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ABSTRAC'Y
Transient minima r~re o f t e n observed in the Interracial tension o f enhanced oil recovery
surfactants against crude oil. One possible explanation for the time-dependence is t h e
interaction o f surfactants from the crude oil with those from t h e aqueous ph~.se at the
interface. The suggested mechanism involves the diffusion o f crude oil surfactants initially
into t h e interface forming a mixed layer responsible for the low tension followed by
solubilisation in t h e bulk aqueous solution. This mechanism has been investigated for a
carboxyhetaine surfactant with de ,~ane and decanoic acid as model oil and oil surfactant,
respectively. ]Rheological pzoperties and mlcellar sizes have been determined For two
regimes corresponding to different degrees o f enhancement o f surfac~ant concentration at
the interface. The lowest tensions are observed close t o the b o u n d a r y between viscous
surfactant solutions c o n t a i n i n g large micelles and a two-liquid-phase region. The low
tensions e x t e n d into the t w o - p h a l ~ e o m p o s i t i o n range. The occurrence o f low Interfaei~l
tensions is postulated to correspond t o the compositions f o r which hydrocarbon soiubll-
isation in the surfactant phase is a maximum.
INTRODUCTION
s a n d p a c k s u s e d as m o d e l r e s e r v o i r s . O n e r e a s o n f o r t h i s f a i l u r e w a s u n -
d o u b t e d l y t h e p r o p e n s i t y t o r e n d e r t h e s a n d oil w e t , t h u s e x t e n d i n g t h e
period required for recovery beyond the timescale of the experiment.
H o w e v e r , o f c o m p a r a b l e i m p o r t a n c e w a s t h e o b s e r v a t i o n t h a t ~d e s p i t e t h e
a c h i e v e m e n t o f v e r y l o w t r a n s i e n t i n t e r r a c i a l t e n s i o n s a g a i n s t c r u d e oil
( t y p i c a l l y ~ 4 × 1 0 -3 m N m -1 a f t e r 3 0 r a i n i n t h e s p i n n i n g d r o p t e n s i o m e t e r ) ,
e q u i l i b r i u m v a l u e s ( ; ~ 2 4 h ) w e r e in t h e r a n g e 0 . 2 - - 1 . 0 m N m - 1 .
U l t r a - l o w t r a n s i e n t t e n s i o n s a r e well k n o w n in l o w - c o n c e n t r a t i o n -
surfactant systems. A mixed anionie/zwitterionic surfactant system in which
t h e s e p h e n o m e n a a r e o b s e r v e d h a s b e e n d e s c r i b e d [ 3 ] . O n e p r o p o s e d ex-
p l a n a t i o n f o r t h e s e t r a n s i e n t t e n s i o n s is i n i t i a l d i f f u s i o n o f c r u d e oil
surfactants to the interface forming a mixed surfactant layer responsible for
t h e l o w t e n s i o n s . S u b s e q u e n t l y , s m a l l o,u a n t i t i e s o f t h e c r u d e oil s u r f a c t a n t s
are solubilised away from the interface into the bulk aqueous surfactant
s o l u t i o n a n d t h e t e n s i o n rises a g a i n . A s t u d y o f t h e i n f l u e n c e o f s u r f a c e -
a c t i v e c o m p o n e n t s o f t h e c r u d e o n r h e o l o g t c a l p r o p e r t i e s o f o i l / w a t e r inter-
faces h a s d e m ~ n . ~ t r a t e d t h e e x i s t e n c e o f v i s c o u s o r v i s c o e l a s t i c f i l m s [ 4 ] .
