of hydrogen, could be identified. This may require catalysis. Scale-up of biologically based technologies into commercial, continuously operating processes would require significant advances in engineering, particularly in separations technology and waste reduction/handling.
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OLEFIN POLYMERIZATION Technical advances in olefin polymerization catalysis (e.g., metallocene catalysts), which provide low-cost, high-performance materials, have affected a broad range of manufacturing industries and, hence, have had a substantial impact on the U.S. economy. Industry continues to pursue technical and economic progress through R&D in this area, but many critical challenges remain to be met for improved product versatility in highperformance engineering plastics, improved surface properties, and improved environmental compatibility. Copolymerized Olefins with a Diverse Class of Polar Unsaturated Monomers R&D should focus on the development of active catalysts to polymerize olefins containing polar unsaturated monomers and to copolymerize unsubstituted olefins with olefins that contain polar substituents (e.g., carbonic, ester, ether, nitrile). The goal is to improve the properties and expand the applications of economical polymers based principally on olefins. Potential applications range from replacements for polyvinyl chloride and acrylonitrile butadiene styrene to new properties, including solvent resistance, high-temperature use, toughness, controllable surface properties, optical clarity, and “smart” polymers that respond to environmental conditions, enable easy mold release, or improve adhesion and paintability. Polyolefin chemistry, including heteroatoms, such as silicones, will provide polymers with desirable properties, especially biocompatibility or conversely hydrophobic properties. The development of multifunctional polymeric systems could provide polymers that are self-healing (capable of overcoming oxidation, depolymerization, cross-link, degradation, embrittleness) or that respond to changing environmental conditions. New ligand synthesis via synthetic combinatorial techniques would accelerate progress and improve the efficiency of research. Precious metal replacements and improved efficiencies of late-transition metals would also be helpful. Recommendation. The Office of Industrial Technologies should support the development of catalysts that can copolymerize olefins with a diverse class of polar unsaturated monomers.
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Tolerant Catalysts The development of high-performance polyolefin and copolymer catalysts that are tolerant of common impurities (e.g., water, amines, and sulfur) could increase the flexibility and efficiency of manufacturing processes. These catalysts could function in a variety of solvating media, including alcohols and water. R&D should be focused on more efficient and selective catalysts, particularly for copolymer systems. Recommendation. The Office of Industrial Technologies should support the development of catalysts that are tolerant of common impurities, such as water and amines. Macromolecular Architectures and Thermoplastic Elastomers Concepts for macromolecular architectures have been demonstrated. R&D should now focus on development of a robust, versatile catalytic system with a macromolecular architecture that can be controlled by monomer and catalyst design combinations. R&D on new macromolecular structures that expand the current limits of polymer properties should be funded by the chemical industry to open new markets for engineering materials. Polymer Recycling Current uses for recycled polymers and unreacted monomers are very limited. The specific properties of polymers and controlled reactivity will be required for efficient recycling. OIT could work with the Environmental Protection Agency or other government agencies to identify additional uses (markets) for recycled polymers that would encourage the chemical industry to invest in recycling processes. Academia and industry should take the lead in this area. ALKYLATION TECHNOLOGY Two major areas are of interest in the fields of petroleum and petrochemicals. The first is aromatic alkylation to prepare petrochemical intermediates, such as ethylbenzene and cumene. The second is paraffinolefin alkylation for the manufacture of motor fuels. The development and introduction of zeolite catalysts in the manufacture of ethylbenzene and cumene has resulted in markedly
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improved selectivity, reduced by-products, and the elimination of environmental and corrosion problems. Therefore, there is little economic or environmental incentive for the development of catalysts in this area. In the alkylation process of paraffin-olefin, there is an incentive to eliminate the environmental hazards of the existing technology. A few new catalysts that are more environmentally friendly have been developed, but they have poorer performance than hydrogen fluoride and sulfuric acid. Research to discover and develop an environmentally clean catalyst system, such as solid catalyst with performance equal to hydrogen fluoride and sulfuric acid, would be beneficial to the petroleum industry. Ultrahigh Selectivity Highly selective alkylation processes would increase carbon efficiency and minimize separation and recycling requirements for solid-supported acid or base catalysts. Capital and operating costs would also be reduced dramatically for the synthesis of fine chemicals, aliphatic and aromatic alkylation, and pharmaceutical intermediates. Improved catalysts would simultaneously improve economics and carbon efficiency and minimize environmental impact. The use of highly selective solid catalysts will most likely also require innovations in process technologies. Recommendation. The Office of Industrial Technologies should support the development of catalysts with ultrahigh selectivity for chemicals and fuels alkylation to reduce by-products and minimize environmental impact. Tolerance to Functional Groups Replacements for common Lewis acids, such as boron trifluoride or aluminum trichloride, would improve efficiency and increase carbon productivity in alkylation processes. Current systems are intolerant of polar functional groups, in which the Lewis acid loses its catalytic property. Lewis acid systems (e.g., transition-metal complexes) should be studied to explore the feasibility for enhanced acid catalysis with tolerances for carbon moieties with polar functional groups. Recommendation. The Office of Industrial Technologies should support the development of catalysts with tolerance to functional groups.
