A study of the properties of drilling fluids containing certain natural organic colloids of Iranian origin

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A STUDY OF THE PROPERTIES OF DRILLING FLUIDS CONTAINING CERTAIN NATURAL ORGANIC COLLOIDS OF IRANIAN ORIGIN

A T hesis P resented to The F a c u l t y o f t h e D e p a r t m e n t o f P e t r o l e u m E n g i n e e r i n g The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a

In P a r tia l F u lfillm en t o f t h e R eq u irem en ts f o r th e Degree M aster of Science i n Petroleum E n g in e e rin g

by G e o rge T c h i l l i n g a r i a n J u n e 1950

UMI Number: EP63278

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion.

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ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 81 0 6- 1346

This thesis, written by ................... G-EOEGE. TCH ILLIEG -A EIM .

under the guidance of h.l a — Faculty C omm ittee, and a p p r o v e d by all its members, has been presented to and acce pted by the Council on Graduate S tu d y and Research in parti al fulfill­ ment of the requirements f o r the degree of ........................ M S .™ ._ 0?..SCIMCE_.EM........................... ..........................

D a te

jJjma.JLS50......................

F aculty C om m ittee

Chairfrittan ....

ACKNOWLEDGEMENTS

The i n v e s t i g a t o r i s g r e a t l y i n d e b t e d t o D r . D. H. L a r s e n , m a n a g e r o f R e s e a r c h and D e v e lo p m e n t o f t h e B a r o l d S a l e s D i v i s i o n , und.er whose d i r e c t i o n t h i s i n v e s t i g a t i o n was u n d e r t a k e n , a n d whose h e l p a n d c r i t i c a l a d v i c e w ere i n ­ v a lu a b le in c a rry in g i t to com pletion. The i n v e s t i g a t o r w o u l d l i k e t o e x p r e s s h i s a p p r e c i a ­ t i o n to th e B aroid S a le s D iv isio n f o r th e use of t h e i r l a b o r a t o r y a n d m a t e r i a l s i n some i n s t a n c e s .

The h e l p ex ­

t e n d e d by t h e men o f B a r o l d L a b o r a t o r y i s a l s o g r e a t l y a p ­ preciated. G-eorge T c h i l l i n g a r i a n

TABLE OF CONTENTS

CHAPTER I.

PAGE

INTRODUCTION

.........................................................................

1

...................................................................

2

The p r o b l e m

S ta te m e n t o f th e problem

...................................

2

I m p o r t a n c e o f t h e s t u d y ..........................................

2

O r g a n i z a t i o n o f t h e t h e s i s ........................................

3

An o u t l i n e o f t h e c o n t e n t s Method o f p r o c e d u r e

4

....................................................................

4

..........................................................

4

...............................................................

4

Foam iness

....................................................................

5

D efin itio n s

....................................................................

5

.........................................................................

5

Gel s t r e n g t h W ater l o s s

P eptize

CLASSIFICATION OF NATURALORGANIC COLLOIDS (GUMS)

III.

..............................................................................

6

THE OCCURRENCE AND ORIGIN OFGUMS IN PLANTS AND THEIR CHEMISTRY

.................................................

13

.........................

13

.....................................................

15

O ccurrence and o r i g i n o f gums C h e m i s t r y o f gums IV.

3

.................................................

V isc o sity

II.

o fthet h e s i s .

PHYSICAL AND CHEMICAL PROPERTIES OF GUMS Physical p ro p e rtie s C o lo r and form

. .

24

.................................................

24

.....................................................

24

iii

CHAPTER

PAGE T aste and sm ell

.....................................................

H a r d n e s s a n d d e n s i t y ..................................

26

P o larizatio n

...............................................................

27

S o lu b ility

...............................................................

27

................................................

28

C h e m ica l p r o p e r t i e s V.

26

COLLOIDAL BEHAVIOR OF THE G-UMS AHD THE THEORY BEHIND THE CONTROL OF FILTRATION CHARACTERISTICS OF MUDS BY USE OF GUMS

. .

C o l l o i d a l b e h a v i o r o f t h e g u m s ............... V iscosity

30

....................................................................

Surface ten sio n Foaming

30

31

.....................................................

33

........................................................................

3^

E f f e c t o f t h e c o l l o i d a l s t a t e o f t h e mudw ater l o s s

................................................ * .

Symptoms o f s a l t c o n t a m i n a t i o n ...........

36

37

Theory b e h in d t h e c o n t r o l o f f i l t r a t i o n c h a r a c t e r i s t i c s o f muds b y u s e o f gums VI.

•

IMPERMEX AND DRISCO SE............................................ Starch

37 AO

.............................................................................

Impermex muds

Ad

...............................................................

Red l i m e b a s e Impermex mud

Al

.............................

A2

E f f e c t o f Impermex on v a r i o u s muds . . . .

V II.

A3

D r i s c o s e ....................................................................

A9

TRAGACANTH G U M ..........................................................

53

iv CHAPTER

PAGE

B o ta n ic a l and g eo g ra p h ica l C o llection

. . . .