In o r d e r t o i n v e s t i g a t e t h e v a l i d i t y o f t h e p r o p o s e d e x p l a n a t i o ] t t h e rela-
tionship between phase behaviour, micellar properties and interracial tension
w a s i n v e s t i g a t e d f o r m i x t u r e s o f h c x a d c . ~ y l d i m e t h y l a m m o n i o m e t h a n e earb-
o x y l a t e ( S , ) a n d d e c a n o i c a c i d ($2) as m o d e l c r u d e oil s u r t ' a c t a n t . M i c e l l a r
sizes w e r e d e t e r m i n e d b y r h e o l o g i c a l m e a s u r e m e n t s in t w o c o t ~ c e n t r a t i o n
r e g i o n s ; 1 . 3 3 X 1 0 - 2 M Sj + 5 . 8 X 1 0 - 4 ~ 5 . 8 X 1 0 - 3 M S= r e p r e s e n t i n g
i n t e l ' f a c e c o n c e n t r a t i o n s s i m i l a r t o t h o s e in t h e b u l k a n d 1 . 5 3 X 1 0 - t M
S, + 5.8 × 1 0 - ~ - - 5 . 8 X 1 0 - = 3 / $ 2 r e f l e c t i n g t h e p o s s i b l e e n h a n c e m e n t o f
t h e cor, centrati(>n o f s u r f a c e - a c t l v e s p e c i e s a t t h e i n t e r f a c e .
Hexadecyldimethylammoniomethane c a r b o x y l a t e w a s p r e p a r e d b y re-
fluxing hexadecyldimethylamine with sodium chloroacetate and separating
t h e NaCI f r o m t h e p r o d u c t b y e x t r a c t i o n . H P L C analy-~is i n d i c a t e d t h e
s u r f a e t a n t w a s ~ 9 9 % p u r e . D e c a n o i c a c i d w a s F l u k a p u r i s s g r a d e . All ~olu-
t i o n s w e r e p r e p a r e d in f i l t e r e d s e a w a t e r a d j u s t e d t o p H 6 . 5 b y HCI a n d
NaOH solutions. Solutions were prepared by heating to 60--70°C for several
hours to ensure intimate mixing of components followed by equilibrating at
room temperature for at least seven days.
Interracial tensions were measured against decmle using the Texas spinning
drop tensiometer. Rheological measurements on the higher concentration
range samples were made using the Weissenberg Rheogonimeter fitted with
5 . 0 c m c o n e - a n d - p l a t e , u s i n g b o t h s t e a d y s h e a r a n d o s c i l l a t o o y mot~.~s. F o r
the lower concentration range a Contraves LS 30 concentric cylinder (low
s h e a r ) v i s c o m e t e r w a s u s e d . All m e a s u r e m e n t s w e r e m a d e a t 25°C.
i
131
THEORY
w h e r e H(r) = n u m b e r o f s p e c i e s w i t h r e l a x a t i o n t i m e T. E q u a t i o n ( 2 A ) is u s e d
w h e n t h e s l o p e o f H ( T ) : I n w is p o s i t i v e a n d E q n ( 2 b ) w h e n i t is n e g a t i v e .
A differe_,~t a p p r o a c h • w a s u s e d f o r d i l u t e s o l u t i o n s . S t e a d y s h e a r m e a s u r e -
ments only were made and for the most viscous (single phase) composition
t h e S i m h a [7,81 e q u a t i o n ( m o d i f i e d b y H o f f m a n n e t al. [ 9 ] ) w a s u s e d t o
o b t a i n a n e s t i m a t e o f m i c e l l e size.
--
0.933 +
p2 *
1
+
1
{rt) d 5d 31n(2p) - X In(2p) - X + 1
where
17 --T/0
{~ } : l i m
e-*0 ~0C
ffi v i s c o s i t y o f t h e s o l u t i o n , ~0 ffi v i s c o s i t y o f t h e s o l v e n t , C = s o l u t i o n c(:n-
centration, d - density of the s o l u t i o n , p = a / b w h e r e a ffi l o n g axis, b -- s h o r t
axis, ~ = 1 . 8 ( f o r r o d s ) .
Since this equation cannot e a s i l y b~ s o l v e d a n a l y t i c a l l y v a l u e s o f p w e r e
selected and the best fit found by iteration.
