Chapter 1

1
Petroleum Emulsions
Basic Principles
Laurier L . Schramm Petroleum Recovery Institute, 3512 33rd Street N.W., Calgary, Alberta, Canada T 2 L 2A6
Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001
This chapter provides an introduction to the occurrence, properties, and importance of petroleum emulsions. From light crude oils to bitumens, spanning a wide array of bulk physical properties and stabilities, a common starting point for understanding emulsions is provided by the fundamental principles of colloid science. These principles may be applied to emulsions in different ways to achieve quite different results. A desirable emulsion that must be carefully stabilized to assist one stage of an oil production process may be undesirable in another stage and necessitate a demulsification strategy. With an emphasis on the definition of important terms, the importance of interfacial properties to emulsion making and stability is demonstrated. Demulsification is more complex than just the reverse of emulsion making, but can still be approached from an understanding of how emulsions can be stabilized.
Importance of Emulsions
I f t w o i m m i s c i b l e l i q u i d s are m i x e d together i n a c o n t a i n e r a n d t h e n shaken, e x a m i n a t i o n w i l l reveal that o n e o f the two phases has b e c o m e a c o l l e c t i o n o f d r o p l e t s that are d i s p e r s e d i n t h e o t h e r phase; a n e m u l s i o n has b e e n f o r m e d ( F i g u r e 1). E m u l s i o n s have l o n g b e e n o f great p r a c t i c a l interest because o f t h e i r w i d e s p r e a d o c c u r r e n c e i n everyday l i f e . S o m e i m p o r t a n t a n d f a m i l i a r e m u l s i o n s i n c l u d e those o c c u r r i n g i n foods ( m i l k , mayonnaise, etc.), c o s m e t ics (creams a n d lotions), p h a r m a c e u t i c a l s (soluble v i t a m i n a n d h o r m o n e p r o d u c t s ) , a n d a g r i c u l t u r a l p r o d u c t s (insecticide a n d h e r b i c i d e e m u l s i o n f o r m u l a t i o n s ) . I n a d d i t i o n to t h e i r w i d e o c c u r r e n c e , e m u l s i o n s have i m p o r 0065-2393/92/0231-0001 $13.25/0 1992 American Chemical Society
In Emulsions; Schramm, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1992.
E M U L S I O N S I N T H E P E T R O L E U M INDUSTRY
Figure 1. Photomicrograph of an emulsified droplet of a crude oil, dispersed in the aqueous solution that was used to release it from the mineral matrix in which it was originally held. An interfacial film is obvious at the surface of the droplet. tant p r o p e r t i e s that may b e desirable, f o r example, i n a n a t u r a l o r f o r m u l a t e d p r o d u c t , o r u n d e s i r a b l e , s u c h as an u n w a n t e d e m u l s i o n i n an i n d u s t r i a l process. P e t r o l e u m e m u l s i o n s m a y not b e as f a m i l i a r b u t have a s i m i l a r l y widespread, long-standing, and important occurrence i n industry. E m u l sions m a y be e n c o u n t e r e d at a l l stages i n the p e t r o l e u m r e c o v e r y a n d p r o cessing i n d u s t r y ( d r i l l i n g fluid, p r o d u c t i o n , process p l a n t , a n d transportation e m u l s i o n s ) . T h i s c h a p t e r p r o v i d e s an i n t r o d u c t i o n to the basic p r i n c i p l e s i n v o l v e d i n the o c c u r r e n c e , m a k i n g , a n d b r e a k i n g o f p e t r o l e u m e m u l s i o n s . C r u d e oils consist of, at least, a range o f h y d r o c a r b o n s (alkanes, n a p h thenes, a n d a r o m a t i c c o m p o u n d s ) as w e l l as p h e n o l s , carboxylic acids, a n d metals. A significant f r a c t i o n o f s u l f u r a n d n i t r o g e n c o m p o u n d s m a y b e present as w e l l . T h e c a r b o n n u m b e r s o f a l l these c o m p o n e n t s range f r o m 1 (methane) t h r o u g h 50 o r m o r e (asphaltenes). S o m e o f these c o m p o n e n t s c a n f o r m films at o i l surfaces, a n d others are surface active. It is perhaps not s u r p r i s i n g , t h e n , that the tendencies to f o r m stable o r unstable e m u l s i o n s o f d i f f e r e n t k i n d s vary greatly a m o n g d i f f e r e n t oils. B e c a u s e o f the w i d e range o f possible c o m p o s i t i o n s , c r u d e oils c a n exhibit a w i d e range o f viscosities a n d densities, so m u c h so that these p r o p e r t i e s are u s e d to d i s t i n g u i s h l i g h t , heavy, a n d b i t u m i n o u s c r u d e oils. O n e set o f definitions c a n be c o m p i l e d as follows ( 1 - 3 ) :
1.
SCHRAMM
Basic Principles Viscosity Range (mPa-s), at Reservoir Temperature < 10,000 < 10,000 < 10,000 > 10,000
3 Density Range (kg/m ), at 15.6 C

3
Hydrocarbon Light crude oil Heavy crude oil Extra heavy crude oil Bitumen (tar)
<934 934-1000 > 1000 >1000
B e c a u s e the viscosities c o r r e s p o n d to a m b i e n t deposit t e m p e r a t u r e s , the v a r i a t i o n i n these p r o p e r t i e s over d i f f e r e n t t e m p e r a t u r e s is e v e n greater t h a n the table suggests. F o r e x a m p l e , b i t u m e n i n the A t h a b a s c a deposit o f n o r t h e r n A l b e r t a is c h e m i c a l l y s i m i l a r to c o n v e n t i o n a l o i l b u t has a viscosity, at reservoir t e m p e r a t u r e , o f about 1 0 mPa-s (1 m i l l i o n times greater t h a n that o f water). D u r i n g h e a t i n g , as part o f an o i l r e c o v e r y process s u c h as hotw a t e r flotation o r i n situ steam flooding, e m u l s i o n s h a v i n g a w i d e range o f viscosities c a n be f o r m e d , p a r t i c u l a r l y i f they are o f the w a t e r d i s p e r s e d i n o i l type. W h e n these d i f f e r e n t k i n d s o f oils are e m u l s i f i e d , the e m u l s i o n s m a y have viscosities that are m u c h greater t h a n , s i m i l a r to, o r m u c h less t h a n the viscosity o f the c o m p o n e n t o i l , a l l d e p e n d i n g o n the nature o f the e m u l s i o n formed.
6
A s s h o w n i n T a b l e I, p e t r o l e u m e m u l s i o n s m a y b e desirable o r u n d e sirable. F o r example, one k i n d o f o i l - w e l l d r i l l i n g fluid (or " m u d " ) is e m u l sion based. H e r e a stable e m u l s i o n (usually o i l d i s p e r s e d i n water) is u s e d to l u b r i c a t e the c u t t i n g b i t a n d to carry cuttings u p to the surface. T h i s e m u l sion is o b v i o u s l y desirable, a n d great care goes i n t o its p r o p e r p r e p a r a t i o n . A n e m u l s i o n may be desirable i n one part o f the o i l p r o d u c t i o n process a n d u n d e s i r a b l e at the next stage. F o r e x a m p l e , i n the o i l fields, an i n s i t u Table I. Examples of Emulsions in the Petroleum Industry Occurrence Undesirable Emulsions Well-head emulsions F u e l oil emulsions (marine) O i l sand flotation process, froth O i l sand flotation process, diluted froth O i l spill mousse emulsions Tanker bilge emulsions Desirable Emulsions Heavy oil pipeline emulsion O i l sand flotation process slurry Emulsion drilling fluid, oil-emulsion mud Emulsion drilling fluid, oil-base mud Asphalt emulsion Enhanced oil recovery i n situ emulsions Usual Type
a
W/O W/O W/O or O/W O/W/O W/O O/W O/W O/W O/W W/O O/W O/W
"W/O means water-in-oil; O/W means oil-in-water. See the section "Definition and Classification of Emulsions".