53

............................................ . . . . .

5^

G rading and m ark e tin g

sources

.......................................

C h e m i s t r y o f gum t r a g a c a n t h

.............................

55 56

E f f e c t o f gum t r a g a c a n t h on v a r i o u s d rillin g flu id s

.....................................................

58

P o s s i b i l i t y o f u s i n g gum t r a g a c a n t h i n s t e a d o f s t a r c h i n h i g h pH mud S t r a i g h t water-gum mud V III.

. . .

59

.......................................

59

GUMS KARAYA, GHATTI AND S H I R A Z .............................

66

Gum K a r a y a V iscosity

....................................................

66

....................................................................

08

E f f e c t o f gum K a r a y a on d i f f e r e n t muds

.

69

Gum G h a t t i .........................................................................

69

C h e m i s t r y o f gum g h a t t i

..................................

72

E f f e c t o f gum g h a t t i on d i f f e r e n t d r i l l i n g flu id

.........................................................................

72

P o s s i b i l i t y o f u s i n g gum g h a t t i i n s t e a d o f s t a r c h i n h i g h pH m u d ............................. Gum S h ir a z

....................................................................

75 75

E f f e c t o f gum S h i r a z on v a r i o u s d r i l l i n g flu id s

....................................................................

75

P o s s i b i l i t y o f u s in g gum S h ir a z I n s t e a d o f s t a r c h i n h i g h pH mud

.........................

83

V

CHAPTER IX.

PAGE

LOCUST BEAN AMD QUINCE SEED The h e m i c e l l u l o s e s : q u in c e s e e d

...................................

85

l o c u s t bean gum and

...............................................................

L ocu st bean gum and l o c u s t k e r n e l gum

85

..

....................

C h em istry o f l o c u s t bean gum

86 88

The e f f e c t o f l o c u s t bean s e e d on v a r i o u s d r illin g flu id s

89

.................................................

P o s s i b i l i t y o f u s in g l o c u s t bean s e e d i n s t e a d o f s t a r c h in h ig h pH mud Quince s e e d

. .

....................................................................

Chemistry of q u in c e seed

91

.............................

E f f e c t o f q u in c e s e e d on v a r i o u s muds

91

97 .

100

P o s s i b i l i t y o f u s in g q u in c e s e e d i n s t e a d o f s t a r c h i n h ig h pH m u d ............................. X.

GUM ARABIC AND OTHER IRANIAN GUMS

....................

108

Gum a r a b l e .........................................................................

108

E f f e c t o f gum a r a b l e on d i f f e r e n t muds

XI.

100

.

109

Other P e r s i a n g u m s .....................................................

109

K u t ir a g u m ....................................................................

112

P e n a e a ..............................................................................

112

K e tir a h -i-a r J e n

. . . . .

.............................

112

B a l u c h i s t a n gum

.....................................................

113

EFFECT OF HIGH TEMPERATURE ON MUDS TREATED WITH DIFFERENT GUMS

.................................................

114

Vi CHAPTER

PAGE

R esults X II.

..............................................................................

SUMMARY AND CONCLUSIONS Summary

APPENDIX A.

119 119

....................................................................

120

............................................................................................

130

......................................................................................................

132

I d e n t i f i c a t i o n o f gums

....................................................

P rep aration of reag en ts B.

.................................................

..............................................................................

C onclusions BIBLIOGRAPHY

115

........................ ....

.

•

F o a m s .................................................................................... O r i g i n a n d m ec h an ism o f foam f o r m a t i o n

133 1^0

.

140

. .

142

....................................................

1^3

.......................................................................................

144

G ib b ’ s law o f s u r f a c e c o n c e n t r a t i o n B re a k in g o f foams N o te

133

. .

LIST OF TABLES PAGE C o m p le te L ist, o f I r a n ia n G u m s .............................

11

C o m p o sitio n o f t h e G u m s ....................................... ....

18

E f f e c t o f Impermex on D i f f e r e n t Muds

.

. .

k6

E f f e c t o f D r i s c o s e on D i f f e r e n t Muds

.

. .

51

....................

57

E f f e c t o f Gum T r a g a ca n th on D i f f e r e n t Muds .

62

E f f e c t o f G-um Karaya on D i f f e r e n t Muds

. .

70

. . .

76

. .

79

E f f e c t o f L ocust Bean Seed on V a r io u s Muds .

93

C o m p o sitio n o f Q uince Seed E x t r a c t s

99

B u f f e r A c tio n i n T ragacan th G-els

E f f e c t o f G-um G-hatti on V a r io u s Muds E f f e c t o f G-um S h ir a z on D i f f e r e n t Muds

. . . .

E f f e c t o f Quince Seed on D i f f e r e n t Muds

. .

105

E f f e c t o f G-um A r a b ic on D i f f e r e n t Muds

. .

111

...................................................................................