132
RESULTS
High c o n c e n t r a t i o n range
TABLE1
T h e inter-facial textsion b e h a v i o u r b e t w e e n d e e a n e a n d s u r f a c t a n t s o l u t i o n s
is s h o w n in T a b l e 2. F o r these samples ( a n d for t h e d i l u t e c o n c e n t r a t i o n
range descrilced b e l o w ) e q u i l i b r i u m interfacial tensions against d e c a n e w e r e
a c h i e v e d in a few m i n u t e s suggesting t h a t it was o n l y n ecessary f o r t h e d r o p
to a t t a i n physical stability w i t h i n t he capillary. T h e shallow m i n i m a with
t i m e o b s e r v e d m a y be d u e to small a m o u n t s o f i m p u r i t i e s in t h e d e c a n e . [n
general, t h e results suggest a t r e n d o f d e c r e a s i n g interfacial ten s io n w i t h
increasing m i c e l l a r weight. C o m p o s i t i o n s in t h e h i g h e r c o n c e n t r a t i o n range
e x i s t e d as single phase, c l e a r s o l u t i o n s u p t o 2.91 X 1 0 -2- M d ec an o ic acid.
A t h i g h e r c o n c e n t r a t i o n s t h e s o l u t i o n s w e r e slightly c l o u d y a l t h o u g h t h e r e
was n o e v i d e n c e o f gross phase s e p a r a t i o n . T h e r e l a x a t i o n ~times (T) fall
generally i n t o t w o ranges; i- ~ 0.3--=0.-t $ a n d T ;~ 1,0 s. T h e i r significance is
discussed b e l o w .
TABLE 2 ."-,!~ " . -
- - , . . ,
Decanole acid Lowest T (ran m-' ) "lime to minimum Equilibrium ? (raN m-, )
O-t. 11,0
O SHEAR RATE :0.S Is-I |
& SHEAR RATE ; 5 " 1 ~ I t~ I
X
0.3 30
o_
..~u.
P! TWO LIQUID
z 0-2 PHASI~S 2o u)
E o
(J
>o (/ii
\
0.! x 1 I°
DISCUSSION
Increasing t h e c o n c e n t r a t i o n o f d e c a n o i c acid s i m u l a t e s t h e d i f f u s i o n o f
c r u d e oil surfactmlts t o t h e i n t e r f a c e w h i c h o c c u r s w h e n c r u d e oil is in con-
t a c t w i t h s u r f a v t a n t s o l u t i o n . This is a c c o m p a n i e d by g r a d u a l l y d e c r e a s i n g
interracial t e n s i o n . T h e d e c a ~ o i c a c i d c o m i c e | l i s e s with th e c a r b o x y b e t a i n e ;
t h e negative citarge o n t h e d e c a n o a t e in teracts s t r o n g l y w i t h t h e positively-
c h a r g e d n i t r o g e n resulting in a d e c r e a s e d negative c h a r g e d e n s i t y a t t h e
surface t h u s l o w e r i n g i n t e z m o l e c u l a r repulsions. T h e s e repulsions are a l r e a d y
r e d u c e d by t he high e l e c t r o l y t e c o n t e n t o f t h e s e a w a t e r s o l v e n t a n d t h u s
c o n d i t i o n s are f a v o u r a b l e f o r t h e f o r m a t i o n o f a s y m m e t r i c micelles [ 9 , 1 1 ] .
T h e m a r k e d viscoelastic e f f e c t s o b s e r v e d in these s y s t e m s suggest t h a t these
micelles are cylindrical. In t h e high c o n c e n t r a t i o n region micelle sizes in-
crease w i t h d e c a n o i c acid c o n c e n t r a t i o n in t h e m o l e c u l a r w e i g h t rmlge 3 X
1 0 s - - 8 X 10 +. S t r o n g i n t e r a c t i o n s w o u l d be e x p e c t e d w i t h i n s u c h asym-
m e t r i c aggregates a n d t he s e m o l e c u l a r weights are ty p ical o f t h o s e observed
in viscoelastic surf:tctant m i x t u r e s . T h e largest aggregates have m o l e c u l a r
weights ~ 8 X 10 + c o r r e s p o n d i n g t o a length o f ~ 7 4 0 n m . [t has b e e n sug-
gest :d t h a t liquid c r ys t a l phases a r e c h a r a c t e r i s e d by l o n g range o r d e r o f at
least 1 0 0 0 n m [ 1 2 | . H e n c e , it is n o t surprising t h a t this c o m p o s i t i o n is close
to t h e l i mi t o f e x i s t e n c e o f t h e isoh-opic liquid phase.