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Reactivity The formation of carbon-carbon bonds is a critical technology with widespread applications and extensive economic impact. Replacements of hydrogen chloride, hydrogen fluoride, and sulfuric acid with solid acids has been delayed by the instability and low number density of acid sites in solid acids. New technologies would increase active-site density, improve stability, or renew surface reactivity. R&D in this area should be supported by industry and academia. ENVIRONMENTAL APPLICATIONS Maintaining the quality of the environment may be the most serious challenge facing the world today. This can be demonstrated from several perspectives. In the continental United States, the federal Clean Air Act of 1990 mandates that a minimum level of air quality be maintained for good health and quality of life. In 1996, substantial portions of the United States did not meet these requirements and, therefore, were classified as nonattainment areas. The population of these areas totaled 113 million people (Environmental Protection Agency (EPA), 1996). It is estimated that by the end of 2000 as much as 60 percent of the population of the United States may reside in nonattainment areas. It is also estimated that the underdeveloped portion of the world is inhabited by 70 percent of the population but currently consumes only 20 percent of the world’s resources. As underdeveloped countries attempt to raise their standards of living, they will also increase their per capita energy consumption, which may substantially increase the environmental burden. A major source of the environmental burden is the combustion of fossil fuels, which results in the emission of nitrogen oxides (NOX), unburned hydrocarbons, and carbon dioxide. The challenge is to reduce these emissions while still allowing industrial growth and higher standards of living. Technology development can contribute to this objective by reducing the pollution from existing means of energy production and by increasing the cost competitiveness of more efficient means of energy production. In the short term, technology for controlling emissions of NOX could reduce emissions from vehicle and stationary sources and enable the widespread use of high-efficiency diesel and lean-burning gasoline engine technologies. These technologies can improve energy efficiency by 20 to 30 percent. In the long term, catalytic technology could speed up the commercialization of fuel cells with substantial improvements in fuel efficiency and markedly lower pollutant emissions. Fuel cells may provide an entirely new mass-produced, energygeneration technology for vehicle
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and stationary power generation. R&D could also focus on the development of a physical understanding of, and quantitative data on, the thermal aging process that occurs in high-temperature catalytic systems. A better quantitative understanding of emissions control, catalytic combustion, and enhanced fuel processing in fuel cells and other processes would have widespread benefits. Pollution Control for Mobile Applications Modern three-way catalysts simultaneously reduce emissions of carbon monoxide, hydrocarbon, and NOX from gasoline-fueled internal-combustion engines operating at the stoichiometric air-fuel composition. Leanburning engines and diesel engines offer fuel economy advantages of 20 to 50 percent, depending on the operating mode or usage cycle. Because lean-burning gasoline engines and diesel engines operate in a fuel-lean mode resulting in high levels of exhaust oxygen, three-way catalyst technology is not applicable for NOX control. In stationary combustion processes with exhaust streams containing high oxygen levels, ammonia-based reductants are very effective but are not attractive for transportation applications because of the toxicity of ammonia. The amount of NOX in lean-engine exhaust environments cannot be controlled by NOX decomposition, by reduction of the NOX with an added hydrocarbon, or by any other current catalyst technology. The availability of a catalyst that could control NOX emissions would enable the rapid development and implementation of engines with increased fuel efficiency, lower pollution, and decreased greenhouse-gas emissions. Another area for R&D would be control of emissions of particulate carbon or soot from diesel engines. Control of Nitrogen Oxides in Lean-Exhaust Environments Catalyst systems using hydrocarbon reductants have been intensively investigated but without success. Future R&D could be focused on nonconventional, speculative approaches. High-throughput testing could be used to identify catalyst compositions for further development; water vapor, trace levels of sulfur, and initial catalyst deactivation would have to be taken into account. R&D should also focus on the development of detailed reaction kinetics and an understanding of reaction mechanisms. OIT should only support work that evaluates catalysts under realistic exhaust-gas conditions and includes measurements of the detailed reaction kinetics.