116

V a r i a t i o n i n Water L oss w i t h Temperature o f 1 p er c e n t B r in e Mud (7*5 p er c e n t W ilm ington S lo u g h +■ 1 / 2 p er c e n t P ara­ fo rm a ld eh y d e) T r e a te d w i t h D i f f e r e n t G-ums

E f f e c t o f D i f f e r e n t Gums ( 1 . 2 gram s/100 c .c .

Mud) on S a t u r a t e d B rin e Mud

c e n t Z e o g e l)

. . .

p er

.................................................

121

v lii TABLE

XVI.

PAGE

E f f e c t o f D i f f e r e n t Gums ( 0 . 6 grms. p e r 100 c . c . Mud) on F r e s h Water Mud (20 p e r c e n t by w e i g h t P- 9 5 Olay + 1 / 2 p e r c e n t p a ra ­ form a ld eh y d e )

XVII.

...............................................................

E ffec t of D iffer en t B r in e Mud (10 p e r

X V III.

E ffec t of D iffe r en t

122

Gums on 10 p e r c e n t c e n t Baroco C lay)

.

. .

126

Gums on 1 p e r c e n t B rin e

Mud (7*5 p e r c e n t W ilm ington S lo u g h + 1 / 2 p er c e n t Ps.raform aldehyde) XIX.

E ffe c t of D iffe r e n t (35 p e r c e n t P - 9 5

..............................

Gums on High pH Mud Clay - 3 # / b b l . C a u s t ic

- 3 # / b b l . Quebracho - 2 # / b b l . Lime) A.

127

R e s u l t s o f T e s t s on V a r io u s Gums

• •

128

.....................

13^

LIST OF FIGURES FIGURE

PAGE

1.

S o u r c e a n d D e r i v a t i o n o f Gums. . . . . . . .

2.

E f f e c t o f Impermex

on F i l t r a t i o n

V iscosity

and Gel S tr e n g th

of A per cent

Zeogel

S a t u r a t e d B r i n e Mud 3*

E f f e c t o f Impermex a n d Gel S t r e n g th W a t e r Mud

4.

12

.....................................................

on F i l t r a t i o n

V iscosity

o f 20 p e r c e n t P-95 F r e s h

..............................................................................

E f f e c t o f T r a g a c a n t h Gum Ho.

50

11 on F i l t r a t i o n

V i s c o s i t y a n d Gel S t r e n g t h o f 20 F r e s h W a te r Mud

A5

per cent

...............................................................

60

5*

E f f e c t o f T r a g a c a n t h Gum Ho. 11 on High pH Mud.

61

6.

E f f e c t of Gum G h a t t i on F i l t r a t i o n V i s c o s i t y a n d Gel S t r e n g t h o f 20 p e r c e n t P-95 F r e s h W a t e r Mud

7.

7^

.............................................................................

E f f e c t o f Gum S h i r a s on F i l t r a t i o n

V iscosity

a n d G el S t r e n g t h o f 20 p e r c e n t P-95 F r e s h W a t e r Mud

........................................................................

•

82

.....................

8A

8.

E f f e c t o f Gum S h i r a s on High pH Mud

9*

E f f e c t o f L o c u s t Bean Se ed on S a t u r a t e d B r i n e Mud (A p e r c e n t Z e o g e l ) ................................

10.

90

E f f e c t o f L o c u s t Bean on F i l t r a t i o n V i s c o s i t y a n d G el S t r e n g t h o f 20 p e r c e n t P-95 F r e s h W a te r Mud

..............................................................................

92

X

FIGURE

PAGE

1 1.

E f f e c t o f L o c u s t Bean Seed on H ig h pH Mud

12.

E f f e c t o f Q u in c e S e e d on F i l t r a t i o n V i s c o s i t y

96

. .

a n d Gel S t r e n g t h o f 20 p e r c e n t P-9 5 F r e s h W a t e r Mud 13*

..............................................................................

101

E f f e c t o f Q u in ce S e e d on F i l t r a t i o n V i s c o s i t y and Gel S t r e n g th o f k p e r c e n t Zeogel S a t u r a t e d B r in e Mud

.....................................................

102

14.

E f f e c t o f Q u in c e S e e d on H i g h pH M u d .....................

103

15*

Gum A r a b i c M o l e c u l e

110

16.

P e r c e n t D e v i a t i o n o f W ater L o s s a t 6 8 ° F . —

...........................................................

A c t u a l fro m C a l c u l a t e d 17.

117

E f f e c t o f D i f f e r e n t Gums on S a t u r a t e d B r i n e Mud

18.

.................................................

p e r c e n t Zeogel)

............................................

3.2L

E f f e c t o f D i f f e r e n t Gums ( 0 . 6 p e r c e n t ) on F r e s h W a t e r Mud (2 0 p e r c e n t b y w e i g h t P-95 Clay) + 1 /2 p e r cent P arafo rm ald e h y d e

•

125

CHAPTER I

INTRODUCTION Every p e tr o le u m e n g i n e e r i s w e l l aware o f the im­ p o r t a n t r o l e p la y e d by d r i l l i n g muds.