e m u l s i o n that is p u r p o s e l y c r e a t e d i n a reservoir as part o f a n o i l r e c o v e r y process m a y change to a d i f f e r e n t , u n d e s i r a b l e type o f e m u l s i o n (water d i s p e r s e d i n oil) w h e n p r o d u c e d at t h e w e l l h e a d . T h i s e m u l s i o n m a y have to be b r o k e n a n d r e f o r m u l a t e d as a n e w e m u l s i o n suitable for t r a n s p o r t a t i o n b y p i p e l i n e to a refinery. H e r e , t h e n e w e m u l s i o n w i l l have to b e b r o k e n a n d w a t e r f r o m t h e e m u l s i o n r e m o v e d ; o t h e r w i s e t h e w a t e r w o u l d cause process i n g p r o b l e m s i n t h e r e f i n i n g process. E m u l s i o n s may c o n t a i n not just o i l a n d water, b u t also s o l i d particles a n d e v e n gas. I n t h e large m i n i n g a n d p r o c e s s i n g operations a p p l i e d to C a n a d i a n o i l sands, b i t u m e n is separated f r o m t h e sand matrix i n large t u m b l e r s as an e m u l s i o n o f o i l d i s p e r s e d i n water, a n d t h e n f u r t h e r separated f r o m the t u m b l e r s l u r r y b y a flotation process. T h e p r o d u c t o f the flotation process is b i t u m i n o u s f r o t h , an e m u l s i o n that m a y b e e i t h e r w a t e r (and air) d i s p e r s e d i n t h e o i l ( p r i m a r y flotation) o r t h e reverse, o i l (and air) d i s p e r s e d i n w a t e r (secondary flotation). I n either case, t h e e m u l s i o n s must b e b r o k e n a n d t h e w a t e r r e m o v e d b e f o r e t h e b i t u m e n c a n b e u p g r a d e d to synthetic c r u d e o i l , b u t t h e p r e s e n c e o f s o l i d particles a n d film-forming c o m p o n e n t s f r o m t h e b i t u m e n c a n m a k e this r e m o v a l step v e r y d i f f i c u l t . S o m e e m u l s i o n s are m a d e to r e d u c e viscosity so that a n o i l c a n b e m a d e to flow. E m u l s i o n s o f asphalt, a s e m i s o l i d variety o f b i t u m e n d i s p e r s e d i n water, are f o r m u l a t e d to b e b o t h less viscous t h a n t h e o r i g i n a l asphalt a n d stable so that they c a n b e t r a n s p o r t e d a n d h a n d l e d . I n a p p l i c a t i o n , t h e e m u l s i o n s h o u l d shear t h i n a n d b r e a k to f o r m a suitable w a t e r - r e p e l l i n g roadway c o a t i n g m a t e r i a l . A n o t h e r example o f e m u l s i o n s that are f o r m u l a t e d for l o w e r viscosity w i t h g o o d stability are those m a d e f r o m heavy oils a n d i n t e n d e d f o r e c o n o m i c p i p e l i n e t r a n s p o r t a t i o n over large distances. H e r e again t h e e m u l s i o n s s h o u l d b e stable f o r transport b u t w i l l n e e d to b e b r o k e n at t h e e n d o f t h e p i p e l i n e . F i n a l l y , m a n y k i n d s o f e m u l s i o n s pose d i f f i c u l t p r o b l e m s w h e r e v e r t h e y may o c c u r . F o r example, c r u d e o i l w h e n s p i l l e d o n t h e o c e a n tends to b e c o m e e m u l s i f i e d i n t h e f o r m o f " c h o c o l a t e m o u s s e " e m u l s i o n s , so n a m e d f o r t h e i r c o l o r a n d s e m i s o l i d consistency. T h e s e w a t e r - i n - o i l e m u l s i o n s w i t h h i g h w a t e r c o n t e n t t e n d to b e q u i t e stable d u e to t h e strong s t a b i l i z i n g films that are present. M o u s s e e m u l s i o n s increase t h e q u a n t i t y o f p o l l u t a n t a n d are u s u a l l y v e r y m u c h m o r e viscous than t h e o i l itself. A l l o f t h e p e t r o l e u m e m u l s i o n applications o r p r o b l e m s just d i s c u s s e d have i n c o m m o n t h e same basic p r i n c i p l e s o f c o l l o i d science that g o v e r n t h e nature, stability, a n d p r o p e r t i e s o f e m u l s i o n s . T h e w i d e s p r e a d i m p o r t a n c e o f e m u l s i o n s i n general a n d scientific interest i n t h e i r f o r m a t i o n , stability, a n d p r o p e r t i e s have p r e c i p i t a t e d a w e a l t h o f p u b l i s h e d l i t e r a t u r e o n t h e subject. T h i s c h a p t e r p r o v i d e s an i n t r o d u c t i o n a n d is i n t e n d e d to c o m p l e m e n t t h e o t h e r chapters i n this b o o k o n p e t r o l e u m e m u l s i o n s . A g o o d starting p o i n t f o r f u r t h e r basic i n f o r m a t i o n is o n e o f the classic texts: B e c h e r ' s Emulsions: Theory and Practice (4) o r S u m n e r ' s Clayton's Theory of Emulsions and
1.
SCHRAMM
Basic Principles
Their Technical Treatment (5) a n d n u m e r o u s o t h e r books o n e m u l s i o n s (611). M o s t g o o d c o l l o i d c h e m i s t r y texts c o n t a i n i n t r o d u c t o r y chapters o n e m u l s i o n s (12-14), a n d some chapters i n specialist m o n o g r a p h s (15,16) give m u c h m o r e d e t a i l e d treatment o f advances i n specific e m u l s i o n areas.
Emulsions as Colloidal Systems

D e f i n i t i o n a n d Classification o f E m u l s i o n s . C o l l o i d a l d r o p lets (or particles o r b u b b l e s ) , as they are u s u a l l y d e f i n e d , have at least o n e d i m e n s i o n b e t w e e n about 1 a n d 1000 n m . E m u l s i o n s are a s p e c i a l k i n d o f c o l l o i d a l d i s p e r s i o n : o n e i n w h i c h a l i q u i d is d i s p e r s e d i n a c o n t i n u o u s l i q u i d phase o f d i f f e r e n t c o m p o s i t i o n . T h e d i s p e r s e d phase is sometimes r e f e r r e d to as t h e i n t e r n a l (disperse) phase, a n d t h e c o n t i n u o u s phase as t h e external phase. E m u l s i o n s also f o r m a rather special k i n d o f c o l l o i d a l system i n that the droplets o f t e n e x c e e d t h e size l i m i t o f 1000 n m . I n p e t r o l e u m e m u l s i o n s one o f the l i q u i d s is aqueous, a n d t h e o t h e r is h y d r o c a r b o n a n d r e f e r r e d to as o i l . T w o types o f e m u l s i o n are n o w r e a d i l y d i s t i n g u i s h e d i n p r i n c i p l e , d e p e n d i n g u p o n w h i c h k i n d o f l i q u i d forms t h e c o n t i n u o u s phase ( F i g u r e 2): 1. o i l - i n - w a t e r (O/W) f o r o i l d r o p l e t s d i s p e r s e d i n w a t e r 2. w a t e r - i n - o i l (W/O) f o r w a t e r droplets d i s p e r s e d i n o i l T h i s k i n d o f classification is n o t always a p p r o p r i a t e . F o r e x a m p l e , O/W/O denotes a m u l t i p l e e m u l s i o n c o n t a i n i n g o i l d r o p l e t s d i s p e r s e d i n aqueous droplets that are i n t u r n d i s p e r s e d i n a c o n t i n u o u s o i l phase. T h e type o f e m u l s i o n that is f o r m e d depends u p o n a n u m b e r o f factors. I f t h e ratio o f phase v o l u m e s is v e r y large o r v e r y s m a l l , t h e n t h e phase h a v i n g t h e s m a l l e r v o l u m e is f r e q u e n t l y t h e d i s p e r s e d phase. I f t h e ratio is closer to 1, t h e n
Figure 2. The two simplest kinds of emulsions. The droplet sizes have been greatly exaggerated.
