Effects of Clay-Mineral Content on the Change in Effective Permeability of Oil Sands to Waters of Different Chemical Composition

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Effects of Clay-Mineral Content on the Change in Effective Permeability of Oil Sands to Waters of Different Chemical Composition

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E f f e c t s o f C l a y - M i n e r a l C o n t e n t on t h e C ha ng e i n E f f e c t i v e P e r m e a b ility o f O il Sands to W aters o f D i f f e r e n t C hem ical C o m p o sitio n By E l l i s

L e C la ir A nders,

LIBRARY COLORADO SCHOOL OF M USJEtS GOLDEN, COLORADO

Jr.

ProQuest N um ber: 10781405

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 10781405 Published by ProQuest LLC(2018). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346

obSo

A th esis

su bm itted

to th e F a c u l t y and th e Board o f

T r u s t e e s o f t h e C o lo r a d o S c h o o l o f M ines i n p a r t i a l f u l ­ f i l l m e n t of the re q u ire m e n ts f o r

the d e g re e of M a ste r o f

S cien ce. Signed:

cji Co

O E l l i s L e C la ir A nders, J r . I G olden, C olorado A p r i l 1 , 1950 A pproved:

Cl

cn

TABLE OF CONTEHTS P a g e No, In tro d u ctio n

1

Im p o rta n c e o f C lay C o n te n t o f S a n d s to n e s

2

W ell C o m p le tio n s

3

S a l t W ater D is p o s a l

5

W ater F lo o d in g

6

C lay M in e ra ls

8

D e fin itio n s

10

C o n s t i t u t i o n o f C lay M a t e r i a l s

11

The C l a y M i n e r a l s

12

!

K a o l i n i t e Group

12

Illite

12

Group

M o n t m o r i l I o n i t e Group

13

M inor Groups

li|.

The S t r u c t u r e o f C l a y M i n e r a l s

1I4.

S tru ctu re

o f M o n tm o rillo n ite

15

S tru ctu re

of I l l i t e

17

S tru ctu re of K a o lin ite

17

Base Exchange i n C lay M i n e r a l s

20

O c c u rre n c e o f C lay M i n e r a l s

22

P r o p e r t i e s o f Clay M a t e r i a l s

23

Procedures

25

N a tu r e o f C hanges U ndergone by C lay M a t e r i a l s i n Sands P o s s ib le A pproaches Fundam ental R e se a rc h

25 * 28 29

TABLE OP CONTENTS ( C o n t . )

R e s e a r c h on N a t u r a l l y O c c u r r in g System s R o u tin e M easurem ents

ILLUSTRATIONS P a g e No* F i g u r e No* 1

S c h e m a tic D iagram o f t h e S t r u c t u r e o f th e M ineral M o n tm o rillo n ite

16

F i g u r e No* 2

S c h e m a tie Diagram o f th e S t r u c t u r e o f the M in e ral I l l i t e

18

F i g u r e No* 3

S c h e m a t i c t> la g r a m o f t h e S t r u c t u r e of th e M ineral K a o lln lte

19

F i g u r e No* k

S c h e m a tic D iagram o f P e rm ea m e ter

33

F i g u r e No*

P h o to g ra p h s o f Perm eam eter

3k

F i g u r e No* 6a

D e t a i l D r a w i n g o f L u c i t e Body o f Perm eam eter C e ll

35

D e t a i l D r a w i n g o f End P i e c e t o Perm eam eter C e ll

35

E x p l o d e d View o f P e r m e a m e t e r C e l l

38

D ia g ra m Showing W o rk ab le Range f o r a C lay-W ater M ixture

Ijl.

F i g u r e No. 6 b F i g u r e No.

7

F i g u r e No. 8

INTRODUCTION

P e r m e a b i l i t y m easurem ents 1.

2.

1 2

9

o f o i l and g a s sa n d s a r e

F a n c h e r , G. H . , L e w i s , J . A . , a n d B a r n e s , K. B . , Some P h y s ic a l C h a r a c t e r i s t i c s o f O il Sands: Min* I n d u s t r y E x p e r . S t a . B u l l * 12, P e n n s y l v a n i a S t a t e C o l l e g e , p . ll* l, 1933. M u s k a t , M o r r i s , The F l o w o f H o m o g e n eo u s F l u i d s t h r o u g h P o r o u s M e d i a , M c G r a w - H i l l Book Company, I n c . , New Y o r k , 1937.

b a s e d on th e sta te s

sim p le,

straig h t-fo rw ard

" D a r c y ’ s Law1* w h i c h

t h a t the v e lo c ity o f f l u i d flow

p o r o u s m e d iu m i s d i r e c t l y p r o p o r t i o n a l

through a s o l i d , to

the p r e s s u r e drop

and p e r m e a b ility and i n v e r s e l y p r o p o r t i o n a l to th e o f the flo w in g f l u i d c e p t w ould i n d i c a t e flu id

is

t h e medium.

th a t the p e rm e a b ility

T his con

to a p a r t i c u l a r

i n d e p e n d e n t o f t h e n a t u r e o f t h e p o r o u s m e d iu m , a n d

th erefo re, has,

and th e l e n g t h o f

v isco sity

f l u i d h a s no e f f e c t upon i t .