A th o r o u g h knowledge

o f d r i l l i n g muds w i l l a i d t h e e n g i n e e r not o n l y i n mud prob­ lem s b u t a l s o i n su ch f i e l d s a s c o r e a n a l y s i s , c o m p le t io n p r a c t i c e , and e l e c t r i c l o g g i n g .

Poor p l a s t e r i n g p r o p e r t i e s

w i t h a t t e n d a n t h ig h f i l t r a t i o n r a t e

( l a r g e w a te r l o s s to th e

f o r m a tio n ) and t h i c k mud s h e a t h , l e a d s t o s t u c k d r i l l p ip e , d i f f i c u l t y i n la n d in g c a s i n g , e t c . ,

and may promote c e r t a i n

t y p e s o f h e a v in g when t h e w a te r f i l t e r s i n t o b e n t o n i t i c and r e la t e d fo r m a tio n s.

F urtherm ore, th e p e n e t r a t i o n o f w a ter

t o g e t h e r w i t h f i n e c o l l o i d a l m a tte r i n t o th e o i l b e a r in g sand may have a marked i n f l u e n c e upon t h e r a t e o f su b seq u e n t p r o ­ d u c t i o n o f o i l from t h a t sand.

I t has b een fou n d t h a t among

th e many f a c t o r s t h a t have a d v e r se e f f e c t on f i l t r a t i o n , t h e presence o f e le c t r o l y t e s , c u la r , i s o u ts ta n d in g .

i n g e n e r a l , and o f s a l t ,

in p a r t i­

The e f f e c t i s one o f f l o c c u l a t i o n o f

th e c o l l o i d s due to n e u t r a l i z a t i o n o f th e n e g a t i v e c h a r g e s on th e c l a y p a r t i c l e s .

T h is r e a c t i o n i s f u r t h e r i n c r e a s e d

on t h e G u lf C oast b e c a u s e h ig h te m p e r a tu r e s r e d u c e d i s p e r s i o n to a minimum c a u s in g i n c r e a s e d f l o c c u l a t i o n i n b o t h f r e s h ­ w a te r and s a l t - w a t e r muds.

The problem o f r e d u c in g w ater

l o s s by th e a d d i t i o n o f d i f f e r e n t I r a n i a n gums a t a tm o sp h e ric

2

and h i g h t e m p e r a t u r e s h a s b e e n i n v e s t i g a t e d i n t h e p r e s e n t w ork a n d many s u c c e s s f u l s o l u t i o n s have b e e n o b t a i n e d . G-urns c o n s i s t e s s e n t i a l l y o f C, H* a n d 0, w i t h a s m a l l amount o f m i n e r a l m a t t e r .

They a r e made up o f s u g a r s c hem i­

c a l l y u n i t e d w i t h an a c i d n u c le u s .

N a t u r a l gums o c c u r a s

e x u d a t e s on t h e t r u n k s a n d ste m s a n d i n t h e k e r n e l s o f v a r i o u s t r e e s and s h ru b s .

The n a t u r a l p r o d u c t s a r e s o r t e d on t h e

b a s i s of tr a d e sta n d a rd s and a re m ille d to produce a v a r i e t y of grades. I.

THE PROBLEM

S tatem ent o f th e problem .

The p u r p o s e o f t h i s t h e s i s

i s t o make a s t u d y o f d i f f e r e n t n a t u r a l o r g a n i c c o l l o i d s o f I r a n i a n o r i g i n and t r e a tm e n t of d i f f e r e n t d r i l l i n g f l u i d s w i t h t h e s e gums. Im portance of the s tu d y .

Successful ro ta ry d r i l l i n g

d e p e n d s t o a g r e a t e x t e n t upon t h e p h y s i c a l a n d c h e m i c a l p r o p e r t i e s o f the c i r c u l a t i n g f l u i d used and th e c o n t r o l o f t h e s e p r o p e r t i e s a s c h a n g i n g c o n d i t i o n s may r e q u i r e . The i m p o r t a n c e a n d c o n t r o l o f f i l t r a t i o n o r w a t e r l o s s , i s obvious.

I t a f f e c t s t h e a n a l y s i s of s i d e - w a l l c o r e s and

i n t e r p r e t a t i o n of e l e c t r i c

logs;

i t c o n t r o l s to a l a r g e ex­

t e n t t h e w o r k o f p r i m a r y c e m e n t i n g , r e d u c e s t h e amount o f expensive f i s h i n g ,

and p e r m i t s t h e ru n n in g o f lo n g s t r i n g s o f

3

casing. W a te r b u i l d i n g c h a r a c t e r i s t i c s o f f r e s h w a t e r mud c an be r e g u l a t e d by a d d i t i o n o f b e n t o n i t i c c l a y s o r o t h e r a g e n ts w h i c h d i s p e r s e mud s o l i d s . salts,

But by d r i l l i n g t h r o u g h s o l u b l e

t h e s a l t s a r e i n c o r p o r a t e d i n t h e mud a n d c a u s e f l o c ­

cu latio n ,

which in t u r n i n c r e a s e s th e w a te r l o s s trem en dou sly.