R e l a x a t i o n times ( p o s i t i o n s o f m a x i m a in t h e r e l a x a t i o n spectra} general-
ly fall i n t o t w o groups viz. 0.3, 0.45 a n d ~ 1.5 s. T h e f o r m e r p r o b a b l y re-
flect o r i e n t a t i o n a l r e l a x a t i o n o f individual mfcelles f o l l o w i n g shearing. T h e
135
l a t t e r c o r r e s p o n d s t o a r e l a x a t i o n t i m e o f t h e m i c e l l a r n e t w o r k since these
c o r r e s p o n d t o t h e t i m e s c a l e o f visually-observed viscoelastic r e l a x a t i o n .
F u r t h e r m o r e , t h e l o n g e r r e l a x a t i o n t i m e is o n l y o b s e r v e d a t h i g h e r d e c a n o i c
acid c o n c e n t r a t i o n s w h e r e t h e large micelles r e q u i r e d f o r fo~li~ing a visco-
elastic n e t w o r k are present.
In t h e l o w c o n c e n t r a t i o n region, t h e micelles increase in size u n t i l t h e y
c a n a c c o m m o d a t e n o f u r t h e r d e c a n o i c acid a n d a s e p a r a t e p h a s e rich in t h e
l a t t e r c o m p o n e n t is f o r m e d . In t h e two-phas~ region it is likely t h a t t h e
u p p e r viscous pha~e c o n t a i n s large c y l i n d r i c a l micelles. As t h e d e c a n o i c a c i d
is f u r t h e r i n c r e a s e d m o r e o f t h e c l o u d y l o w e r ~p h as e rich in act.J is e v i d e n t .
T h e c o m p o s i t i o n r a t i o a t w h i c h t h e viscosity m a x i m u m o c c u r s c o r r e s p o n d s
t o t h a t a t t h e h i g h e r c o n c e n t r a t i o n s . This in d icates t h a t t h e c o n c e p t o f a
critical d e c a n o i c acid level e x t e n d s over a w i d e c o n c e n t r a t i o n range.
T h e interracial t e n s i o n in b o t h high a n d l o w c o n c e n t r a t i o n ranges de-
creases w i t h i n c r e ~ i n g m i c e l l a r size a n d r e m a i n s l o w b e y o n d t h e l i m i t o f
e x i s t e n c e o f a single phase in t h e d i l u t e region. T h e interracial t e n s i o n be-
t w e e n d e c a n e a n d t h e u p p e r clea~" pha se is o f t h e s a m e o r d e r as t h a t for t h e
w h o l e c o m p o s i t i o n . ( T h e o p a c i t y p r e v e n t e d t h e t e n s i o n o f t h e lower, c l o u d y ,
ph as e against d e c a n e f r o m being m e a s u r e d in t h e s p i n n i n g d r o p t e n s i o m e t e r . )
T h e interfacial t e n s i o n b e h a v i o u r o f c r u d e o i l / c a r b o x y b e t a i n e s o l u t i o n s
can thus be e x p l a i n e d by t h e f o l l o w i n g m e c h a n i s m . I m m e d i a t e l y a f t e r t h e
f o r m a t i o n o f t h e interface, t h e t e n s i o n b e t w e e n t h e small micelles in t h e
z w i t t e r i o n i c s u r f a c t a n t s o l u t i o n a n d c r u d e oil is relatively high (0.3 m N
m - I ). S u r f a c t a n t s f r o m t h e c r u d e oil d iffu se r a p i d l y t o t h e i n t e r f a c e a n d t h e
m i c e l l a r size increases. As t h e pha s e b o u n d a r y is a p p r o a c h e d , t h e s u r f a c t a n t
m i x t u r e b e c o m e s m o r e oil s ol ubl e e n h a n c i n g t h e l i k e l i h o o d o f t h e forrnatiozz
o f small a m o u n t ~ o f t hi r d pha s e a t t h e i n t e r f a c e . S u c h t h i r d phases
are k n o w n t o be associated with u l t r a - l o w t e n s i o n s [ 2].