T his r e q u i r e m e n t

h o w e v e r , b e e n f o u n d t o b e m o re t h e e x c e p t i o n t h a n t h e

ru le ^ i n n a tu r a l occurring' ro c k s. 3.

M uskat, M o r r is , P r o d u c t io n R e s e a rc h — P r e s e n t and F u t u r e : P e tro le u m T echnology, v o l . 1, no. 7, pp. 9 -1 6 , J u l y 19^9

Im p o rta n c e o f th e Clay C o n te n t o f S a n d s to n e s Hocks w h ic h c o n t a i n i n t e r g r a n u l a r m a t e r i a l s o f a n a r ­ g illa c e o u s n atu re

t o w a t e r o f a much 5 6 lo w er m agnitude th a n t h e i r p e r m e a b i l i t i e s to d ry a i r .

if.. ^ 5.

J o h n s t o n , N o r r i s , a n d B e e s o n , C. M . , W a t e r P e r m e a b i l i t y o f R e s e rv o ir Sands: P e tro le u m D e v e l. and T ech n o lo g y , p p . 1*3 - 5 $ , I 9 l t 5 . Y u s t e r , S . T # , H o m o g e n eo u s P e r m e a b i l i t y D e t e r m i n a t i o n : D r i l l i n g a n d P r o d u c t i o n P r a c t i c e , Am. P e t r o l e u m I n s t . , pp.

6.

show p e r m e a b i l i t i e s

3 5 6 - 3 6 3 , 19I1-6.

S ta n d a rd P rocedure f o r D eterm ining P e rm e a b ility of P o r o u s M e d i a , Am. P e t r o l e u m I n s t . Code No. 2?> 2d e d . , A p ril 19^2.

T h is r e d u c t i o n i n p e r m e a b i l i t y seems t o depen d up o n b o t h t h e c o n s t i t u t i o n o f th e i n t e r g r a n u l a r m a t e r i a l s and th e i o n i c c o n t e n t and c o m p o s itio n o f th e w a t e r . t h a t o i l w e ll com pletions in

I t has been observed

the s o - c a lle d

(th o se c o n ta in in g clay m a te r ia ls )

" d ir ty sands"

show l o w p r o d u c t i v i t y i n ­

d i c e s w h e n c o m p l e t e d w i t h w a t e r - b a s e m ud, a n d t h i s f a c t h a s been the p r i n c i p a l cause of

the developm ent o f o i l - b a s e

muds • Q u alitativ ely ,

p e t r o l e u m e n g i n e e r s a n d g e o l o g i s t s know

t h a t th e above s ta te m e n ts a re

tru e,

b u t the q u a n t i t a t i v e

e f f e c t s o f a n y o n e m i n e r a l i n t h e p o r o u s mfedium o r o f a n y one p a r t i c u l a r c a t i o n i n th e f l o w i n g w a t e r a r e unknown. is,

then,

It

t h e p u r p o s e o f t h i s p a p e r t o make t h e s e e f f e c t s

b e t t e r u n d e r s t o o d a n d t o p o i n t t h e way t o i n v e s t i g a t i o n s whioh sh o u ld c l a r i f y

the e f f e c t s

of i n d iv i d u a l chem ical

r a d i c a l s on p a r t i c u l a r c la y m i n e r a l s . In

t h r e e I m p o r t a n t p h a s e s o r o p e r a t i o n s o f o i l and g a s

p r o d u c t i o n th e c la y e y c o n t e n t of a sand c a n c au se c o m p li­ c a t i o n s w hich a r e c o s t l y . d i s p o s a l by i n j e c t i o n

T hey a r e w e l l c o m p l e t i o n s , w a t e r

to subsurface

stra ta ,

and w a t e r f l o o d ­

in g . W ell C o m p le tio n s The c o m p l e t i o n o f o i l a n d g a s w e l l s b y r o t a r y d r i l l i n g req u ires

t h a t some t y p e o f c i r c u l a t i n g f l u i d

w ith the w a lls of the h o le .

T his c i r c u l a t i n g f l u i d

a l l y a s o - c a l l e d w a t e r - b a s e m u d. th e w a te r to form a c o l l o i d a l a ls

(such as barium s u l f a t e

give

t h e mud p r o p e r w e i g h t ;

give d e s ir a b le

be i n c o n t a c t

B en to n ite

su spension;

is usu­

i s m ixed w i t h

w eig h tin g m a te ri­

and I r o n o x i d e ) a r e a d d e d t o v a rio u s c h e m ic a ls a r e added to

v a l u e s o f pH a n d v i s c o s i t y .

A ll of these

w a t e r - b a s e muds h a v e a t e n d e n c y t o l o s e w a t e r

(or f i l t r a t e )

t o a p o r o u s m e d iu m w h e n i n c o n t a c t t h e r e w i t h a n d u n d e r p r e s ­ sure.

The w a t e r m o v e s f r o m t h e mud i n t o

zon and l e a v e s a f i l t e r

the producing h o r i ­

cak e on th e w a l l s o f

the h o l e .

As

th e w a t e r moves I n t o a sand w h ich c o n t a i n s c l a y m a t e r i a l s w ith in the i n t e r s t i c e s , sw ell,

t h e c l a y s e v i d e n t l y b eco m e h y d r a t e d ,

and c a u s e a s u b s t a n t i a l r e d u c t i o n i n p e r m e a b i l i t y .