Methods u s e d i n c o n t r o l l i n g f i l t r a t i o n o f f r e s h w a t e r muds a r e no l o n g e r a p p l i c a b l e . The p r e s e n t r e s e a r c h was p a r t l y c o n d u c t e d t o w a r d s f i n d ­ i n g m eth o d s o f i m p r o v i n g t h e f i l t r a t i o n c h a r a c t e r i s t i c o f s a l t itfater muds, w h i c h p r e s e n t a c u t e p r o b l e m s i n p s . r t s o f West T e x a s . d rillin g

The same p r o b l e m i s g o i n g t o b e e n c o u n t e r e d i n

in th e salt-dom e a re a o f I r a n . II.

ORGANIZATION OF THE THESIS

An o u t l i n e o f t h e c o n t e n t s o f t h e t h e s i s .

The i n f o r ­

m ation a s s e m b le d i n th e f o l l o w i n g c h a p t e r s i s in th e f o l l o w ­ in g o r d e r:

C h a p ters I I ,

I I I and IV c o v e r b a s i c in f o r m a tio n

n e c e s s a r y f o r t h e c o m p lete u n d e r s ta n d in g o f gums, namely: (l)

c l a s s i f i c a t i o n of n a tu r a l organic c o llo id s ,

(2 ) t h e o c ­

c u r r e n c e a n d o r i g i n o f gums i n p l a n t s a n d t h e i r c h e m i s t r y a n d (3 ) p h y s i c a l a n d c h e m i c a l p r o p e r t i e s o f gums.

The i n f o r ­

m ation in c l u d e d in th e s e c h a p t e r s i s g a th e r e d from v a r i o u s books and the I r a n i a n M i n i s t r y of A g r i c u l t u r e .

C hapter V

d e s c r i b e s c o l l o i d a l b e h a v i o r o f gums a n d t h e t h e o r y b e h i n d

4

the c o n tr o l of f i l t r a t i o n gums.

c h a r a c t e r i s t i c s o f muds b y u s e o f

C h a p t e r s VI t h r o u g h X i n c l u s i v e ,

in d iv id u ally .

t r e a t v a r i o u s gums

They i n c l u d e b o t h c h e m i s t r y o f gums a nd t h e i r

e f f e c t on v a r i o u s d r i l l i n g f l u i d s .

C hapter XII i n c lu d e s

summary a n d c o n c l u s i o n s , w h i l e c h a p t e r XI shows t h e e f f e c t o f h i g h t e m p e r a t u r e on muds t r e a t e d w i t h d i f f e r e n t gums. III.

METHOD OF PROCEDURE

The A m e ric an P e t r o l e u m I n s t i t u t e h a s recommended s t a n d ­ a r d methods f o r t e s t i n g d r i l l i n g f l u i d s ,

and d e t a i l e d p r o ­

c e d u r e s may be f o u n d i n t h e i r p u b l i c a t i o n e n t i t l e d A. P. I . Code No. 2 9 , ’’Recommended P r a c t i c e on S t a n d a r d F i e l d P r o ­ c e d u r e f o r t e s t i n g D r i l l i n g F l u i d s , ” 2nd e d i t i o n

(1942).

A ll

t e s t s made f o r t h i s work w e re made i n c o m p l i a n c e w i t h t h i s code. V iscosity.

V i s c o s i t y was m e a s u r e d w i t h t h e S t o r m e r

v i s c o s i m e t e r a t 600 r . p . m . G-el s t r e n g t h .

(c en tip o ises).

T h i s was r e c o r d e d i n g r a m s .

Minimum

w e i g h t r e q u i r e d t o e f f e c t a movement o f a p p r o x i m a t e l y o n e q u a r t e r r e v o l u t i o n o f t h e s p i n d l e a f t e r t h e b:heak i s s l o w l y released.

Ten m i n u t e s g e l s t r e n g t h — minimum w e i g h t r e ­

q u i r e d t o c a u s e r o t a t i o n a f t e r 10 m i n u t e s p e r i o d o f q u i e s c e n c e . W a te r l o s s .

T h i s was d e t e r m i n e d a t room t e m p e r a . t u r e

5

w ith th e B aroid lo w -p re ssu re w all b u ild in g t e s t e r a t a p r e s ­ s u r e o f 100 l b s . p e r s q .

in.

C o r r e c t e d 30 m i n u t e w a t e r l o s s

i s used. Foam iness.

I n d e t e r m i n i n g f o a m i n e s s t h e muds t r e a t e d

w i t h gums w ere a l l o w e d t o s t a n d f o r o n e - h a l f h o u r a n d r e c o r d e d a s i n c r e a s e i n v o lu m e i n c c . p e r e a c h 100 c c .

o f o r i g i n a l mud.

A n t i f o a m i n g a g e n t u s e d i n t h e p r e s e n t w ork was “o c t y l w alco h o l (2 -e th y l hexanol).