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Recommendation. The Office of Industrial Technologies should support a study to evaluate “step-out” innovative catalyst strategies for controlling of nitrogen oxide emissions in lean environments. Control of Particulate Emissions Despite substantial efforts, no satisfactory method of controlling particulate emissions from diesel engines has been developed. Porous, ceramic-wall, flow filters can effectively remove particulates, but the buildup of carbon increases the pressure drop in the filter, and oxidation of the collected carbon results in excessive temperatures and short filter life. Innovative catalytic approaches to controlling diesel particulates could include using fuel additives that lead to a catalytic component in the diesel exhaust. R&D should consider cost, the possible creation of a new pollutant species, and the effect of the additive on the engine. Approaches that do not require a fuel additive might be developed based on studies of the oxidation of solid carbon on catalytic surfaces. OIT could coordinate its efforts with those of the EPA and other federal agencies to evaluate innovative approaches to controlling of diesel particulates. Catalytic Sensors Any engine or power plant equipped with technology for controlling pollution will most likely have to be equipped with sensors (onboard diagnostics) to improve engine control and to assess whether the pollution system is functioning properly. Current configurations include oxygen sensors to monitor hydrocarbon removal by three-way catalysts. This works well when hydrocarbons are high but not when emissions are reduced. Hydrocarbon sensors based on the combustion of the hydrocarbon species might be used, but they would have to be accurate enough to detect extremely low hydrocarbon concentrations consistent with emission regulations for modern engines. This technology would also be applicable to a wide variety of combustion systems, as well as to the control and optimization of combustion processes. (Several IOF industries identified a need for sensors in fuel cells and fuel-processing systems for fuel cells.) Measuring Combustion Exhaust Streams R&D should focus on the development of sensors capable of measuring NOx, carbon monoxide, and unburned hydrocarbon at
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concentrations ranging from 1 to 1,000 parts per million (ppm), with a target of 1 to 25 ppm for all three pollutants. Sensors should be tested with realistic gas compositions and temperatures. This R&D could be done by interdisciplinary groups with expertise in the sensing platform, electronics and data handling, catalytic processes, and the synthesis of catalytic materials and should be supported by industry. Monitoring Fuel Quality Proton-exchange membrane (PEM) fuel cell systems are extremely sensitive to sulfur compounds and carbon monoxide. The presence of sulfur compounds at the 1 ppm level will shorten the life of fuel processor system catalysts. Carbon monoxide must be below 10 ppm for fuel cell electrode performance to be acceptable. In both cases, a sensor would ensure proper system performance and system control in case of an upset in inlet conditions. Interdisciplinary R&D on sensors is likely to have substantial payoffs and should be supported by industry. Fuel Cell Systems Significant advances have been made in the development of the PEM and solid- oxide fuel cell systems, which are the prime candidates for the next generation of stationary applications and vehicles fueled by natural gas and liquid fossil fuels. PEM fuel cell systems are especially attractive for vehicles and small dispersed-power applications. Solid-oxide fuel cells can use hydrocarbon fuels, especially methane, but PEM systems require hydrogen fuel that is free of sulfur and has low concentrations of carbon monoxide. Ideally, hydrocarbon fuels could be used with systems on board the vehicle to convert the hydrocarbon fuel to a hydrogen stream with the required purity. R&D could focus on efficient, durable systems for converting liquid hydrocarbon fuel to hydrogen. Although fuel-processing technologies are already being commercialized on a large scale and are widely used in the chemical and petroleum industry, reducing these technologies to compact, fast-response systems on board vehicles will require significant advancements. New systems will also be required to convert natural gas for stationary, dispersed-power generation, and to convert liquid fuels for vehicles.
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Converting Hydrocarbon Fuels to Hydrogen Continued development of innovative steam reforming and partial-oxidation systems could yield significant reductions in the size of processing units and decrease response times. Industry is hoping for nonpyrophoric catalyst systems, including reforming and shift catalysts, to meet the demands of small fuel-processing systems that can operate intermittently. Advanced research and innovative “step-out” approaches should be considered and supported by industry. Metal-Sintering Processes of Supported Metal Catalysts Supported metal-catalyst systems are used in numerous industrial processes important to a clean environment and to industry in general, such as fuel cell electrode catalysis, automotive emissions control, fuel processing to produce hydrogen for fuel cells, and a variety of other petroleum and chemical processes. Supported-metal catalysts are subject to loss in activity from a variety of mechanisms, including chemical poisoning and thermal sintering. In many processes, especially those operating at high temperature, the predominate mechanism of activity loss is thermal sintering. Although some work was done in this area with the advent of automotive emissions control in the early 1970s, the sintering process of both the support and the supported metal catalyst is not well understood. Companies directly involved in the development of automotive emission-control catalysts have developed practical solutions that minimize sintering, but thermal deactivation remains a significant deactivation mode for catalytic converters. A fundamental understanding of the sintering of both the substrate and catalyst is critical for processes using supported noble-metal catalysis under hightemperature conditions. This understanding would accelerate the development of current and next-generation materials. Mechanistic Understanding of the Sintering of Metals on a Support The committee believes OIT should fund a program with a comprehensive approach to developing a quantitative kinetic understanding of the sintering of metals on supports. The approach should include the development of a physically realistic sintering mechanism based on elementary chemical steps, followed by the measurement of kinetics for these processes. This multiyear effort should involve interdisciplinary groups and should be reviewed periodically to assess whether it is addressing proposed objectives.