o t h e r factors d e t e r m i n e the o u t c o m e . T a b l e I lists some s i m p l e examples o f p e t r o l e u m e m u l s i o n types. T w o v e r y d i f f e r e n t b r o a d types o f c o l l o i d a l dispersions have b e e n d i s t i n g u i s h e d since G r a h a m i n v e n t e d the t e r m " c o l l o i d " i n 1861. O r i g i n a l l y , c o l loids w e r e s u b d i v i d e d i n t o l y o p h o b i c a n d l y o p h i l i c c o l l o i d s (if the d i s p e r s i o n m e d i u m is aqueous t h e n the terms h y d r o p h o b i c a n d h y d r o p h i l i e , respec tively, are used). L y o p h i l i c c o l l o i d s are f o r m e d spontaneously w h e n the t w o phases are b r o u g h t together, because the d i s p e r s i o n is t h e r m o d y n a m i c a l l y m o r e stable t h a n the o r i g i n a l separated state. T h e t e r m l y o p h i l i c is less f r e q u e n t l y u s e d i n m o d e r n p r a c t i c e because m a n y o f the dispersions that w e r e o n c e t h o u g h t o f as l y o p h i l i c are n o w r e c o g n i z e d as single-phase sys tems i n w h i c h large m o l e c u l e s are d i s s o l v e d . L y o p h o b i c c o l l o i d s , w h i c h i n c l u d e a l l p e t r o l e u m e m u l s i o n s other t h a n the m i c r o e m u l s i o n s , are not f o r m e d spontaneously o n c o n t a c t o f the phases because they are t h e r m o d y n a m i c a l l y unstable c o m p a r e d w i t h the separated states. T h e s e dispersions c a n b e f o r m e d b y o t h e r means, h o w e v e r . M o s t p e t r o l e u m emulsions that w i l l be e n c o u n t e r e d i n p r a c t i c e c o n t a i n o i l , w a t e r , a n d an e m u l s i f y i n g agent. T h e e m u l s i f i e r may c o m p r i s e one o r m o r e o f the f o l l o w i n g : s i m p l e i n o r g a n i c electrolytes, surfactants, m a c r o m o l e c u l e s , o r finely d i v i d e d solids. T h e e m u l s i f y i n g agent may be n e e d e d to r e d u c e i n t e r f a c i a l t e n s i o n a n d a i d i n the f o r m a t i o n o f the i n c r e a s e d i n t e r f a c i a l area w i t h a m i n i m u m o f m e c h a n i c a l energy i n p u t , o r it m a y b e n e e d e d to f o r m a p r o t e c t i v e film at the d r o p l e t surfaces that acts to p r e v e n t coalescence w i t h other d r o p l e t s . T h e s e aspects w i l l b e discussed later; the r e s u l t i n g e m u l s i o n may w e l l have c o n s i d e r a b l e stability as a metastable d i s p e r s i o n . M o s t k i n d s o f e m u l s i o n s that w i l l b e e n c o u n t e r e d i n p r a c t i c e are l y o p h o bic, metastable e m u l s i o n s . H o w e v e r , t h e r e r e m a i n some grey areas i n w h i c h the d i s t i n c t i o n b e t w e e n l y o p h i l i c a n d l y o p h o b i c dispersions is not c o m p l e t e l y clear. A s p e c i a l class o f aggregated surfactant m o l e c u l e s t e r m e d " m i c e l l e s " a n d the m i c r o e m u l s i o n s o f e x t r e m e l y s m a l l d r o p l e t size are u s u ally b u t not always c o n s i d e r e d to be l y o p h i l i c , stable, c o l l o i d a l dispersions and w i l l be d i s c u s s e d separately. Stability. A c o n s e q u e n c e o f the s m a l l d r o p l e t size a n d p r e s e n c e o f an i n t e r f a c i a l film o n the droplets i n e m u l s i o n s is that q u i t e stable dispersions o f these species c a n be m a d e . T h a t is, the s u s p e n d e d d r o p l e t s d o not settle out o r float r a p i d l y , a n d the d r o p l e t s d o not coalesce q u i c k l y . S o m e use o f the t e r m stability has already b e e n m a d e w i t h o u t d e f i n i t i o n . C o l l o i d a l species c a n c o m e together i n v e r y d i f f e r e n t ways. I n the d e f i n i t i o n o f e m u l s i o n stability, stability is c o n s i d e r e d against three d i f f e r e n t processes: c r e a m i n g (sedimentation), aggregation, a n d coalescence. C r e a m i n g is the opposite o f s e d i m e n t a t i o n a n d results f r o m a density d i f f e r e n c e b e t w e e n the t w o l i q u i d phases. I n aggregation t w o o r m o r e droplets c l u m p together, t o u c h i n g o n l y at c e r t a i n p o i n t s , a n d w i t h v i r t u a l l y no change i n
1.
SCHRAMM
Basic Principles
total surface area. A g g r e g a t i o n is sometimes r e f e r r e d to as flocculation o r c o a g u l a t i o n . I n coalescence t w o o r m o r e d r o p l e t s fuse t o g e t h e r to f o r m a single larger u n i t w i t h a r e d u c e d total surface area. I n aggregation t h e species r e t a i n t h e i r i d e n t i t y b u t lose t h e i r k i n e t i c i n d e p e n d e n c e because the aggregate moves as a single u n i t . A g g r e g a t i o n o f droplets m a y l e a d to coalescence a n d the f o r m a t i o n o f larger droplets u n t i l the phases b e c o m e separated. I n coalescence, o n the o t h e r h a n d , t h e o r i g i n a l species lose t h e i r i d e n t i t y a n d b e c o m e part o f a n e w species. K i n e t i c stability c a n thus have d i f f e r e n t meanings. A n e m u l s i o n c a n b e k i n e t i c a l l y stable w i t h respect to coalescence b u t unstable w i t h respect to aggregation. O r , a system c o u l d b e k i n e t i c a l l y stable w i t h respect t o aggregation b u t unstable w i t h respect to s e d i m e n t a t i o n o r flotation. Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 I n s u m m a r y , l y o p h o b i c e m u l s i o n s are t h e r m o d y n a m i c a l l y unstable b u t may b e relatively stable i n a k i n e t i c sense. S t a b i l i t y must b e u n d e r s t o o d i n terms o f a clearly d e f i n e d process. M i c r o e m u l s i o n s . I n some systems t h e a d d i t i o n o f a f o u r t h c o m p o nent, a cosurfactant, to a n o i l - w a t e r - s u r f a c t a n t system c a n cause the i n t e r f a c i a l t e n s i o n to d r o p t o near-zero values, easily o n t h e o r d e r o f 10~ to 1(* m N / m ; l o w i n t e r f a c i a l t e n s i o n allows spontaneous o r n e a r l y spontaneous e m u l s i f i c a t i o n to v e r y s m a l l d r o p l e t sizes, c a . 10 n m o r s m a l l e r . T h e droplets c a n b e so s m a l l that they scatter little l i g h t ; t h e e m u l s i o n s appear to b e transparent a n d d o n o t break o n s t a n d i n g o r c e n t r i f u g i n g . U n l i k e coarse e m u l s i o n s , these m i c r o e m u l s i o n s are usually t h o u g h t to b e t h e r m o d y n a m i cally stable. T h e t h e r m o d y n a m i c stability is f r e q u e n t l y a t t r i b u t e d to t r a n sient negative i n t e r f a c i a l tensions, b u t this hypothesis a n d t h e q u e s t i o n o f w h e t h e r m i c r o e m u l s i o n s are r e a l l y l y o p h i l i c o r l y o p h o b i c dispersions are areas o f some d i s c u s s i o n i n t h e literature (17). A s a p r a c t i c a l matter, m i c r o e m u l s i o n s c a n b e f o r m e d , have some special qualities, a n d c a n have i m p o r t a n t applications.