Muds w ere p r e p a r e d i n t h e l a b o r a ­

t o r y a n d a g e d f o r s e v e r a l week s. Two h u n d r e d c c . s a m p l e s o f muds w e re t a k e n a n d d i f f e r ­ e n t a m o u n ts o f gums a d d e d ( r e c o r d e d i n g ram s o f gum p e r 100 cc.

o f m ud).

A f t e r a d d i t i o n o f gum, s a m p l e s w e r e d i s p e r s e d

w i t h a h i g h s p e e d s t i r r e r f o r h a l f an h o u r .

On a l l o w i n g

s a m p l e s t o s t a n d f o r 45 h o u r s , t h e y w ere s t i r r e d f o r a n o t h e r h a l f hour, b e fo r e ru n n in g t e s t s . G-urns w e r e u s e d i n a powder f o r m . IV. P ep tize. so lu tio n ;

DEFINITIONS

P h y s ic a l Chem istry.

to c o n v e r t i n t o a s o l .

To b r i n g i n t o c o l l o i d a l

CHAPTER I I

CLASSIFICATION OF NATURAL ORGANIC COLLOIDS (GUMS) W a t e r - s o l u b l e gums h ave b e e n known s i n c e B i b l i c a l tim es.

C om m ercially th e term embraces a g ro u p o f s u b s ta n c e s

whose p r o p e r t i e s o f f o r m i n g v i s c o u s a d h e s i v e s ,

je llie s,

or

p a s t e s , h a v e e a r n e d a p l a c e f o r them i n t h e a r t s a n d i n d u s ­ trie s. The d e s i g n a t i o n o f “w a t e r - s o l u b l e gums” i s a misn om er i n many w a y s , a s t h e m a t e r i a l s a r e n o t s o l u b l e i n t h e s t r i c t ­ ly s c ie n tif ic

sense as s a l t ,

sugar, and o th e r c r y s t a l l i z a b l e

m a t e r i a l s a r e s o l u b l e ; t h e gums a r e n o t c r y s t a l l o i d s b u t co llo id s. strict

They do n o t show c r y s t a l f o r m b u t a r e i n t h e

s e n s e am o rp h o u s ; t h e y have n e i t h e r m e l t i n g p o i n t n o r

fre e z in g p o in t nor b o ilin g po in t c h a r a c te r is tic s .

They a r e

o rg a n ic su b s ta n c e s o f i n d e f i n i t e com position as th e y a p p ea r t o be c o m p l e x e s a s s o c i a t e d w i t h p l a n t l i f e p r o c e s s e s . The a p p e l l a t i o n o f "gum" i n commerce i s v e r y w id e a nd confused in i t s

ap p licatio n .

O f t e n t h e t e r m i s em p lo y ed f o r

m a t e r i a l s w hich a f f e c t th e se n se s of to u c h ,

taste,

and s i g h t

i n a m e a s u r e summed up a s a p r o p e r t y o f " g u m m i n e s s . 11

I t is

d i f f i c u l t t o d e f i n e , b u t v i s u a l a n d manua l e x a m i n a t i o n o f a m a t e r i a l may c a u s e t h e o b s e r v e r t o c a l l i t gum. I n t i i i s t h e s i s t h e t e r m "gum” w i l l be l i m i t e d t o t h e

7

t r e e e x u d a tio n s of w hich a r a b l e , g h a t t i , k a ra y a ,

and tra g a ­

c a n t h a re exam ples; and t h e seed e x t r a c t s o f w hich l o c u s t b e a n , l o c u s t k e r n e l , a n d q u i n c e s e e d gums a r e t y p i c a l . T hes e m a t e r i a l s a r e a l l w a t e r - l o v i n g c o l l o i d s — t h e y may a p p a r e n t l y d i s s o l v e ,

but a c tu a lly d is p e rs e o r sw ell or

a b s o r b w a t e r t o fo rm c o m m e r c i a l l y v a l u a b l e a n d i n t e r e s t i n g su b stances.

They a r e h y d r o p h i l i c a n d o r g a n i c - s o l v e n t p h o b i c .

I t i s i n te r e s ti n g to note th a t resin o u s m a te ria ls in c o n tra s t t o t h e gums a r e h y d r o p h o b i c a n d o r g a n i c s o l v e n t p h i l l c . Tlie h u n d r e d s o f names o f t h e n a t u r a l gums d e n o t e t h e g e o g ra p h ic a l a re a s in which th ey a re g a th e r e d ,

the d i s t r i c t s

and p o r t s o f w h o le s a le c o l l e c t i o n and t h e p o i n t s a t which t h e y e n t e r commerce, t h e g r a d i n g a n d d i s t r i b u t i o n c e n t e r s . Such n o m e n c l a t u r e i n e v i t a b l y l e a d s t o c o n f u s i o n o m i t t i n g t h a t i n t e n t i o n a l l y c a u s e d b y t r a d e r s f o r t h e i r own a d v a n t a g e . i s a d v isab le to t r e a t w ith

It

n a t u r a l gums i n t h e g r o u p s o r i g i n a t i n g

s p e c i f i c s p e c i e s o f t r e e s o r p l a n t s , w h ich can be l i s t e d

as follo w s: 1.