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Recommendation. The Office of Industrial Technologies should support the development of a basic understanding of the sintering of supported metals. Model System A study of the sintering of supported metals will be limited by an inability to measure the sintering process with well characterized materials. A model system, such as a planar polycrystalline-oxide surface with deposited metal particles, could provide a convenient system for obtaining sintering data via transmission electron microscopy, scanning electron microscopy, or tunneling microscopy. An interdisciplinary team could provide both the catalysis and the instrumentation (e.g., electron microscopy or tunneling microscopy) capabilities. The committee believes that commercial corporations and universities should investigate and, if appropriate, use planar model systems to study the sintering of supported metals.
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3 Policy-Related Issues
The continued growth of the U.S. chemical industry in an increasingly competitive global market will depend on the continuous development and implementation of leading-edge technologies that enable U.S. chemical producers to deliver safer, better, and cheaper products. In the past, growth was dependent on informal, quasicooperative interactions between the three principal sectors of the U.S. research infrastructure: academia, government, and industry. This infrastructure can provide a pool of talent for continuing the tradition of innovation and productivity. DOE, the National Aeronautics and Space Administration, the U.S. Department of Commerce, and the U.S. Department of Defense have encouraged cooperative R&D via agreements that have stimulated strong interest in industry, academia, and government. Unfortunately, because of complex funding mechanisms and uncertainties about ownership of proprietary information, this approach may no longer be viable. The number of agreements, which peaked at more than 500 in 1994, had dropped to approximately 100 in 1996 (Via, 1998). The committee encourages industry and academia to take advantage of the tremendous capabilities of the national laboratories, especially for interdisciplinary research, to expand the limits of science and technologies in the national interest. This will require that issues related to intellectual property be resolved. From industry’s point of view, approaches such as those practiced by the Advanced Technology Program (ATP) of the National Institute of Standards and Technology, could serve as a model for expanded programs at DOE national laboratories. ATP addresses the issues most important to industry: ownership of intellectual properties and proprietary information. Large companies and small business have different needs. While the interests of large companies are focused on intellectual property rights, the interests of small businesses, except for biochemical and biomedical companies, tend to be focused on ensuring access to experts who can answer questions. These differences were the subject of discussion at OIT Customer Day (February 16, 2000). Under ATP, an industry can either
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own or have the first right of refusal to technologies developed by the industry-government partnership. The industry partner also has the right to license the technology to a third party. In this respect, these partnerships differ from the cooperative R&D agreements (CRADAs), under which government owns the intellectual properties, and licensing details are negotiated between the parties. INNOVATION In the last decade or so, as a result of changes in financial markets and the global economy, industry has shifted the focus of its research to short-term process and product development to meet specific needs. The committee believes that OIT, unlike industry, should fund R&D on high-risk, innovative approaches that have high potential payoffs to address targeted needs well into the future. Catalysis, although critical to the chemical industry, is also a component of a number of other national critical technologies and is vital to energy security (Jackson, 2000; Phillips, 1991). Therefore, governmentsupported research would be in the national interest, as long as it is focused on precompetitive, high-risk, innovative research. Short-term, applied research should continue to be supported by industry. Recommendation. The Office of Industrial Technologies should support precompetitive, high-risk, innovative research that has a high potential payoffs of addressing targeted industry needs. COMPUTATIONAL TECHNOLOGY, COMBINATORIAL CHEMISTRY, AND DATA MANAGEMENT High-throughput computational screening has advanced catalytic science, but this technology has not been widely used for the rapid synthesis of a multicomponent catalysts. In addition, combinatorial chemistry could be expanded to enable rapid screening of the chemical properties produced from these new catalysts, as well as to evaluate properties, such as rheology and other physical properties, from small-scale samples. The use of computational technology for predicting the effect of a catalyst on a chemical structure and its performance remains elusive. Advancement of this tool will have a broad impact on catalytic research and the entire chemical industry. Recommendation. The Office of Industrial Technologies should assist industry in supporting the development of improved high-throughput
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screening and computational technologies that will benefit the entire chemical industry. FUNDING FOR CATALYSIS RESEARCH Catalysis and related process technologies are critical to the U.S. chemical industry, as well as the rubber, cement, pharmaceutical, and petrochemical industries. Catalysis is involved in more than 25 percent of the U.S. gross domestic product and is critical to the manufacture of more than 60 percent of industrial products. Industry still provides a significant percentage of total funding for catalysis R&D. The committee estimates that approximately $1 billion is spent annually on catalysis research, at least 90 percent of which is geared toward short-term applied research, process and product development, environmental issues, and technical supports. According to the National Science Foundation, of the $158 billion allocated for industrial research in 1997, 6.6 percent was spent on exploratory, basic research, 20 percent was spent on applied research, and 73 percent was spent on development (NSF, 1997). Currently, federal funding for catalysis research comes mainly comes from DOE and the U.S. Department of Commerce (supplemented by the National Science Foundation) through ATP (see Table 3-1 ). Funding by OIT (shown in Table 3-2 ) for catalysis research is estimated to be about one-third of OIT’s total budget for chemical research. TABLE 3-1 Funding by the U.S. Department of Commerce for Catalysis Research Year
Amount ($ millions)
Number of Projects
1994
3.99
2
1995
50.69
9
1997
1.72
1
1998
5.93
3
1999
29.48
2
Source: ATP, 2000. OIT’s budget of approximately $4 million is used to support 20 catalysis research projects. If the number of projects were reduced and the R&D coordinated with R&D by other federal agencies, the combined budget would achieve a critical mass to support many high-impact research projects.