3
M i c r o e m u l s i o n s c a n f o r m t h e basis f o r a n e n h a n c e d o i l r e c o v e r y ( E O R ) process (18-20). I n an o i l - c o n t a i n i n g reservoir, t h e relative o i l a n d w a t e r saturations d e p e n d u p o n t h e d i s t r i b u t i o n o f p o r e sizes i n t h e r o c k as f o l l o w s . T h e c a p i l l a r y pressure ( F ) , o r pressure d i f f e r e n c e across a n o i l - w a t e r i n t e r face s p a n n i n g a p o r e , is
c
P = 2y cos I r
c
(1)
w h e r e 7 is the o i l - w a t e r i n t e r f a c i a l t e n s i o n ; is t h e contact angle, w h i c h is the angle m e a s u r e d t h r o u g h t h e w a t e r phase at t h e p o i n t o f o i l - w a t e r - r o c k contact; a n d r is t h e p o r e r a d i u s . T h e basis f o r this e q u a t i o n is d i s c u s s e d f u r t h e r i n a later section. I n a n i d e a l i z e d w a t e r - w e t reservoir, t h e i n t e r f a c i a l t e n s i o n is fixed at some v a l u e , a n d t h e contact angle is z e r o . A n analogy c a n be d r a w n w i t h t h e rise o f w a t e r i n c a p i l l a r y tubes o f d i f f e r i n g r a d i i . I n a
p
reservoir c o n s i s t i n g o f s u c h c a p i l l a r y tubes that c o n t a i n w a t e r a n d o i l , w a t e r w i l l b e i m b i b e d most strongly i n t o the smallest radius pores, d i s p l a c i n g any o i l present i n t h e m , u n t i l t h e hydrostatic a n d c a p i l l a r y pressures i n t h e system balance. T h e largest pores w i l l r e t a i n h i g h o i l contents. N o w as w a t e r is i n j e c t e d d u r i n g a secondary r e c o v e r y process, the a p p l i e d w a t e r pressure increases a n d the larger pores w i l l i m b i b e m o r e water, d i s p l a c i n g o i l , w h i c h may b e r e c o v e r e d at p r o d u c i n g w e l l s . T h e r e is a p r a c t i c a l l i m i t t o t h e extent that t h e a p p l i e d pressure c a n b e c h a n g e d b y p u m p i n g w a t e r i n t o a reservoir, h o w e v e r , so that after w a t e r - f l o o d i n g some r e s i d u a l o i l w i l l still b e left i n the f o r m o f o i l ganglia t r a p p e d i n the larger pores w h e r e the viscous forces o f t h e d r i v i n g w a t e r - f l o o d c o u l d n o t c o m p l e t e l y o v e r c o m e the c a p i l l a r y forces h o l d ing the o i l i n place. Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 T h e ratio o f viscous forces t o c a p i l l a r y forces correlates w e l l w i t h r e s i d ual o i l saturation a n d is t e r m e d t h e c a p i l l a r y n u m b e r (N ). O n e f o r m u l a t i o n o f t h e c a p i l l a r y n u m b e r is
c
N = 7]v/y
c
(2)
w h e r e a n d are the viscosity a n d v e l o c i t y , respectively, o f the d i s p l a c i n g fluid; a n d y is t h e i n t e r f a c i a l t e n s i o n . T h e f u n c t i o n a l f o r m o f t h e c o r r e l a t i o n is i l l u s t r a t e d i n F i g u r e 3 . D u r i n g w a t e r - f l o o d i n g , N is about 10~ , a n d at t h e

c 6
10"
10"
10"
10"
10"
Capillary Number
Figure 3. A generalized capillary number correlation. (Courtesy of K. Taylor, Petroleum Recovery Institute, Calgary.)
1.
SCHRAMM
Basic Principles
e n d o f the w a t e r - f l o o d the r e s i d u a l o i l saturation is still a r o u n d 4 5 % . H o w c o u l d a tertiary r e c o v e r y process b e d e s i g n e d so that the r e m a i n i n g o i l c o u l d be r e c o v e r e d ? L o w e r i n g the r e s i d u a l o i l saturation r e q u i r e s i n c r e a s i n g the c a p i l l a r y n u m b e r . T h i s increase c o u l d be d o n e b y r a i s i n g the viscous forces, that is, viscosity a n d v e l o c i t y , b u t i n p r a c t i c e the d e s i r e d o r d e r s - o f - m a g n i t u d e increase w i l l not be a c h i e v e d . B u t , a d d i n g a suitable surfactant a n d cosurfactant to the w a t e r w i l l decrease the i n t e r f a c i a l t e n s i o n f r o m about 30 m N / m b y 4 orders o f m a g n i t u d e a n d t h e r e b y increase the c a p i l l a r y n u m b e r to about 10" .
2
T h e m i c e l l e s present also h e l p to s o l u b i l i z e the released o i l d r o p l e t s ; h e n c e , this process is sometimes r e f e r r e d to as m i c e l l a r flooding. T h e e m u l sions c a n b e f o r m u l a t e d to have m o d e r a t e l y h i g h viscosities that h e l p to achieve a m o r e u n i f o r m d i s p l a c e m e n t front i n the reservoir; this u n i f o r m f r o n t gives i m p r o v e d sweep efficiency. T h u s , a n u m b e r o f factors c a n b e adjusted w h e n u s i n g a m i c r o e m u l s i o n system f o r e n h a n c e d o i l recovery. T h e s e are discussed i n d e t a i l i n C h a p t e r 7. M a k i n g E m u l s i o n s . M u c h o f this c h a p t e r is c o n c e r n e d w i t h e m u l s i o n p r o p e r t i e s a n d stability, a n d as a p r a c t i c a l matter chemists f r e q u e n t l y have to c o n t e n d w i t h a l r e a d y - f o r m e d e m u l s i o n s . N e v e r t h e l e s s , a f e w c o m ments o n h o w e m u l s i o n s m a y b e m a d e are a p p r o p r i a t e . T h e b r e a k i n g o f e m u l s i o n s w i l l be discussed later. E m u l s i o n s o f any significant stability c o n t a i n o i l , water, a n d at least one e m u l s i f y i n g agent. T h e e m u l s i f y i n g agent m a y l o w e r i n t e r f a c i a l t e n s i o n a n d t h e r e b y m a k e it easier to create s m a l l d r o p l e t s . A n o t h e r e m u l s i f y i n g agent may b e n e e d e d to stabilize the s m a l l droplets so that t h e y d o not coalesce to f o r m larger d r o p l e t s , o r e v e n separate out as a b u l k phase. Just a straightfor w a r d casual m i x i n g o f these c o m p o n e n t s s e l d o m , h o w e v e r , p r o d u c e s an e m u l s i o n that persists for any l e n g t h o f t i m e . I n the classical m e t h o d o f e m u l s i o n p r e p a r a t i o n , the e m u l s i f y i n g agent is d i s s o l v e d i n t o the phase i n w h i c h it is most s o l u b l e , after w h i c h the s e c o n d phase is a d d e d , a n d the w h o l e m i x t u r e is v i g o r o u s l y agitated. T h e agitation is c r u c i a l to p r o d u c i n g sufficiently s m a l l d r o p l e t s , a n d f r e q u e n t l y , after an i n i t i a l m i x i n g , a s e c o n d m i x i n g w i t h v e r y h i g h a p p l i e d m e c h a n i c a l shear forces is r e q u i r e d . T h i s latter m i x i n g carrbe p r o v i d e d b y a p r o p e l l e r - s t y l e m i x e r , b u t m o r e c o m m o n l y a c o l l o i d m i l l o r u l t r a s o u n d generator is e m p l o y e d . A m e t h o d r e q u i r i n g m u c h less m e c h a n i c a l energy uses phase i n v e r s i o n (see also the d i s c u s s i o n o f phase i n v e r s i o n t e m p e r a t u r e i n the section " E m u l s i f y i n g A g e n t s " ) . F o r example, i f u l t i m a t e l y a W / O e m u l s i o n is d e s i r e d , t h e n a coarse O / W e m u l s i o n is first p r e p a r e d b y the a d d i t i o n o f m e c h a n i c a l energy, a n d the o i l content is progressively i n c r e a s e d . A t some v o l u m e f r a c t i o n above 6 0 - 7 0 % , the e m u l s i o n w i l l s u d d e n l y i n v e r t a n d p r o d u c e a W / O e m u l s i o n o f m u c h s m a l l e r w a t e r d r o p l e t sizes t h a n w e r e the o i l d r o p l e t s i n the o r i g i n a l O / W e m u l s i o n .