G-ums f r o m t h e A c a c i a s p e c i e s o f t r e e s

(G-um A r a b i c

a s an e x a m p le ) 2.

A nogeissus

species

( G - h a tti a s a t y p i c a l one)

3*

A strag alu s

species

(sourceof T ragacanth)

P r u n u s s p e c i e s ( c h e r r y gum a s an e x a m p le ) 5*

S t e r c u l i a s p e c i e s ( w it h Karaya a s a s p e c i f i c c a s e ) .

8

The gums f r o m t h e same s p e c i e s o f t r e e s a r e c h e m i c a l l y s i m i l a r i n t h a t t h e same c o m p o n e n ts a r e f o u n d , w h i l e gums from d i f f e r e n t

sp e c ie s d i f f e r c h em ic ally and p h y s i c a l ly .

The gums a r e u n c r y s t a l l l z a b l e a n d a r e u s u a l l y compos ed of carbon,

h y d r o g e n a n d o x yg e n i n t h e m a i n .

They h a v e t h e

c h a r a c t e r i s t i c p r o p e r t y o f form ing v i s c o u s s o l u t i o n s o r m u c i l a g e s e i t h e r by “ d i s s o l v i n g ” i n w a t e r o r b y a b s o r b i n g many t i m e s t h e i r own v olu m e o f t h a t s o l v e n t .

The c o l l o i d a l

s o l u t i o n s a r e formed r a t h e r th a n th e t r u e s o l u t i o n s o f c r y s t a l l i z a b l e m a t e r i a l s such a s formed from s a l t or sugar (su c ro se ).

(sodium c h l o r i d e )

C o m m e rcia l gums c o n t a i n more o r l e s s

m i n e r a l m a t t e r , c h i e f l y c a l c i u m , magnesium, a n d p o t a s s i u m . N i t r o g e n i s o f t e n p r e s e n t b u t i s n o t c o n s i d e r e d an e s s e n t i a l co n stitu en t. proteins,

I n t h i s s e n s e t h e t r u e gums d i f f e r f r o m t h e

o f w h i c h n i t r o g e n i s a n e s s e n t i a l c o m p o n e n t.

G-ums e x h i b i t e n d l e s s d i f f e r e n c e s i n g e n e r a l a p p e a r ­ ance, e s p e c ia lly c o lo r,

a n d in p h y s i c a l and c h e m ic a l p r o p e r ­

t i e s s u c h a s t h e more o b v i o u s a n d c o m m e r c i a l l y i m p o r t a n t one o f v i s c o s i t y o r a d h e s iv e n e s s and s o l u b i l i t y . d i s t i n g u i s h e d from r e s i n s ,

A ll are re a d ily

o l e o - r e s i n s and b a lsam s and p ro ­

d u c t s o f a r u b b e r y n a t u r e t o w h i c h t h e t e r m “ gum” i s

some­

tim es wrongly a p p l i e d , by th e f a c t t h a t th e y a r e m is c ib le w i t h w a t e r i n a l l p r o p o r t i o n s an d a r e I n s o l u b l e i n l i q u i d s such as a lc o h o l, benzene,

e t h e r , c h lo ro fo rm , t u r p e n t i n e and

f i x e d o i l s which d i s s o l v e r e s i n s .

On h e a t i n g ,

t h e y decompose

9

com pletely w ith o u t m e ltin g ,

u s u a l l y sho w in g c h a r r i n g .

The

t r u e gums a r e g e n e r a l l y d i v i d e d i n t o two m ain c l a s s e s o r g r o u p s — a) s o l u b l e gums: — t y p i f i e d b y gum a r a b l e a n d s i ­ m i l a r gums, w h i c h d i s s o l v e i n w a t e r f o r m i n g more o r l e s s t r a n s ­ p a re n t, v is c o u s and a d h e siv e s o l u t i o n s ,

a n d b ) i n s o l u b l e gums:

— w h i c h , when p l a c e d i n w a t e r a b s o r b i t a n d s w e l l i n t o a t h i c k j e l l y o r j e l l y - l i k e m ucilage o r w ith s u f f i c i e n t w ater p r e s e n t f i n a l l y b r e a k down i n t o a v e r y t h i c k t r a n s l u c e n t s o l u ­ tio n .

The b e s t known gums b e l o n g i n g t o t h i s g r o u p a r e gum

t r a g a c a n t h a n d t h e s o - c a l l e d “ t r a g a c a n t h s u b s t i t u t e 1’ gums s u c h a s k a r a y a gum, c a r o b s e e d gum a n d hog gum o r k u t i r a gum.

G-ums

o f t h i s c l a s s a r e y i e l d e d by s e v e r a l s p e c i e s o f S t e r c u l i a . There i s a l s o w hat m ig h t be c o n s i d e r e d t o be a t h i r d g r o u p of gums — gums w i t h p r o p e r t i e s I n t e r m e d i a t e b e t w e e n t h e above two c l a s s e s . gum s.”