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TABLE 3-2 Funding by OIT for Chemical and Catalysis Research Year
Chemical Research ($ millions)
Catalysis Research ($ millions, estimated)
1998
11.4
3.5–4.0
1999
12.4
4.0
2000
12.5
4.0
2001 (projected)
12.5
4.0
Source: OIT, 2000. Recommendation. The Office of Industrial Technologies should consider reducing the number of projects it funds and coordinating its projects with those of other federal agencies to provide enough critical mass to support innovative research in many areas. PROPOSAL REVIEW PROCESS It is essential that industry involvement be promoted in the proposal review process. Currently, all proposals are reviewed by committees with members drawn from academia and national laboratory staff, with some level of participation by industry. In addition, the review process is inefficient. Even though many CRADAs are small (in the range of $100,000), it may take as long as a year for a proposal to be approved. In addition, industry is required to submit a complicated, lengthy proposal. As a result, the level of industrial participation is declining. OIT could adopt a two-step approach to streamlining the process, a preliminary review step and a final review step. The preliminary review would require evaluating short, focused proposals (two to five pages) describing the problem to be addressed, the current state of technology, the innovative approach to be taken, and a paragraph describing the contributions expected of each team member. The proposals selected for further consideration would be followed by longer proposals (10 to 15 pages) addressing the critical issues. This approach would encourage broad-based participation by the academic and industrial scientific community and would improve the efficiency of the proposal process. Recommendation. The Office of Industrial Technologies should promote industry involvement in the proposal review process and also streamline this review process.
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POLICY-RELATED ISSUES
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PROGRAM METRICS The value of OIT’s research program would be enhanced by the establishment of aggressive objectives and a formal assessment process. At the moment, OIT uses an informal assessment procedure judging the success of a program by the number of papers published or patents issued. The committee believes the assessment should be based on the impact of the developed technology on real applications. Each program should undergo a formal annual review, as well as semiannual assessments by industry participants. The assessments should include both performance-specific targets and increases in the knowledge base that could become a basis for future research. At the termination of a program, an overall assessment should be made to provide internal guidance for future proposals and programs. Recommendation. The Office of Industrial Technologies (OIT) should establish aggressive objectives and procedures for assessing the progress of each program. Programs should be formally reviewed annually by OIT and semiannually by industry participants. RESEARCH CENTERS The U.S. catalyst research community is facing increased global competition from private and governmentsupported research centers in Europe and Japan. Britain, the Netherlands, Germany, and France have all established government/industry research centers to maximize available funding and talent. The Institute for Environmental Catalysis at Northwestern University as one response by the U.S. government to multidisciplinary academic/industry initiatives in Europe and Japan. In addition, the national laboratories have valuable capabilities and facilities for catalysis research, such as chemical kinetics instrumentation, molten carbonate fuel cells, scalable computing (Ames Laboratory), bioprocessing (Oak Ridge National Laboratory), computational science membrane reactors (Argonne National Laboratory), biocatalysis engineering (Brookhaven National Laboratory), biocatalysis and photocatalysis thermochemistry (National Renewable Energy Laboratory), energy-research scientific computing, combinatorial chemistry (Lawrence Berkeley Laboratory), chemical process development, biocatalysis, plasma exhaust catalysis (Pacific Northwest National Laboratory), high-performance computing, reactor hydrodynamics, polymerization catalysis (Sandia National Laboratories), high-performance computing, supercritical fluids, fuel cells, biocatalysis (Los Alamos National Laboratory).
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POLICY-RELATED ISSUES
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Based on these capabilities, a number of virtual centers of excellence could be created to enhance collaborative research and knowledge integration. Such a strategy could be coordinated by trade associations, like the ones that developed Vision 2020. National laboratories, industry, and academia would all greatly benefit from this interaction. Addressing the multidisciplinary problems associated with surface, analytical, inorganic, organometallic, and synthetic chemistry, as well as the engineering requirements for developing new catalytic science and technologies, will require a critical mass of talent and funding. Despite the high overhead of the national laboratories compared to academic or industry facilities, the national laboratories offer unique capabilities. Overhead might be reduced by drawing on the pool of talented postdoctoral fellows who could work under the guidance of national laboratory staff for a nominal cost. Team members need not be in the same location. Many large chemical companies already have virtual catalyst research centers with members located in company laboratories around the world. Recommendation. The Office of Industrial Technologies should encourage and facilitate the formation of “virtual catalyst research centers” based on the unique capabilities of the national laboratories.