10
Physical Characteristics of Emulsions

A p p e a r a n c e . N o t a l l e m u l s i o n s e x h i b i t t h e classical " m i l k y " o p a q u e ness w i t h w h i c h they are u s u a l l y associated. A t r e m e n d o u s range o f appear ances is possible, d e p e n d i n g u p o n the d r o p l e t sizes a n d t h e d i f f e r e n c e i n refractive i n d i c e s b e t w e e n t h e phases. A n e m u l s i o n c a n b e transparent i f e i t h e r t h e refractive i n d e x o f each phase is t h e same, o r alternatively, i f t h e d i s p e r s e d phase is m a d e u p o f droplets that are s u f f i c i e n t l y s m a l l c o m p a r e d with the wavelength of the illuminating light. Thus an O/W microemulsion o f e v e n a c r u d e o i l i n w a t e r may b e transparent. I f t h e droplets are o f t h e o r d e r o f l - d i a m e t e r , a d i l u t e O / W e m u l s i o n w i l l take o n a s o m e w h a t m i l k y - b l u e cast; i f t h e droplets are v e r y m u c h larger, the o i l phase w i l l b e c o m e q u i t e d i s t i n g u i s h a b l e a n d apparent. Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 P h y s i c a l l y t h e nature o f the s i m p l e e m u l s i o n types c a n b e d e t e r m i n e d b y m e t h o d s s u c h as Texture. T h e texture o f an e m u l s i o n f r e q u e n t l y reflects that o f the external phase. T h u s O / W e m u l s i o n s u s u a l l y f e e l w a t e r y o r c r e a m y , a n d W / O e m u l s i o n s f e e l o i l y o r greasy. T h i s d i s t i n c t i o n b e c o m e s less e v i d e n t as the e m u l s i o n viscosity increases, so that a v e r y viscous O / W e m u l s i o n m a y f e e l o i l y . Mixing. A n e m u l s i o n r e a d i l y mixes w i t h a l i q u i d that is m i s c i ble w i t h the c o n t i n u o u s phase. T h u s , m i l k (O/W) c a n b e d i l u t e d w i t h water, a n d mayonnaise (W/O) c a n b e d i l u t e d w i t h o i l . U s u a l l y , a n e m u l s i o n that retains a u n i f o r m a n d m i l k y appearance w h e n greatly d i l u t e d is m o r e stable t h a n o n e that aggregates u p o n d i l u t i o n (15). Dyeing. E m u l s i o n s are most r e a d i l y a n d consistently c o l o r e d b y dyes s o l u b l e i n t h e c o n t i n u o u s phase. Conductance. O / W e m u l s i o n s u s u a l l y have a v e r y h i g h spe cific c o n d u c t a n c e , l i k e that o f t h e aqueous phase itself, b u t W / O e m u l s i o n s have a v e r y l o w specific c o n d u c t a n c e . A s i m p l e test apparatus is d e s c r i b e d i n r e f e r e n c e 15. Inversion. I f a n e m u l s i o n is v e r y c o n c e n t r a t e d , i t w i l l p r o b a bly i n v e r t w h e n d i l u t e d w i t h a d d i t i o n a l i n t e r n a l phase. Fluorescence. I f t h e o i l phase fluoresces, then fluorescence
m i c r o s c o p y c a n b e u s e d to d e t e r m i n e the e m u l s i o n type as l o n g as t h e d r o p l e t sizes are larger t h a n the microscope's l i m i t o f r e s o l u t i o n (>0.5 ) . E m u l s i o n s d o n o t always o c c u r i n t h e i d e a l i z e d f o r m o f droplets o f one phase d i s p e r s e d i n another. T h e o c c u r r e n c e o f m u l t i p l e e m u l s i o n s , o f t h e
1.
SCHRAMM
Basic Principles
11
types O/W/O a n d W / O A V , has already b e e n m e n t i o n e d . P e t r o l e u m e m u l sions m a y also o c c u r w i t h i n another type o f c o l l o i d a l d i s p e r s i o n . F o r e x a m p l e , i n a gas-flooding e n h a n c e d o i l r e c o v e r y process o n e o f t h e ways t o i m p r o v e t h e areal sweep efficiency, that is, to m a x i m i z e t h e a m o u n t o f t h e r e s e r v o i r c o n t a c t e d b y i n j e c t e d fluids, is t o inject t h e gas as p a r t o f a f o a m . H o w e v e r , most s u c h foams are d e s t a b i l i z e d b y contact w i t h e v e n s m a l l amounts o f c r u d e o i l . T h e m e c h a n i s m o f d e s t a b i l i z a t i o n appears (21 ) t o i n v o l v e e m u l s i f i c a t i o n o f the o i l i n t o droplets that are s m a l l e n o u g h to p e r m i t t h e i r passage i n s i d e t h e foam's l a m e l l a r s t r u c t u r e . S u c h e m u l s i f i e d o i l d r o p lets are s h o w n i n F i g u r e 4. O n c e i n s i d e t h e f o a m l a m e l l a e , t h e o i l d r o p l e t s have a d e s t a b i l i z i n g effect o n t h e f o a m b y p e n e t r a t i n g t h r o u g h a n d p o s s i b l y s p r e a d i n g over t h e aqueous-gas interface. T h e l i m i t i n g step, h o w e v e r , is a p p a r e n t l y the e m u l s i f i c a t i o n a n d i m b i b i t i o n o f o i l i n t o t h e f o a m . Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 D r o p l e t Sizes. A s stated p r e v i o u s l y , c o l l o i d a l d r o p l e t s are b e t w e e n about 10" a n d 1 i n d i a m e t e r , a n d i n p r a c t i c e , e m u l s i o n droplets are o f t e n larger (e.g., t h e fat droplets i n m i l k ) . I n fact, e m u l s i o n droplets u s u a l l y
3
Figure 4. Photomicrograph of an enhanced oil recovery process foam contain ing emulsified crude-oil droplets. The droplets have traveled within the narrow lamellae to accumulate and sometimes coalesce in the plateau borders of the foam, where they are held preferentially. The presence of such emulsified oil droplets in the foam structure has a destabilizing effect on the foam.