(The te r m s " h y d r a t e " and " h y d r a t i o n " a r e l o o s e l y u s e d i n th e o il

i n d u s t r y and a r e

so u se d h e r e i n .

o f w a te r w ith the c la y s

is not n e c e ssa rily im p lied .)

red u c tio n in p erm eab ility reduces from th e

sand i n t o

A chem ical co m b in atio n

the flow r a t e

T his

of f l u i d s

the w e ll bore u n d e r any s e t of p r e s s u r e

c o n d itio n s. The N a r a n j a " L " s a n d o f

th e San J o a q u i n F i e l d ? i n

- - - - - - - - - - - - - - - - -

7.

- - - - - - - - - -

- - -

- - - - - - - - - - -

- - - - T - —

B a r r e t t , R. C*, a n d W oods, R. W ., R e s e r v o i r S t u d y — N a r a n j a "L" S a n d — G u a r i o Dome, S a n J o a q u i n F i e l d : Un­ p u b lish ed r e p o r t,

V enezuela has

show n t h e e f f e c t s o f h y d r a t i o n o f c l a y s w i t h i n

the

th is fie ld

sand.

In

t h e N a r a n j a "L" s a n d h a s p e r m e a b i l i ­

t i e s u p to 50 m i l l i d a r c y s and a n a v e r a g e n e t sand t h i c k n e s s of 2 5.3 f e e t .

The f i r s t w e l l c o m p l e t e d i n

d u c e d I4.86 b a r r e l s o f o i l p e r d a y i n i t i a l l y choke. tie s

th is

sand p r o ­

through a 5/ l 6 w

S e v e ra l l a t e r w e l l s , how ever, had i n i t i a l

o f lifO b a r r e l s p e r d a y o r l e s s .

d rilled

to d eep er h o riz o n s ,

l e f t exposed process.

to th e d r i l l i n g

T h e s e w e l l s .w e re t h e n

a n d t h e N a r a n j a "L " s a n d w a s flu id

during

the deepening

A c i d i z a t i o n w i t h "mud a c i d " wa s t r i e d

tem pt to i n c r e a s e

p ro d u ctiv i­

the p r o d u c tio n r a t e ,

in an a t ­

b u t In m ost c a se s

t h i s was u n s u c c e s s f u l . L ater d r illin g

through

t h e N a r a n j a "L " s a n d w a s d o n e

w i t h o i l - b a s e mud, a n d t h e w e l l s h a d i n i t i a l p r o d u c t i o n r a t e s o f a p p r o x i m a t e l y I4.OO b a r r e l s was a t t r i b u t e d the

of o i l p e r day.

T his In c re a s e

to th e f a c t t h a t the c la y m a t e r i a l s w ith in

sand were n o t h y d r a t e d ,

and t h e r e f o r e ,

the norm al p e r ­

m e a b i l i t y was u n a f f e c t e d . It

is q u ite

p o ssib le

th at if

s u f f i c i e n t know ledge were

a v a i l a b l e of c la y c o n t e n t and e f f e c t s th ese c la y s,

of v a r io u s w a te r s upon

a d r i l l i n g mud w i t h a w a t e r b a s e c o u l d b e m i x e d

a n d s u c c e s s f u l l y u s e d w h i c h w o u l d b e much c h e a p e r a n d s a f e r to use

t h a n o i l - b a s e mud f o r d r i l l i n g

su c h a s th e one d e s c r i b e d .

through fo rm a tio n s

S a l t W ater D is p o s a l A very la r g e p e rc e n ta g e o f the o i l produced i n th e U n ite d S t a t e s i s p ro d u ce d from f o r m a tio n s w hich have a c t i v e w ater d r iv e s ,

and m i l l i o n s o f b a r r e l s o f t h i s .w ater

s a l t w a te r) a re produced w ith the o i l .

(u su ally

The w a t e r h a s a l m o s t

n o c o m m e r c i a l v a l u e a n d m u s t be d i s p o s e d o f i n some m a n n e r . T he common p r a c t i c e i s

to i n j e c t

t h i s produced w a te r back

in to

the a q u i f e r of the p ro d u cin g h o riz o n o r to i n j e c t i t

in to

o t h e r p o r o u s and p e rm e a b le s t r a t a . Many o i l w e l l s p r o d u c e a s m uch a s 5 0 0 , 0 0 0 b a r r e l s o f

s a l t w a t e r d u r i n g t h e i r econom ic l i f e .