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REFERENCES
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References
ATP (Advanced Technologies Program). 2000. Available on line at: http://www.atp.nist.gov/ ACS (American Chemical Society). 1996. Technology Vision 2020: The U.S. Chemical Industry. Washington, D.C.: American Chemical Society . Arne, M. 1986. Ethylene by the Oxidative Dehydrogenation of Ethane. PEP Review 85-2-2. Menlo Park, Calif.: SRI International. Barton, D.H.R. 1993. The Activation of Dioxygen and Homogeneous Catalytic Oxidation. New York: Plenum Press. Basset, J.M. 1999. Oxide supported surface organometallic complexes as a new generation of catalysts for carbon-carbon bond activation . Journal of Applied Catalysis 182 A(1): 1–8. DOC (U.S. Department of Commerce). 1996. Meeting the Challenge: The U.S. Chemical Industry Faces the 21st Century. Washington, D.C.: U.S. Department of Commerce. EPA (Environmental Protection Agency). 1996. The Green Book: Non-Attainment Areas for Criteria Pollutants. Available on line at: http:// www.epa.gov/oar/oaqps/greenbk/ Gupta, M., C. Hagen, W.C. Kaska, R.E. Cramer, and C.M. Jensen. 1997. Catalytic dehydrogenation of cycloalkanes to arenes by a dihydrio Iridium P-C-P pincer complex. Journal of the American Chemical Society 119 (4): 840–841. Haruta, M. 1997. Copper, silver and gold in catalysis. Catalysis Today36(1): 153–166. Haynes, V.F. 1998. Vision 2020 Catalysis Report: Roadmap for Research on Catalysis. Brecksville, Ohio: The B.F. Goodrich Company. Jackson, N.B. 1997. Catalyst Technology Roadmap Report. SAND97-1424. Albuquerque, N.M.: Sandia National Laboratories. Jackson, N.B. 2000. Partnership at the National Laboratories: Catalysis as a Case Study. Pp. 97–113 in Research Teams and Partnerships. Washington D.C.: National Academy Press. Keller, G.E., and M.M. Bhasin . 1982. Synthesis of ethylene via oxidative coupling of methane. Journal of Catalysis. 73: 9. National Science Foundation. 1997. Available on line: http://www.nsf.gov/search97cgi/vtopic.
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OIT (Office of Industrial Technologies). 2000. Available on line at: http://www.oit.doe.gov/ Periana, R.A., D.J. Taube, S. Gamble, H. Taube, T. Satoh and H. Fuji. 1998. Platinum catalysts for the high-yield oxidation of methane to a methanol derivative. Science 280 : 560–564. Phillips, W. 1991. First Report of the National Critical Technologies Panel. Arlington, Va.: National Critical Technologies Panel. Rulkens, R. , and T.D. Tilley. 1998. Molecular precursor route to active and selective vanadia-silica-zirconia heterogeneous catalysts for the oxidative dehydrogenation of propane. Journal of the American Chemical Society 120: 9959–9960. Shilov, A.E. 1984. Activation of Saturated Hydrocarbons by Transition Metal Complexes. Dordrecht, The Netherlands: D. Reidel Publishing Co. Thorsteinson, E.M. 1981. Low Temperature Oxydehydrogenation of Ethane to Ethylene. U.S. patent 4250346, 10 February 1981. Union Carbide Corporation. Via , F.A. 1998. Challenges and Opportunities for Chemical Research in the 21st Century: An Industrial Perspective. Pp. 137–162 in Chemical Research: 2000 and Beyond, edited by P. Barkan. Washington, D.C.: American Chemical Society.