12
have diameters greater t h a n 0.2 a n d m a y b e larger t h a n 50 . E m u l sion stability is not necessarily a f u n c t i o n o f d r o p l e t size, a l t h o u g h t h e r e m a y b e a n o p t i m u m size f o r a n i n d i v i d u a l e m u l s i o n type. C h a r a c t e r i z i n g a n e m u l s i o n i n terms o f a g i v e n d r o p l e t size is v e r y c o m m o n b u t g e n e r a l l y i n a p p r o p r i a t e because t h e r e is i n e v i t a b l y a size d i s t r i b u t i o n . T h e size d i s t r i b u t i o n is u s u a l l y r e p r e s e n t e d b y a h i s t o g r a m o f sizes, o r , i f there are suffi cient data, a d i s t r i b u t i o n f u n c t i o n . I n some e m u l s i o n s , a d r o p l e t size d i s t r i b u t i o n that is h e a v i l y w e i g h t e d t o w a r d t h e s m a l l e r sizes w i l l represent t h e most stable e m u l s i o n . I n s u c h cases changes i n the size d i s t r i b u t i o n c u r v e w i t h t i m e y i e l d a measure o f the stability o f the e m u l s i o n s . T h e d r o p l e t size d i s t r i b u t i o n also has a n i m p o r t a n t i n f l u e n c e o n the viscosity. F o r electrostatically o r sterically i n t e r a c t i n g d r o p lets, e m u l s i o n viscosity w i l l b e h i g h e r w h e n droplets are smaller. T h e viscos ity w i l l also b e h i g h e r w h e n the d r o p l e t sizes are relatively h o m o g e n e o u s , that is, w h e n t h e d r o p l e t size d i s t r i b u t i o n is n a r r o w rather t h a n w i d e (4). I f t h e d r o p l e t size is large e n o u g h , t h e n o p t i c a l m i c r o s c o p y c a n b e u s e d to d e t e r m i n e t h e size a n d size d i s t r i b u t i o n . E m u l s i o n s w i t h somewhat s m a l l er d r o p l e t sizes c a n b e c h a r a c t e r i z e d b y u s i n g cryogenic-stage s c a n n i n g e l e c t r o n m i c r o s c o p y . I f t h e e m u l s i o n c o n c e n t r a t i o n is not too h i g h , a n d the droplets are v e r y s m a l l , l i g h t scattering c a n y i e l d d r o p l e t size i n f o r m a t i o n . W h e n a b e a m o f l i g h t enters a n e m u l s i o n , some l i g h t is a b s o r b e d , some is scattered, a n d some is t r a n s m i t t e d . M a n y d i l u t e , fine e m u l s i o n s s h o w a noticeable t u r b i d i t y g i v e n b y I //
t t
=expM)
0
(3)
w h e r e I is the i n t e n s i t y o f t h e t r a n s m i t t e d b e a m , I is the i n t e n s i t y o f the i n c i d e n t b e a m , is t u r b i d i t y , a n d I is t h e l e n g t h o f the p a t h t h r o u g h the s a m p l e . F r o m R a y l e i g h t h e o r y , t h e i n t e n s i t y o f l i g h t scattered f r o m e a c h d r o p l e t d e p e n d s largely o n its size a n d shape a n d o n t h e d i f f e r e n c e i n refractive i n d e x b e t w e e n the d r o p l e t a n d the m e d i u m . F o r a n e m u l s i o n , e a c h s p h e r i c a l d r o p l e t scatters l i g h t h a v i n g a n i n t e n s i t y l at a distance f r o m t h e d r o p l e t , a c c o r d i n g to t h e f o l l o w i n g r e l a t i o n s h i p :
d
I /I ocr /x K*
d 0 e 2
(4)
w h e r e is t h e w a v e l e n g t h o f t h e l i g h t a n d r is t h e d r o p l e t radius. T h e scattering i n t e n s i t y is p r o p o r t i o n a l to l/ , so b l u e l i g h t ( = 4 5 0 n m ) is scattered m u c h m o r e t h a n r e d l i g h t ( = 650 n m ) . W i t h i n c i d e n t w h i t e light, a d i l u t e e m u l s i o n o f O . l - 1 - size droplets w i l l , therefore, t e n d t o appear b l u e w h e n v i e w e d at right angles t o t h e i n c i d e n t l i g h t b e a m . I f t h e droplets are s m a l l e r t h a n 5 0 n m o r so, the e m u l s i o n w i l l appear to b e transparent.
4
1.
SCHRAMM
Basic Principles
13
T h e s e approaches
to d e t e r m i n i n g d r o p l e t size d i s t r i b u t i o n s are d i s
c u s s e d i n d e t a i l i n C h a p t e r 3.
Conductivity.
Conductivity can be used to distinguish O/W f r o m
W / O e m u l s i o n s b e c a u s e the c o n d u c t i v i t y is v e r y h i g h w h e n t h e aqueous phase is c o n t i n u o u s a n d c o n d u c t i v i t y is v e r y l o w w h e n o i l is t h e c o n t i n u o u s phase. O f the n u m e r o u s equations p r o p o s e d (4) to d e s c r i b e t h e c o n d u c t i v i t y o f e m u l s i o n s (#c ), t w o are c i t e d h e r e f o r i l l u s t r a t i o n . I f t h e c o n d u c t i v i t y o f

E
the d i s p e r s e d phase ( K ) is m u c h s m a l l e r t h a n that o f t h e c o n t i n u o u s phase

d
(fCc), * C
*D>
_8KC(2-0)(1-0)
(4 + ) ( 4 - )
w h e r e is the dispersed-phase v o l u m e f r a c t i o n . If, o n t h e o t h e r h a n d , t h e c o n d u c t i v i t y o f t h e d i s p e r s e d phase (#c ) is m u c h greater t h a n that o f t h e

D
c o n t i n u o u s phase ( K ) , K <K K ,
C C D
(1
0
)(2
(1-0(2-) F u r t h e r discussion o f emulsion conductivity a n d some practical exam ples f o r e m u l s i o n s flowing i n p i p e l i n e s are g i v e n i n C h a p t e r 5 .
Rheology.
Bulk Viscosity Properties.
T h e rheological properties
o f a n e m u l s i o n are v e r y i m p o r t a n t . H i g h viscosity m a y b e t h e reason that a n e m u l s i o n is t r o u b l e s o m e , a resistance to flow that must b e dealt w i t h , o r a d e s i r a b l e p r o p e r t y f o r w h i c h a n e m u l s i o n is f o r m u l a t e d . T h e s i m p l e s t d e s c r i p t i o n applies to N e w t o n i a n b e h a v i o r i n l a m i n a r flow. T h e viscosity, rj, is g i v e n i n t e r m s o f t h e shear stress, , a n d shear rate, 7, b y : = 177
(7)
w h e r e 1 has units o f m i l l i p a s c a l seconds. M a n y c o l l o i d a l d i s p e r s i o n s , i n c l u d 7 i n g t h e m o r e c o n c e n t r a t e d e m u l s i o n s , d o n o t o b e y the N e w t o n i a n e q u a t i o n . F o r n o n - N e w t o n i a n fluids, t h e coefficient o f viscosity is n o t a constant, b u t is i t s e l f a f u n c t i o n o f t h e shear rate, thus:
7=17(7)7
( )
8
A c o n v e n i e n t w a y to s u m m a r i z e t h e flow p r o p e r t i e s o f fluids is b y p l o t t i n g flow curves o f shear stress versus shear rate ( versus 7 ) . T h e s e
14
curves c a n be c a t e g o r i z e d i n t o several r h e o l o g i c a l classifications. E m u l s i o n s are f r e q u e n t l y p s e u d o p l a s t i c : A s shear rate increases, viscosity decreases. T h i s k i n d o f flow b e h a v i o r is also t e r m e d s h e a r - t h i n n i n g . A n e m u l s i o n may also e x h i b i t a y i e l d stress, that is, the shear rate (flow) remains z e r o u n t i l a t h r e s h o l d shear stress is reachedthe y i e l d stress ( ) t h e n p s e u d o p l a s t i c o r N e w t o n i a n flow begins. P s e u d o p l a s t i c flow that is t i m e d e p e n d e n t is t e r m e d t h i x o t r o p i c . T h a t is, at constant a p p l i e d shear rate, viscosity decreases, a n d i n a flow c u r v e hysteresis occurs. Several o t h e r r h e o l o g i c a l classifications are c o v e r e d i n the G l o s s a r y : dilatancy, rheopexy, a n d rheomalaxi^. E v e n viscos ity i t s e l f is r e p r e s e n t e d i n m a n y ways, as s h o w n i n T a b l e I I .
S o m e v e r y u s e f u l d e s c r i p t i o n s o f e x p e r i m e n t a l t e c h n i q u e s have b e e n g i v e n b y W h o r l o w (22) a n d others (23, 24). V e r y o f t e n m e a s u r e m e n t s are m a d e w i t h an e m u l s i o n sample p l a c e d i n the annulus b e t w e e n t w o c o n c e n t r i c c y l i n d e r s . T h e shear stress is c a l c u l a t e d f r o m the m e a s u r e d t o r q u e r e q u i r e d to m a i n t a i n a g i v e n r o t a t i o n a l v e l o c i t y o f o n e c y l i n d e r w i t h respect to the other. K n o w i n g the geometry, the effective shear rate c a n b e c a l c u l a t e d f r o m the r o t a t i o n a l v e l o c i t y . O n e reason for the relative lack o f r h e o l o g i c a l data f o r e m u l s i o n s , c o m p a r e d w i t h that f o r o t h e r c o l l o i d a l systems, is the d i f f i c u l t y associated w i t h p e r f o r m i n g the measurements i n these sys tems. A s suggested b y F i g u r e 5, for a p r a c t i c a l O / W e m u l s i o n , the s a m p l e m a y c o n t a i n s u s p e n d e d particles i n a d d i t i o n to the o i l d r o p l e t s . I n attempt i n g to c o n d u c t a m e a s u r e m e n t , a n u m b e r o f changes m a y o c c u r i n the sample
Table II. Glossary of Bulk Viscosity Terms Term Absolute viscosity Symbol Explanation = /7 and can be traced to fundamental units independent of the type of instrument = /7 but as determined for a nonNewtonian fluid, usually by a method suitable only for Newtonian fluids
Apparent viscosity
T|APP
Differential viscosity Specific increase in viscosity Intrinsic viscosity Reduced viscosity Relative viscosity
= dT/d"y
$ [] Red
nsp = nRei - 1 [] = lim -o lim ^ ^sv/C [] = lim ->o lim _> (1/C) In n j
C 0 C 0 Re
nRed = Tjsp/C nRei = / T o = viscosity of the pure solvent or dispersion | medium
1.