R e g u lato ry b o d ies

w ith in m ost s t a t e s larg e q u a n titie s 8.

r e g u l a t e and d i r e c t th e d i s p o s a l o f t h e s e 8 of w ater. I n K a n s a s i t i s common p r a c t i c e

H a t f i e l d , J . R . , and H i c k s , L. B . , S a l t W a te r D i s p o s a l P r a c tic e s In K ansas: Am. P e t r o l e u m I n s t . P a p e r No, 851-23-B , p r e s e n te d a t S p rin g M eeting of M id -C o n tin en t D i s t r i c t a t T u l s a , O k l a h o m a , M a r c h 2 3 - 2 5 * 1 9 lf 9 .

to i n j e c t t h i s produced w a te r i n t o

th e lo w e r A rbuckle l im e ,

G r a n i t e W ash, R eagan S an d , o r D a k o ta S e c t i o n . I n c a s e s where th e

s a l t w ater i s r e - i n j e c te d

to the

a q u i f e r o f t h e h o r i z o n f ro m w h ic h i t was p r o d u c e d , horizons fo r

th e m ost p a r t take

p ro p erly f i l t e r e d .

the w a te r r e a d i l y

If

it

Is

the d i f f i c u l t i e s

encoun­

te r e d in f o r c in g h o riz o n s o th e r th a n the p ro d u c tiv e

zone t o

tak e the 9.

w a te r^

Q uite p o s s ib ly

these

a r e i n some m e a s u r e t r a c e a b l e

to h y d r a tio n

S tan d ard P rocedure f o r D eterm ining P e r m e a b ility of Porous M e d i a , Am. P e t r o l e u m I n s t . Code No. 27# 2d e d . , A p r i l 19k2.

of c lay m a te r ia ls w ith in the pore spaces. W ater F lo o d in g The I n j e c t i o n o f w a t e r i n t o o i l

sands f o r

the p u rpose

o f i n c r e a s i n g o i l r e c o v e r y i s a common p r a c t i c e sta te s.

The r a t e

sands d eterm in es quired

a t w h ic h w a t e r c a n be I n j e c t e d t o some e x t e n t t h e

in several in to

the

tim e w h ich w i l l be r e ­

to flo o d a p a r t i c u l a r p iec e of p r o p e r ty .

S everal

i n v e a t i g a t o r s ^ ' ^ ' ^ ’^plJj- have found t h a t c e r t a i n 10. 11. 12. 13.

llj..

J o h n s t o n , N o r r i s , a n d B e e s o n , C. M., W a t e r P e r m e a b i l i t y o f R e s e rv o ir Sands: P e tro le u m D e v e l. and T ech n o lo g y , p p . 1*3-55, 191*5. H u g h e s , R. V . , a n d P f i s t e r , R. J . , A d v a n t a g e s o f B r i n e s i n S e c o n d a r y R e c o v e r y o f P e t r o l e u m by W a t e r - F l o o d i n g : P e tro le u m D e v e l. and T ech n o lo g y , pp. 1 8 7 -2 0 1 , 19^7. B e c k s t r o m , R. E . , a n d Van T u y l , F . M . , E f f e c t o f F l o o d ­ in g O il Sands w ith A lk a lin e S o lu tio n s : Am. A s s o c . P e tr o le u m G e o l o g i s t s B u l l . , p p .11 , 223-237* 1927. S m i t h , K. W ., C l a r k , A. P . , a n d Y u s t e r , S . T . , B r i n e s a s Flooding L iq u id s: P ro c ee d in g s of th e S eventh S e c o n d a r y R e c o v e r y C o n f e r e n c e , The P e n n s y l v a n i a S t a t e C o l l e g e , N o vem ber 19l|.2. B r e s t o n , J . N . , a n d J o h n s o n , W. E . , E f f e c t o f pH o n W a t e r - I n t a k e R a t e o f O i l S a n d s : P r o d u c e r s M o n t h l y 9# ( 1 2 ) , p p . 1 9 - 2 3 , O c t o b e r 19^5*

a r t i f i c i a l b r i n e s and p ro d u c e d s a l t w a t e r s w i l l flo w th r o u g h sand sam p les m ore r e a d i l y

than w i l l f r e s h w a te r.

J o h n s t o n a n d B e e s o n ^ s t u d i e d some 1 2 0 0 s a m p l e s f r o m 15.

Loc. C i t . ,

p p . lj.3 -55 .

9lf w e l l s i n C a l i f o r n i a ,

and th e y found t h a t th e r a t i o

to s a l t w ater p e rm e a b ilitie s

of a ir

v a r i e d f r o m 1 . 0 t o o v e r 3 000

a nd t h a t t h e r a t i o was g r e a t e r t h a n 10 i n s c o r e s o f c a s e s . They a l s o f o u n d t h a t t h e i n d i c a t e d p e r m e a b i l i t i e s i n c r e a s e d

f o r m any s a m p l e s a s t h e creased.

sa lin ity

of the flo w in g w a te rs i n ­

They c o n c lu d e d t h a t " R e s u l t s o b s e r v e d to d a t e

a p p e a r to be s a t i s f a c t o r i l y

e x p l a i n e d by th e p r e s e n c e i n th e

sand of h y d r a ta b le m a t e r i a l s , search i s w arranted, an aly sis,

such as c la y s .

F u rth er r e ­

as fo r In sta n ce w ith p e tro g ra p h ic

to prove o r d isp ro v e

th is h y p o th esis."

They d i d

n o t , h o w e v e r , make a n y d e t e r m i n a t i o n s o f a m o u n t s o r t y p e s of c lay m a te r ia ls p re s e n t. Sm ith, 16 .

C lark,

and Y u s t e r 1 ^ r a n a s e r i e s o f e x p e r i m e n t s

Loc. C i t .

on s e v e r a l gro u p s o f c o re s b o th i n of o il

to d eterm in e

m edia.