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APPENDIX A
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Appendix A Invited Speakers
November 9, 1999 Program Overview of DOE’s OIT James Quinn Office of Industrial Technologies Catalysis Program at OIT Brian Valentine Office of Industrial Technologies January 27, 2000 INSITE® and Other Single-Site Polyolefin Catalyst Technology James Stevens Dow Chemical Company Biocatalysis Research Robert Dorsch E.I. du Pont de Nemours and Company Catalysis Research in U.S. DOE National Laboratories Thomas Baker Los Alamos Laboratory Catalysis Research in Fine Chemicals Tom Verhoeven Merck and Company, Inc. Environmental Catalyst Research Ronald Heck Engelhard Corporation
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APPENDIX A 46
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APPENDIX B
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Appendix B Biographical Sketches of Committee Members
Stanley A. Gembicki (chair) is chief technology officer at UOP Corporation, where he has worked for 27 years. Dr. Gembicki has broad expertise in chemical engineering research, the development of new applications for catalysts, and the commercialization and scale-up of new catalytic processes. He has held numerous positions, including head of catalyst development, head of separation-process development, director of process research, and director of research, where he oversaw a redesign of UOP’s research and development program. He is UOP’s representative to the Industrial Research Institute and the Council of Chemical Research and is currently a member of the International Scientific Board for the 12th International Congress on Catalysis. Ralph A. Dalla Betta is vice president of Catalytica, Inc., where he has worked for 23 years, and vice president and chief scientist of Catalytica Combustion Systems, Inc. While at Catalytica, he has been involved in the development of Fischer-Tropsch catalyst systems with high selectivity for selected product fractions, highperformance, catalytic sensor systems for combustion-system monitoring, low-cost catalytic processes for the manufacture of pharmaceutical intermediates, and other specialty chemicals, rapid methods of catalyst characterization, the preparation and production of high-stability catalytic materials, including noble metal catalysts, and the development of catalytic combustion catalysts and combustion-system components. He is a member of the American Chemical Society and the North American Catalysis Society. Francis G. Dwyer retired in 1993 as senior scientist and manager of catalysis research and development at the Mobil Research and Development Corporation, where he had worked for 40 years. He is currently a consultant to the chemical industry. During his career, he has been intimately involved with the research, development, and commercialization of catalysts, the introduction and development of zeolite catalysts in the catalytic cracking technology associated with ZSM-5 catalysts. He is a member of the of petroleum, and the development of the broad catalyst and process National Academy of Engineering and is currently chair of the National
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APPENDIX B
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Research Council Standing Committee on Program and Technical Review of the U.S. Army Soldier and Biological Chemical Command. Robert J. Farrauto is a research fellow at Engelhard Corporation, where he has worked for 24 years. His research interests include the development of catalysts for environmental applications for stationary and mobile sources, fuel processors for fuel cells, and the production of nitric acid. Dr. Farrauto is the author of more than 60 journal articles and coauthor of two books, one on the fundamentals of industrial catalytic processes and one on catalytic air-pollution control. He holds more than 25 U.S. patents and is a member of the American Chemical Society and the American Institute of Chemical Engineers. Dr. Farrauto is the North American and South American editor of Applied Catalysis B: Environmental. Randolph L. Greasham is director of bioprocess research and development at Merck and Company, where he has worked for 16 years. Previously, he worked at the International Minerals and Chemical Corporation for 10 years in research and management positions. His research interests include biological catalysis, fermentation biochemistry, and microbial genetics. Dr. Greasham is the author or coauthor of 40 journal articles and six book chapters and holds one U.S. patent. He has served on the advisory board of the Center for Biocatalysis and Bioprocessing at the University of Iowa and the National Institute of Health Biotechnology Training Program Review Committee. He is a member of the American Chemical Society, the American Society of Microbiology, and the Society of Industrial Microbiology. James F. Roth retired from Air Products and Chemicals, Inc., as corporate chief scientist and founder and director of the Corporate Science Center. Prior to his tenure with Air Products, Dr. Roth spent 20 years as a scientist and research director with Monsanto Company. He is currently a consultant to the chemical industry. He brings to the panel his broad industrial experience in the scale-up and commercialization of catalytic processes, as well as his knowledge of the chemical intermediates industry. He is the author of more than 35 papers and holds numerous U.S. and foreign patents. He was associate editor of Applied Catalysis and a member of the editorial board of Catalysis Today. He has received numerous awards, is a member of the National Academy of Engineering (NAE), and has served on the National Research Council Committee on New Directions in Catalyst Science and Technology and the NAE Chemical Engineering Peer Committee.
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APPENDIX B
49