SCHRAMM
Basic Principles
15
c h a m b e r that make the measurements i r r e p r o d u c i b l e a n d not representative o f t h e o r i g i n a l e m u l s i o n (25). T h e s e changes m a y i n c l u d e creaming o f the droplets, causing a n o n u n i f o r m distribution w i t h i n t h e c h a m b e r , o r e v e n r e m o v a l o f a l l droplets i n t o a n u p p e r phase away f r o m t h e r e g i o n i n w h i c h measurements are made c e n t r i f u g a l separation o f o i l , water, a n d s o l i d phases, m a k i n g the e m u l s i o n r a d i a l l y i n h o m o g e n e o u s , a n d p o s s i b l y b r e a k i n g the e m u l s i o n s h e a r - i n d u c e d coalescence o r finer d i s p e r s i o n o f d r o p l e t s , c h a n g i n g t h e p r o p e r t i e s o f t h e sample Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 s e d i m e n t a t i o n o f the solids, c a u s i n g a n o n u n i f o r m d i s t r i b u t i o n w i t h i n t h e c h a m b e r , o r even r e m o v a l o f a l l solids f r o m t h e r e g i o n i n w h i c h measurements are m a d e It is f r e q u e n t l y desirable to b e able to d e s c r i b e e m u l s i o n viscosity i n terms o f t h e viscosity o f t h e c o n t i n u o u s phase (%) a n d t h e a m o u n t o f e m u l s i f i e d m a t e r i a l . A v e r y large n u m b e r o f equations have b e e n a d v a n c e d f o r e s t i m a t i n g suspension (or e m u l s i o n , etc.) viscosities. M o s t o f these are e m p i r i c a l extensions o f E i n s t e i n ' s e q u a t i o n f o r a d i l u t e suspension o f spheres: = (1
0
+ 2.5)
(9)
Figure 5. Some rheological measurement problems that may be encountered with practical oil-field emulsions. Initially, the O/W sample contained in the cylinders on the left may be homogeneous, containing oil droplets (), fine particles (), and large particles (o). After some time, the sample may become quite stratified, as shown at right.
16
0
w h e r e is the m e d i u m viscosity a n d is the dispersed-phase v o l u m e f r a c t i o n a n d is <1. F o r e x a m p l e , the e m p i r i c a l equations t y p i c a l l y have the f o r m (4): = %(1 +
0
+
2
4- )
(10) may
w h e r e the a s are e m p i r i c a l constants, a n d the e m p i r i c a l equations i n c l u d e other t e r m s , as i n the T h o m a s e q u a t i o n , = + 2 . 5 + 1 O . 5 0 + 0.00273 exp (16.60) ]
2
(11)
T h e s e equations assume N e w t o n i a n b e h a v i o r , o r at least a p p l y to the N e w t o n i a n r e g i o n o f a flow c u r v e , a n d they usually a p p l y i f the droplets are not too large a n d i f t h e r e are no strong electrostatic interactions. A m o r e d e t a i l e d treatment o f these relationships is given i n C h a p t e r 4. E m u l s i o n s c a n show v a r y i n g r h e o l o g i c a l , o r viscosity, behaviors. S o m e times these p r o p e r t i e s are d u e to the e m u l s i f i e r o r o t h e r agents i n the e m u l s i o n . H o w e v e r , i f the i n t e r n a l phase has a s u f f i c i e n t l y h i g h v o l u m e f r a c t i o n (typically a n y w h e r e f r o m 10 to 50%) the e m u l s i o n viscosity i n creases because o f d r o p l e t " c r o w d i n g " or s t r u c t u r a l viscosity a n d b e c o m e s n o n - N e w t o n i a n . T h e m a x i m u m v o l u m e f r a c t i o n possible for an i n t e r n a l phase made u p o f u n i f o r m , i n c o m p r e s s i b l e spheres is 74%, a l t h o u g h e m u l sions w i t h an i n t e r n a l v o l u m e f r a c t i o n o f 9 9 % have b e e n m a d e (15). F i g u r e 6 shows h o w e m u l s i o n viscosity tends to v a r y w i t h v o l u m e f r a c t i o n ; the d r o p i n viscosity at = 0.74 signifies i n v e r s i o n . A t this p o i n t the dispersed-phase v o l u m e f r a c t i o n b e c o m e s 0.26, i n this e x a m p l e , a n d the l o w e r value o f is r e f l e c t e d b y a m u c h l o w e r viscosity. I f i n v e r s i o n does not o c c u r , t h e n the viscosity continues to increase. T h i s c o n d i t i o n is true f o r b o t h W / O a n d O / W types. A g r a p h i c a n d i m p o r t a n t example is f u r n i s h e d b y the o i l s p i l l " c h o c o l a t e m o u s s e " e m u l s i o n s f o r m e d w h e n c r u d e o i l spills i n t o seawater. T h e s e w a t e r i n - o i l e m u l s i o n s have h i g h w a t e r contents that may e x c e e d 7 4 % a n d r e a c h = 0.80 o r m o r e w i t h o u t i n v e r t i n g . A s t h e i r c o m m o n n a m e i m p l i e s , these mousse e m u l s i o n s not o n l y h a e viscosities that are m u c h h i g h e r t h a n the o r i g i n a l c r u d e o i l b u t can b e c o m e s e m i s o l i d . W i t h i n c r e a s i n g t i m e after a s p i l l , these e m u l s i o n s w e a t h e r (the o i l b e c o m e s d e p l e t e d i n its l o w e r b o i l i n g fractions), a n d a p p a r e n t l y the e m u l s i o n s b e c o m e m o r e stable, m o r e s o l i d l i k e , a n d c o n s i d e r a b l y m o r e d i f f i c u l t to h a n d l e a n d break.
,r
Interfacial Viscosity. T h e f o r e g o i n g d i s c u s s i o n o f r h e o l o g y has dealt w i t h the b u l k viscosity p r o p e r t i e s . A closely r e l a t e d a n d v e r y i m p o r t a n t p r o p e r t y is the i n t e r f a c i a l viscosity, w h i c h c a n be t h o u g h t o f as the t w o d i m e n s i o n a l e q u i v a l e n t o f b u l k viscosity, operative i n the o i l - w a t e r i n t e r f a c i a l r e g i o n . A s d r o p l e t s i n an e m u l s i o n a p p r o a c h each other, the t h i n n i n g o f
1.
SCHRAMM
Basic Principles
17
Inversion at
0.2
0.4
0.6
0.8
1.0
Volume Fraction of Oil

Figure 6. The influence of volume fraction on the emulsion type and viscosity of a model emulsion. (Reproduced with permission from reference 4. Copyright 1965 Robert E. Krieger, Inc.)
the films b e t w e e n t h e droplets, a n d t h e i r resistance to r u p t u r e , are t h o u g h t to b e o f great i m p o r t a n c e to t h e u l t i m a t e stability o f the e m u l s i o n . T h u s , a h i g h i n t e r f a c i a l viscosity can p r o m o t e e m u l s i o n stability b y r e t a r d i n g the rate o f d r o p l e t coalescence, as discussed i n later sections. F u r t h e r details o n the p r i n c i p l e s , m e a s u r e m e n t , a n d applications to e m u l s i o n stability o f i n t e r f a c i a l viscosity w e r e r e v i e w e d b y M a l h o t r a a n d W a s a n (26).