T h es e h av e b e e n t e r m e d * f e e m i - i n s o l u b l e

They p a r t i a l l y d i s s o l v e i n w a t e r l e a v i n g a s w o l l e n

j e l l y , which w i l l p a ss i n t o s o l u t i o n w i t h the a d d i t i o n o f more w a t e r ,

i.e .

th e y form t h i n j e l l i e s .

The s o - c a l l e d

“ P e r s i a n i n s o l u b l e gum," b e l i e v e d t o be d e r i v e d f r o m a s p e c i e s o f P r u n u s a n d i m p o r t e d f r o m t h e P e r s i a n G-ulf a t one t i m e , i s a g o o d e x am p le o f t h i s c l a s s o f gum.

C o m m e r c i a l l y , s u c h gums

a r e c o n s i d e r e d I n f e r i o r t o b o t h t r a g a c a n t h a n d gum a r a b l e . A ll these v a r i e t i e s are p re se n t in Ir a n .

The s e e d s

o f some t r e e s a n d p l a n t s i n I r a n y i e l d a l s o h e m i c e l l u l o s e s . Com ple te l i s t o f I r a n i a n gums a n d t h e names u n d e r w h i c h t h e y

10

a r e known i n d i f f e r e n t p a r t s o f t h e w o r l d , i s p r e s e n t e d i n Table I .

The l o c a l name o r t r a d e v a r i a n t i s i n t h e f i r s t

co lu m n , t h e p r o v i n c e o f o r i g i n i n t h e s e c o n d c o lu m n , t h e b o t a n ­ i c a l s o u r c e i s i n t h e t h i r d co lu m n , a n d t h e p r e s e n t d a y c l a s ­ s i f i c a t i o n i n t h e U n i t e d S t a t e s i n t h e l a s t c o lu m n . G-ums a r e o b t a i n e d by t a p p i n g o r c o l l e c t i n g f r o m t r e e s an d s h r u b s ,

s e p a r a t i o n fro m marine p l a n t l i f e ,

by m i l l i n g

fr o m some s e e d s o r e x t r a c t i o n f r o m o t h e r s , t h e r m a l t r e a t m e n t o f s t a r c h e s from k e r n e l s o r r o o t c r o p s , ch em ical p r o c e s s in g o f c e l l u l o s e from t r u n k s of t r e e s o r from th e c o t t o n p l a n t , a s w e ll as s e p a r a t i o n of anim al b y -p ro d u c ts a n d p u r i f i c a t i o n procedures.

S o u r c e a n d d e r i v a t i o n o f gums w h i c h a r e t r e a t e d

i n trie p r e s e n t work a r e i l l u s t r a t e d i n F i g u r e 1.

11

TABLE I COMPLETE LIST OF IRANIAN G-UMS Province of O rigin

Name A rrehbor

Type

P r e s e n t Day C lassificatio n

A strag alu s

T ragacanth

A stragalus

K urdistan

A stragalus

T ragacanth

Basra

K husestan

A stragalus

T ragacanth

Bassora

K husestan

S tercu lia

Karaya

Bushire

Fars (P e rsia)* A strag alu s

T ragacanth

C hatira**

Khorasan

A stragalus

T ragacanth

Cydonium

A ll p a r ts

Cydonium

Q u in c e Seed

E a s t I n d i a n G-um

A cacia

A rabic

G-avan

A stragalus

T ragacanth

H alusia

A stragalus

T ragacanth

Karai

A stragalus

T ragacanth

Katad

A stragalus

T ragacanth

K atira-i-h en d i

S tercu lia

Karaya

Persian T ragacanth

A stragalus

T ragacanth

S hiras

Fars (P ersia)

A nogelssus

G h atti

Smyrna T ragacanth

K urdistan

A stragalus

T ragacanth

Suleim anaya

A zerbaejan

A stragalus

T ragacanth

W h ite L e a f G-um

K urdistan

A stragalus

T ragacanth

*The p r o v i n c e i n t h e s o u t h e r n p a r t o f I r a n . Er­ r o n e o u s l y u s e d i n E u r o p e a n l a n g u a g e s t o d e s i g n a t e t h e name o f th e whole c o u n tr y I r a n . A l s o known a s K a t y r a , K e t t i r a , K a t h i r a , a n d K a t i r a .

F I G.

Trees

and

S eed

NO.

Pod s

Seeds

and Legumes

and

F r u 11 s

_

.

1

.

Collect i on a pp i n g

and C leaning

Separation 1 1

1

r

■

C 1e a n i n g

M e c h a m ca I

and

and

Milling

D ry i n g

I '

L________ A caci a G ha t t i . ^ Ka ra y a

Locust

India n

Locust

Gums

Gums

Seed

X

PsyH. u m

Gum

S e ed s

Q u i n ce

Ke r ne l

Seed

Gum

T ra g a c a n t h P e rs i a n

F 1a

Bean

Guar