T hey f o u n d

th e p r e s e n c e and a b s e n c e

the p o s s i b l e u s e s of b r i n e s a s f lo o d in g t h a t th e b r i n e flo w r a t e s w ere h i g h e r

th a n f r e s h w a t e r r a t e s and t h a t th e r e s i d u a l o i l w ere lo w e r w ith b r i n e s . b rin e,

they found

th at

satu ratio n s

When f r e s h w a t e r w a s r e p l a c e d w i t h th e f lo w r a t e s would i n c r e a s e and

t h a t the b rin e r a t e s

slow ly approached

th eir

th eo re tic al

liq u id p e rm e ab ility .

*These t e s t s w e r e made o n c o r e s f r o m

the B rad fo rd sa n d . L a t e r s t u d i e s made by B a t e s , 17.

G ruver,

and Y u s t e r ^ ^

B a t e s , T . F . , G r u v e r , R. M ., a n d Y u s t e r , S . T . , The C lay C o n te n t o f O il Sands: P r o d u c e r s M onthly 1 0 , ( 1 0 ) , p p . l 6 - 1 9 # A u g u s t 19M>.

showed t h e c h i e f c l a y m i n e r a l I n

t h e B r a d f o r d s a n d t o be

Illite . *»o B re sto n and Johnson*v s tu d ie d

t h e e f f e c t o f pH o n w a t e r

8

18.

Loc. C i t.

c o n d u c t i v i t y o f o i l - c o n t a i n i n g sa n d s on u n e x t r a c t e d r a d i a l cores of B radford, w aters

B a rtle sv ille ,

(pH o f a b o u t 2 . 5 ) a n d s a l t w a t e r s

gave h ig h e r c o n d u c t i v i t i e s 8 . 5 ),

and S ig g ln s

sands.

The a c i d

(sodium c h l o r i d e )

than b a s ic w a te rs

(pH o f a b o u t

a n d t h e e f f e c t s e e m e d t o be r e v e r s i b l e . T h e s e i n v e s t i g a t i o n s seem t o p r o v e t h a t t h e p e r m e a b i l i ­

t y o f a s a n d s t o n e d e p e n d s i n many c a s e s u p o n t h e f l u i d f l o w i n g , and th e y i n d i c a t e

type of

t h a t m uch c a n be d o n e t o

im p ro v e t h e r a t e s a t w h ic h sa n d c a n be f l o o d e d by s e l e c t i o n o f a p r o p e r f l o o d i n g medium. It

seems w o r t h w h i l e ,

th erefo re,

th a t fu rth e r in v estig a-

t i o n s b e made i n o r d e r

to t i e

down t h e v a r i o u s o b s e r v e d

e f f e c t s m o re c l o s e l y .

B efore

th is

m u s t b e known o f t h e n a t u r e

c a n be d o n e ,

som ething

a n d p r o p e r t i e s o f t h e c l a y ma­

t e r i a l s w h i c h may b e p r e s e n t i n o i l

sa n d s and s a n d s t o n e s .

CLAY MINERALS Clay m a t e r i a l s a r e

i m p o r t a n t i n many d i f f e r e n t a n d d i s ­

t i n c t p h a s e s o f m odern l i f e ,

and t h i s f a c t h a s b e e n th e m ain

r e a s o n f o r o u r p r e s e n t know ledge o f t h e i r n a t u r e and p r o p e r ­ tie s.

T hey a r e v i t a l i n a g r i c u l t u r e b e c a u s e t h e y c o m p r i s e

an e s s e n tia l p a rt of s o ils ;

in c o n stru c tio n en g in eerin g ,

s t r u c t u r e s a r e b u i l t on them and w i t h them ; i n t h e c e r a m i c , rubber, trie s,

paper, m etal-fo u n d in g ,

cem ent,

a n d many o t h e r i n d u s -

th e y a r e an i m p o r t a n t raw m a t e r i a l .

19

They a r e w i d e l y

19.

G r i m , R. E . , M o d e r n C o n c e p t s o f C l a y M a t e r i a l s : Jour. G eo lo g y , v o l . L . , n o . 3 , p . 225, A p ril-M a y , 19^2.

used in

the p e tro le u m r e f i n i n g i n d u s t r y

c o lo r of o i l s ,

to im prove th e

o r r e s i n o u s m a t e r i a l , and 20 a s a c a t a l y s t in c ra c k in g crude o i l s . The c l a y m a t e r i a l s 20.

are

N e l s o n , W. L . , P e t r o l e u m R e f i n e r y E n g i n e e r i n g , McGrawH i l l Book C om pany, I n c . , New Y o r k , p p . 5^-1-567* 1 9 3 6 . the b a s i c

many o f sh ales. 21.

to remove a s p h a l t i c

i n g r e d i e n t i n d r i l l i n g muds,

the h o r iz o n s d r i l l e d 21

and th e y fo rm

th ro u g h --su c h as heaving

T hey o c c u r t o some e x t e n t i n a l m o s t a l l

o i l and

F r o s t , J . M ., I l l , G e o l o g i c A s p e c t s o f H e a v i n g S h a l e i n Texas C o a s ta l P l a i n : Am. A s s o c . P e t r o l e u m G e o l o ­ g i s t s B u l l . , v o l . 23, n o . 2, p p . 2 1 2 -2 1 9 » F e b r u a r y 1939.

gas sands.