Martin B. Sherwin is currently managing director of ChemVen Group, Inc., which he founded in 1996. Prior to this, Dr. Sherwin was with W.R. Grace and Company for 17 years, where he was vice president and president for five years of the Commercial Development Division, a new ventures operation. Before that he was executive vice president of the Research Division. For 14 years prior to joining W.R. Grace and Company, he was a member of the team that formed and built Chem Systems, Inc., an international consulting and research firm in the chemicals sectors, where he held several key positions. Earlier he spent five years at Halcon International in the areas of petrochemical process development, design, and start-up. Dr. Sherwin has developed a wide range of products, including first-of-a-kind petrochemical processes and catalysts, spiral wound-polymer membranes for natural gas purification, biopesticides, and metal-supported auto catalysts. He is a fellow of the American Institute of Chemical Engineers, a member of the American Chemical Society, a member of the National Academy of Engineering, and a member of the National Research Council Board on Chemical Sciences and Technology. Francis A. Via has been manager of catalyst research at the GE Corporate Research and Development Center in Schenectady, New York, since 1988. Prior to joining GE, Dr. Via held a variety of positions at Stauffer Chemical Company, including group leader, Organic Synthesis; section manager, Catalyst and Materials Research; and assistant to the director. In 1988, he became director of contract research for the newly created corporate research programs in the United States. In this capacity, he was responsible for cooperative discovery research with universities and national laboratories in catalysts, polymers, materials, and biotechnology. Dr. Via is a fellow of the American Association for the Advancement of Science, and a member of the Chemical Sciences Roundtable of the National Academy of Sciences. He has been a board member of the Council of Chemical Research, chair of the External Research Director’s Network of the Industrial Research Institute, and a member of several professional committees for government-industry collaborative research. Barbara K. Warren was named manager of recruiting, workforce planning, and university relations at Union Carbide in 1998 after 24 years in the Research and Development Department. Dr. Warren has undertaken fundamental research on heterogeneous catalysis (including methane oxidation to ethylene and fuels, propane and ethane oxidation, catalyzed hydrocarbon cracking, direct propylene epoxidation, mechanisms of ethylene epoxidation, catalyzed ethylene oxide hydrolysis, olefin metathesis, and mechanisms of alkoxylation) and homogeneous catalysis (including ethanol from synthesis gas and ethylene glycol from synthesis
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APPENDIX B
50
gas). In addition, she has designed and built pilot plants and developed and automated continuous reactors. She is the author of eight technical publications, the coeditor of a book, and holder of eight U.S. patents. Dr. Warren has been an officer of the Tri-State Catalyst Society and the North American Catalysis Society and has chaired a division of the American Chemical Society, where she organized five international symposia. She is also a member of the American Institute of Chemical Engineers. Joseph R. Zoeller is a research associate in the Chemical Processes Research Laboratory at Eastman Chemical Company, where he has worked for 18 years. He brings to the panel expertise in catalytic process technologies and experience in the chemical-intermediates industry. Dr. Zoeller’s current research interests include new catalysts and processes for the generation of acetic acid, acetic anhydride, methyl acetate, propionic acid, and propionic anhydride from synthetic gas. He is the author of 16 journal articles and five book chapters, coeditor of a book on acetic acid and its derivatives, and holder of 34 U.S. patents, with 20 additional patents pending. He is a member of the American Chemical Society, an associate editor of Catalysis Today, and a member of the Board of Advisors of Industrial Catalysis News.
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GLOSSARY
51
Glossary
alkane activation alkylation technology asymmetric and chiral synthesis alternative resource atom economy biomimetic catalyst cofactor regeneration
the selective functionalization of the carbonhydrogen bond in paraffins to make either a useful hydrocarbon product or an organometallic intermediate catalytic processes for reacting paraffins with olefins to produce higher molecular-weight paraffins the synthesis of molecules with one or more asymmetric (synonymous with chiral) centers a noncrude-oil-based resource getting higher yields without having to use protecting groups, as well as producing stoichiometric by-products, especially salts (which must usually be disposed of) a synthetic catalytic system that uses biological systems as a model to simulate or reproduce the action or active site of an enzyme (e.g., porphyrins with a macrocycle possessing ternary structure) some enzyme reactions require a cofactor, such as nicotinamide adenine dinucleotide (NAD+), to catalyze a reaction, yielding a reduced cofactor (NADH); the oxidized form of the cofactor may be regenerated by using the reduced cofactor in an NADH-dependent enzyme reaction
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GLOSSARY
enantiomeric entity enzyme stability enzyme activity fine chemical ligand
an optically active isomer a measure of enzyme resistance to various environmental parameters, both physical and chemical acceleration of reactions by decreasing the free energy of activation a high-value, low-volume chemical (e.g., a pharmaceutical) 1. In inorganic chemistry, a molecule or ion that binds to a metal cation to form a complex. 2. In biochemistry, a molecule that binds to a receptor, having a biological effect. macromolecular archi- the three-dimensional topology and structure of large molecules, such as enzymes or polymers tecture olefin polymerization the combination of olefins to produce high molecular-weight polymers racemate a one-to-one mixture of enantiomeric molecules; it has a zero optical rotation regiospecificity specificity for a particular region of a molecule renewable resource a carbon resource available from biological or agricultural sources selective oxidation the oxidation of hydrocarbons to produce oxygenates with minimal side reactions and minimal carbon dioxide formation stereochemistry a description of the three-dimensional spatial relationships between atoms in a molecule stereoisomer two or more molecules with identical molecular formulas but different spatial orientations
52
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GLOSSARY
stereospecificity stereoselectivity
53
specificity for a particular stereoisomer preference for a particular stereoisomer, commonly applied to molecular binding, reaction kinetics, etc. substrate specificity preference for a particular reactant, applied to an enzyme’s preference to react with a particular compound(s) synthetic versatility a synthesis technique generally employing a reagent or catalyst that causes a reaction and has broad applicability thermoplastic elastomer an elastic polymer that softens or melts on heating and becomes rigid again on cooling
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GLOSSARY 54
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ACRONYMS
ATP
CRADA
DOE
NOx
IOF
OIT
PEM
ppm
R&D
55
Acronyms
Advanced Technical Program cooperative research and development agreement U.S. Department of Energy nitrogen oxides Industries of the Future Program Office of Industrial Technologies proton-exchange membrane parts per million research and development