S u b s e q u e n t l y , t h e s u r f a c t a n t s o f t h e t y p e originating in c r u d e oil m a y
d i f f u s e a w a y f r o m t he interracial l a y e r i n t o t h e b u l k a q u e o u s s o l u t i o n w h e r e
t h e y are solubilised b y t h e large excess o f s u r f a c t a n t r e m a i n i n g there.
C o n s e q u e n t l y , t h e t e n s i o n rises f r o m u l t r a - l o w values b u t r e m a i n s a t 1 m N
m - ' c o m p a r e d with 28 m N m - l for d e c a n e against s eaw ater. This In-
dicates t h a t a substantial a m o u n t o f s u r f a c t a n t n : m a i n s at t h e interface.
T h e o c c u r r e n c e o f interracial t e n s i o n m i n i m a at i n t e r f a c e s has b e e n dis-
c u s s e d in t e r m s o f mass t r a n s f e r a n d a d s o r p t i o n / d e s o r p t i o n barriers b y R u b i n
a n d R a d k e [ 1 3 ] . T h e s e a u t h o r s e m p h a s i s e t h a t t h e high w a t e r : o i l p h as e
v o l u m e ra t i o in t h e s p i n n i n g d r o p t e n s i o m e t e ~ m a y a c c e n t u a t e o b s e r c e d
t e n s i o n m i n i m a . Nevertheless, e x p e r i m e n t s have s h o w n t h a t these effects are
m a n i f e s t e d in sand p a c k oil d i s p l a c e m e n t tests f o r this s u r f a c t a n t system.
I t is i m p o r t a n t t o n o t e t h a t this p a p e r r e p o r t s phase b e h a v i o u r in t h e
a b s e n c e o f h y d r o c a r b o n . Solubilised h y d r o c a r b o n s w o u l d increase micelle
size a n d possibly c a us e t h e pha s e s e p a r a t i o n t o o c c u r a t a l o w e r d e c a n o i c
acid c o n c e n t r a t i o n .
136
CONCLUSIONS " +
ACKNOWLEDGEMENTS
REFERENCES
1 M.H. A k s t i n a t , 1 9 8 1 E u r o p e a n 8 y m p o s l u r n o n E n h a n c e d Oil R e c o v e r y P r o c e e d i n g s ,
P l e n u m , N e w Y o r k , N Y , 1 9 8 1 , p. 43.
O_ D . O . S h a h , 1 9 8 1 E u r o p e a n Symposium o n E n h a n c e d Oil R e c o v e r y P r o c e e d i n g s ,
P l e n u m , N ~ w Y o r k , N Y , 1081, p . I .
3 E.L. N e u s t a d t e r a n d P.A. Wheeler+ in p r e ~ .
4 C.E. B r o w n , E . L N e u s t a d t e r a n d K.P. W h i t t i n g h a m , P r e c . Syrup. E n h a n e e d Oil
R e c o v e r y b y DLsplaeement w i t h Saline S o l u t i o n s , M a y 1 9 7 7 .
5 H.A. Barnes, A . I ~ E a s t w o o d a n d lB. Yates, H h e o l . A c t a , 14 ( 1 9 7 f i ) 53.
6 J . D . Ferry~ Viscoelastic P r o p e r t i e s o f P o l y m e r s , Wiley, N e w Y o r k , NY, 2 n d e d n ,
1970.
7 R. Slmhm, J. Phys. C h e m . , 4 4 ( 1 9 4 0 ) 25.
8 R. S t m h a , J. C1hem. Phys., 13 ( 1 9 4 5 ) 188.
9 H. H o f f m a n n , O. Platz a n d W. U l b r l e h t , J. P h y s . C h e m . , 8 5 ( 1 9 8 1 ) 1 4 1 8 .
I 0 C. T a n f o r d , J. Phys. C h e m . , 7 8 ( 1 9 7 4 ) 2 4 6 9 .
11 N. PilpeI, Trans. Faraday Soc., 6 2 ( 1 9 / ; 6 ) 2 9 4 1 .
12 G . J . T . "lHddy, phys. R e p . , 57 ( 1 9 8 0 ) I .
13 E. R u b i n a n d G.J. R a d k e , C h e m . Eng. Set., 3 5 ( 1 9 8 0 ) 1 1 2 9 .