The e c o n o m i c i m p o r t a n c e o f

these m a te r ia ls h as

stim u lated a g re a t deal of s c ie n tif ic

r e s e a r c h and i n v e s t i ­

g a t i o n by p e o p le p r i m a r i l y i n t e r e s t e d

in each of

the v a r i -

o u s l n d u 8 t r l e 9 . 2 2 ' 23 ' ^ * 25 , 2 6 , 2 7 , 2 8 , 2 9 , 3 0 , 3 1 , 3 2 . 3 3 22. 23.

2k* 25. 26.

27. 28.

^

G r i m , R. E . , L o c . C i t . N e l s o n , W, L . , L o c . C i t . F r o s t , J . M ., I l l , L o c . C i t . G r i m , R. E . , P r o p e r t i e s o f C l a y : I l l i n o i s G eol. Survey C i r c u l a r ij.9* 1 9 3 9 . R o s s , C. S . , a n d H e n d r i c k s , S . B . , M i n e r a l s o f t h e M o n t m o r i l l o n i t e G r o u p - - T h e ir O r i g i n and R e l a t i o n to S o i l s and C la y s : U. S . G e o l . S u r v e y P r o f . P a p e r 2 0 5 - B , G r i m , R. P e t r o g r a p h i c and C eram ic P r o p e r t i e s o f P en n sy lv an ian S hales of I l l i n o i s : J o u r . Am. C e r a m i c S o c i e t y , v o l . 2k, n o . 1 , p p . 2 3 - 2 8 , 194* N o r t o n , F . H . , A p p l i c a t i o n s o f Modern C la y R e s e a r c h I n C eram ics: J o u r . G e o l o g y , v o l . L , n o . 3* P P . 3 2 0 - 3 3 0 * A p r i l - M a y , 19k2*

29. 30. 31. 32.

33.

K e l l e y , W. P . , M o d e r n C l a y R e s e a r c h e s i n R e l a t i o n t o A g ricu ltu re: J o u r . G e o lo g y , v o l . 2, n o . 3 , p p . 3 0 7 319* A p r i l - M a y , 1 9 ^ 2 . W i n t e r k o r n , H. F . , A p p l i c a t i o n s o f M o d e rn C l a y R e ­ search es in C o n stru c tio n E n g in eerin g : J o u r . G eology, v o l . L , n o . 3* P P . 2 9 1 - 3 0 6 , A p r i l - M a y , 19^2* S c h r o t e r , G. A . , a n d C a m p b e l l , I v a n , G e o l o g i c a l F e a ­ t u r e s o f Some D e p o s i t s o f B l e a c h i n g C l a y : Am. I n s t . M i n . M e t . E n g . T e c h . P a p e r 1 1 3 9 - H , 1 9 ^4-0 . F a n c h e r , G. H . , a n d O l i p h a n t , S . C . , The N a t u r e o f H a s t i n g s D r i l l i n g Mud by S u p e r c e n t r i f u g e a n d X - r a y A n aly sis: P e tr o le u m D e v e l. and T e c h n o lo g y , p p . 2212 3 2 , 191*3. R o s s , C. S . , a n d K e r r , P. F . , The C l a y M i n e r a l s a n d T h eir I d e n tity : J o u r . Sedim entary P e tro lo g y , 1, 1931.

com bined w orks r e f e r e n c e d t i o n s make a v a i l a b l e

h e r e , p l u s many o t h e r I n v e s t i g a ­

to those In the p e tro leu m p ro d u c tio n

in d u s try a w e alth of v a lu a b le in fo rm a tio n concerning

these

im portant m a te ria ls . D e fin itlo n s Ihe

term " c la y " i s

e r a l i s w ell understood;

a common one w h o s e m e a n i n g i n g e n ­ how ever, i t

g ive a p r e c is e d e f i n i t i o n of the the

term " c la y " c a r r i e s w ith i t

n a tu ra l m a te ria l w ith p la s tic

is

term .

to

As g e n e r a l l y u s e d ,

th ree im p lica tio n s:

p ro p erties,

com p o sitio n of p a r t i c l e s of very f in e co m p ositio n of c r y s t a l l i n e

very d i f f i c u l t

(2 ) an e s s e n tia l

size,

and

(3 ) a b a sic

fragm ents of m in e ra ls

e s s e n t i a l l y h y d r o u s alum inum s i l i c a t e s

or,

(l) a

th a t are

o ccasio n ally ,

h y d r o u s m agnesium s i l i c a t e s . ^ 3^.

G r i m , R. E . , M o d e r n C o n c e p t s o f C l a y M a t e r i a l s : C it. The t e r m " s h a l e ” I s g e n e r a l l y u s e d

Loc.

t o d e s i g n a t e ma­

t e r i a l w hich d i f f e r s fro m c l a y o n ly i n t h a t i t

i s lam inated

and s l i g h t l y more i n d u r a t e d .3 5 35.

Ib id . "Clay m a t e r i a l "

i s used in

t h i s p a p e r to d e s i g n a t e any

n a t u r a l m a t e r i a l h aving the th re e re q u ire m e n ts l i s t e d p r e ­ v io u sly .

T herefore,

it

i n c l u d e s muds, c l a y s ,

sh ales,

so ils,

e tc . C o n s t i t u t i o n o f C lay M a t e r i a l s A n a l y s e s o f many c l a y m a t e r i a l s b y X - r a y ,

o p tic al,

c h e m ic a l, d e h y d r a t io n , and th e rm a l m ethods have

shown t h a t

they g e n e r a lly a re a g g re g a te s of e x tre m e ly sm all p a r t i c l e s o f o n e o r m o r e s p e c i e s o f a s m a l l g r o u p o f m i n e r a l s known as the c la y m i n e r a l s . ^ 36.

G r i m , R. E . ,

P r o p e r t i e s of C lay:

(except fo r a llo p h an e ). cates,

Loc. C i t.

They a r e h y d r o u s alum inum s i l i ­

f r e q u e n t l y w i t h r e p l a c e m e n t o f t h e alum inum by i r o n

and m agnesium . m aterials

p u lg ite ,

In a d d itio n

to

the c la y m i n e r a l s ,

c o n ta in sm all q u a n t i t i e s o f q u a r t z ,

org an ic m a tte r.

37.

The c l a y m i n e r a l s a r e c r y s t a l l i n e

A ll of the c la y m in e r a ls ,

the c la y

lim o n lte,

and

except a tta -

occur in f l a t flak e-sh ap ed or p l a t e - l i k e p a r ti c le s ? ?

G rim , R. E . , Modern C o n c e p t s o f C la y M a t e r i a l s : C i t., p. 229. The c l a y m i n e r a l s u s u a l l y o c c u r i n p a r t i c l e s l e s s

a b o u t 5 m icro n s in d ia m e te r . The c r y s t a l l i n e

Loc.

th an

(One m i c r o n e q u a l s 0 * 0 0 1 mm.)

clay m in erals are

th e d o m in a n t com ponents o f

clay m a te ria ls ,

and t h e i r p r o p e r t i e s m ust be a c c o u n t e d f o r

on th e b a s i s o f th e c r y s t a l l i n e 38.

com ponents.^®

Ib id . The C l a y M i n e r a l s D e ta ile d m in e r a lo g lc a l a n a ly s e s i n r e c e n t y e a r s have

in d ic ate d m in erals: 39.

the e x is te n c e K a o lin ite,

G r i m , R. E . ,

A lm ost a l l these

of th ree

im p o rtan t groups of c la y 39 and M o n t m o r i l l o n l t e .

Illite ,

P r o p e r t i e s of C lay:

Loc. C i t . ,

p . I4.6 7 .

c l a y s a r e com posed o f one o r more members o f

th re e groups. K a o l i n i t e Group The m o s t common m em b er o f t h i s g r o u p i s K a o l i n i t e

w hich h as th e c o m p o s itio n . N a c rite have the

^ H ) qA1^S1|^0^ q .

D ic k ite and

same c o m p o s i t i o n a s K a o l i n i t e b u t h a v e

s l i g h t l y d i f f e r e n t c r y s ta llo g r a p h ic form s. c o n stitu e n ts of a rg illa c e o u s I4.O.

se d im e n ts.^

Loc.

lik e K a o lin ite ex cep t w ith a

h ig h e r s ilic a - to - a lu m in a m o lecu lar r a t i o ,

b u t o n l y a few

o c c u rre n c e s of a n a u x lte have been r e p o r te d . Illite The I l l i t e

to ,

The o t h e r m em ber

G r i m , R. E . , M o d e r n C o n c e p t s o f C l a y M a t e r i a l s : C i t . , p. 233.

o f th e group i s A n a u x lte ,

rare

They a r e r a r e

m in erals are

the w h ite m icas.

Group

sim ilar to ,

but not id en tical

These m i n e r a l s have b een r e f e r r e d

to

as "m ica-lik e

clay m in e ra l,"' " s e r l c i t e - l i k e m in e ra l,"

"p o tash -b e a rin g c lay m in e ra l."

These m in e r a l s c o n t a i n l e s s

p o t a s h a n d m o r e w a t e r t h a n do t h e w h i t e m i c a s ,

and th e y

d i f f e r f r o m t h e m i n some p h y s i c a l p r o p e r t i e s . ^ 14.1 .

Ib id .,

p.

and B r a d l e y ^

k-2.

and

G rim , B ra y ,

231. suggested

t h e name I l l i t e

a s a g r o u p name a n d

G r i m , R, E . , B r a y , R. H . , a n d B r a d l e y , W. P . , The M i c a i n A r g illa c e o u s Sedim ents: Am. M i n e r a l o g i s t , v o l . 2 2 , pp. 813-829, 1937.

advanced the g e n e r a l fo rm u la

(OH)]+Kr ( A l ^ . F e ^ . M g ^ . M g 6 )

S ig .y .A l^O ^Q w here y v a r i e s from 1 . 0 to 1 .5*

S p ecific

nam es h a v e n o t b e e n g i v e n t o t h e members o f t h e g r o u p a s y e t. M o n t m o r i l l o n i t e Group T his group ta k e s i t s l o n i te w hich p ro b a b ly h a s 11H2 O.

the co m p o sitio n

The a l u m i n u m i s u s u a l l y p a r t i a l l y

n e siu m and f e r r i c th e alum inum , tro n ite iro n . lj-3.

name f r o m t h e m i n e r a l M o n t m o r i l ­

iro n .

r e p l a c e d by m a g ­

I f magnesium c o m p l e t e l y r e p l a c e s

t h e name S a p o n i t e i s

i s used i f

(O H ^A I^SIqC ^q.

th e alum inum i s

ap p lied .

The name N o n-

c o m p l e t e ly r e p l a c e d by

A l l members o f th e g r o u p h a v e an e x p a n d i n g l a t t i c e ^ Ross,

C. S . ,

and H e n d r ic k s ,

S. B . , L o c. C i t . ,

a n d t h i s h a s come t o b e t h e d i a g n o s t i c group.

p.

29.

c rite rio n fo r th is

M inor G roups The g r o u p s o f m i n o r I m p o r t a n c e a r e H a l l o y s i t e , p u lg lte ,

A llo p h a n e , and C hlorifclc M ica.

r a t h e r I n d i s t i n c t and o f l i t t l e

A tta-

These g ro u p s a re

im portance in s tu d ie s of

th i s type. The S t r u c t u r e

of C lay M in e ra ls

A v a s t amount o f d a t a h a s b een a c c u m u la te d on th e la ttic e

stru c tu re

of th ese m in erals sin ce the a p p lic a tio n

of X -ray d i f f r a c t i o n a n a l y s i s . s tr u c tu r e s are

still

broader fe a tu re s

The d e t a i l s o f

some o f t h e

a m a tte r of c o n tro v e rs y , b u t the

se em t o b e w e l l e s t a b l i s h e d . ^

Two s t r u c -

P a u l i n g , L . , The S t r u c t u r e o f M i c a s a n d R e l a t e d M in ­ e rals: P ro c . N at. Acad. S c i . , v o l. 16, pp. 123-129, 1930. t u r a l u n i t s a re in v o lv ed in m in erals.

th e atom ic l a t t i c e s

of th ese

One i s

t h e a l u m i n a o r alum inum h y d r o x i d e u n i t ,

w hich c o n s i s t s o f

two s h e e t s o f c l o s e l y p a c k e d o x y g e n s o r

h y d r o x y l s b e tw e e n w h ic h alum inum atom s a r e embedded i n su c h a p o sitio n

th at

hy d ro x y ls.

th e y a r e e q u i d i s t a n t from s i x oxygens o r

T w o - t h i r d s o f t h e p o s s i b l e alum inum p o s i t i o n s

are occupied in

th is u n it,

and i t

is

the G ib b s ite

The s e c o n d u n i t c o n s i s t s o f a s h e e t o f (SiOf^) g r o u p s l i n k e d

tetrah ed ral s ilic a

to form a h e x a g o n a l netw ork o f

p o s i t i o n Si^O^o * h e n i n d e f i n i t e l y r e p e a t e d . atom s a r e i n sa tisfie d

tetrah e d ral p o sitio n s,

by t h r e e

stru c tu re .

The s i l i c o n

th re e v a le n c e s b ein g

oxygens i n the o v e r ly in g s h e e t .

f o u r t h s i l i c o n v alen cy i s

sa tisfie d

t h e com­

The

below by a n o x y g e n atom

in

the G ib b s ite

sh eet.

Grim, R. E . , M o d e r n C o n c e p t s o f C l a y M a t e r i a l s : c it.,

pp.

S tru ctu re

of M o n tm o rillo n ite

The comm only a c c e p t e d sists

of

k6.

silic a

I b i d . , pp.

tetrah ed ral

tatio n e x ists lo o s e ly held

groups^

in

The

and e v i d e n t l y l i t t l e

the

o r no o r i e n ­

The u n i t s a r e

to g e th e r in the c d i r e c t i o n w ith w a ter p r e s e n t The a m o u n t o f w a t e r b e t w e e n t h e u n i t s

and d i m e n s i o n s i n

t h e c d i r e c t i o n v a ry so t h a t th e

m in eral i s

said

is

to t h a t o f P y r o p h y llite i f

to have an expanding l a t t i c e .

betw een th e u n i t s . the d is ta n c e

(F igure 1 ) .

th e a and b d i r e c t i o n s .

betw een th e u n i t s .

sim ilar

s h e e t b e t w e e n tw o

s t a c k e d one ab o v e t h e o t h e r i n

d ir e c tio n of the c - a x is ,

of

of M o n tm o rillo n ite con­

238-2^3.

s tr u c tu r a l u n its are

v aries,

stru ctu re

s t r u c t u r a l u n i t s o f one G i b b s i t e

sh eets of

Loc.

237- 23 8 .

The l a t t i c e

no w a t e r i s p r e s e n t

In th e ab sen ce of w a te r

(See F i g u r e l )

betw een the u n i t s m easured betw een th e c e n t e r s

the oxygens i s

3 .0 A n g stro m s, and c d im e n s io n s v a ry from

9 . 6 A ngstrom s to a b o u t 2 1 . ^ A n g stro m s.

H e n d ric k s, N elson,

and A l e x a n d e r ^ h a v e p r e s e n t e d e v id e n c e

to i n d i c a t e

I4.7 .

th at

the

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