Properties of the Interfaces

I n s i m p l e two-phase c o l l o i d a l systems, a t h i n i n t e r m e d i a t e r e g i o n o r b o u n d ary, k n o w n as t h e interface, lies b e t w e e n the d i s p e r s e d a n d d i s p e r s i n g phases. Interfacial p r o p e r t i e s are v e r y i m p o r t a n t because e m u l s i f i e d d r o p lets have a large i n t e r f a c i a l area, a n d even a modest i n t e r f a c i a l energy p e r u n i t area c a n b e c o m e a c o n s i d e r a b l e total i n t e r f a c i a l energy to b e a c c o m m o d a t e d . F o r example, suppose w e w i s h to e m u l s i f y o n e b a r r e l (159 L ) o f o i l i n t o w a t e r . F o r this i l l u s t r a t i o n c o n s i d e r the o i l t o b e i n 1 large d r o p that w e r e p e a t e d l y s u b d i v i d e i n t o d r o p s o f h a l f the p r e v i o u s radius. T h u s , t h e i n i t i a l d r o p o f r = 33.6 c m b e c o m e s eight drops o f r = 16.8 c m , a n d so o n . F i g u r e 7 shows that the total surface o r i n t e r f a c i a l area p r o d u c e d increases b y a factor o f 2 w i t h each cut. T h e i n i t i a l i n t e r f a c i a l area o f 1.42 m increases to 7.4 1 0
2 5
18
cm
tm
nm
Sphere Radius
Figure 7. Total area and energy changes involved in emulsifying 1 barrel of oil into water by dispersing into progressively finer droplets. m b y the t i m e droplets o f 0.64- radius have b e e n p r o d u c e d . T h i s i n crease is greater t h a n 5 orders o f m a g n i t u d e ! T h e larger i n t e r f a c i a l area w i l l have a significant total free energy as s h o w n i n F i g u r e 7. I f the i n t e r f a c i a l t e n s i o n is 35 m N / m , t h e n b y the t i m e the d r o p l e t size is r = 0.64 , the total e n e r g y w i l l have i n c r e a s e d f r o m 0.05 1 0 to 2.6 1 0 J . T h i s 2.6 1 0 J o f energy h a d to be a d d e d to the system to achieve the e m u l s i f i c a t i o n . I f this a m o u n t o f energy cannot be p r o v i d e d , f o r e x a m p l e , b y m e c h a n i c a l shear, t h e n a n o t h e r alternative is to use surfactant c h e m i s t r y to l o w e r the i n t e r f a c i a l free energy, o r i n t e r f a c i a l t e n s i o n .
2 4 4 4
T h e energy p l o t t e d i n F i g u r e 7 was o b t a i n e d b y m u l t i p l y i n g the total area b y the i n t e r f a c i a l t e n s i o n . N o w i f a s m a l l quantity o f a surfactant was a d d e d to the water, p o s s i b l y a f e w tenths o f a p e r c e n t , that l o w e r e d the i n t e r f a c i a l t e n s i o n to 0.35 m N / m , it w o u l d l o w e r the a m o u n t o f m e c h a n i c a l energy n e e d e d i n the example b y a factor o f 100. F r o m the area p e r m o l e c u l e that the a d s o r b e d e m u l s i f y i n g agent o c c u p i e s , the m i n i m u m a m o u n t o f e m u l s i f i e r n e e d e d f o r the e m u l s i o n c a n also be e s t i m a t e d . I n p r a c t i c e , l o w e r i n g i n t e r f a c i a l t e n s i o n alone m a y not be sufficient to stabilize an e m u l sion, i n w h i c h case o t h e r i n t e r f a c i a l p r o p e r t i e s m u s t be adjusted as w e l l . T h e s e s i m p l e calculations d o , h o w e v e r , s h o w h o w i m p o r t a n t the i n t e r f a c i a l p r o p e r t i e s c a n b e c o m e w h e n c o l l o i d a l - s i z e d species are i n v o l v e d , as i n e m u l sions.
1.
SCHRAMM
Basic Principles
19
Surface a n d Interfacial Tensions, R e g a r d i n g the m o l e c u l e s i n a l i q u i d , t h e attractive v a n d e r W a a l s forces b e t w e e n m o l e c u l e s are felt e q u a l l y b y a l l m o l e c u l e s except those i n t h e i n t e r f a c i a l r e g i o n . T h i s i n e q u a l i t y i n t h e van d e r W a a l s forces p u l l s t h e i n t e r f a c i a l m o l e c u l e s t o w a r d the i n t e r i o r o f the l i q u i d . T h e interface thus has a t e n d e n c y to contract spontaneously. F o r this reason, droplets o f l i q u i d a n d b u b b l e s o f gas t e n d to adopt a s p h e r i c a l shape, because this shape reduces t h e surface free energy. F o r two i m m i s c i b l e l i q u i d s , a s i m i l a r situation applies, except that i t m a y n o t b e so i m m e d i ately obvious h o w t h e interface w i l l t e n d to c u r v e . T h e r e w i l l still b e a n i m b a l a n c e o f i n t e r m o l e c u l a r forces a n d a c o n f i g u r a t i o n that m i n i m i z e s t h e i n t e r f a c i a l free energy. T h e surface free energy has units o f m i l l i j o u l e s p e r square m e t e r (1 m j / m = 1 erg/cm ), r e f l e c t i n g the fact that area expansion r e q u i r e s energy. Surface free energies are usually d e s c r i b e d i n terms o f c o n t r a c t i n g forces a c t i n g p a r a l l e l to t h e surface o r interface. Surface t e n s i o n ( 7 ) , o r i n t e r f a c i a l t e n s i o n (7), is t h e force p e r u n i t l e n g t h a r o u n d a surface, o r t h e free energy r e q u i r e d to create n e w surface area. T h u s , t h e units o f surface a n d i n t e r f a c i a l t e n s i o n are m i l l i n e w t o n s p e r m e t e r (1 m N / m = 1 dyne/cm). T h e s e units f o r surface a n d i n t e r f a c i a l t e n s i o n are n u m e r i c a l l y e q u a l t o t h e surface free energy. I n t e r f a c i a l tensions are f r e q u e n t l y i n t e r m e d i a t e b e t w e e n t h e values o f t h e surface tensions o f t h e l i q u i d s i n v o l v e d a n d are smallest w h e n t h e l i q u i d s are the most c h e m i c a l l y s i m i l a r (for p u r e l i q u i d s ) .
2 2 0
M a n y m e t h o d s f o r t h e m e a s u r e m e n t o f surface a n d i n t e r f a c i a l tensions, details o f the e x p e r i m e n t a l t e c h n i q u e s , a n d t h e i r l i m i t a t i o n s are d e s c r i b e d i n several g o o d reviews (27-29). S o m e methods that are u s e d most i n e m u l s i o n w o r k are t h e d u N o u y r i n g , d r o p w e i g h t o r v o l u m e , p e n d a n t d r o p , a n d the s p i n n i n g d r o p . T h e s p i n n i n g d r o p t e c h n i q u e is a p p l i c a b l e t o t h e v e r y l o w i n t e r f a c i a l tensions e n c o u n t e r e d i n t h e e n h a n c e d o i l r e c o v e r y a n d m i c r o e m u l s i o n fields (30). I n a l l cases, w h e n solutions r a t h e r t h a n p u r e l i q u i d s are i n v o l v e d , a p p r e c i a b l e changes c a n take p l a c e w i t h t i m e at t h e surfaces a n d interfaces. Young-Laplace Equation. I n t e r f a c i a l t e n s i o n causes a pressure d i f f e r e n c e to exist across a c u r v e d surface, the pressure b e i n g greater o n t h e concave side (i.e., o n t h e i n s i d e o f a d r o p l e t ) . I n an interface b e t w e e n phase A i n a d r o p l e t a n d phase s u r r o u n d i n g t h e d r o p l e t , t h e phases w i l l have pressures p a n d p . I f t h e p r i n c i p a l r a d i i o f c u r v a t u r e are R a n d R , t h e n
A B x 2
Ap=p -p
A
= 7 ( l / B + l/R )
1 a
A B
(12)
E q u a t i o n 12 is t h e Y o u n g - L a p l a c e e q u a t i o n (31). It shows that p > p ; t h e pressure i n s i d e a d r o p l e t exceeds that outside. F o r s p h e r i c a l droplets i n a n emulsion, Ap=p -p
A B
= 2y/R
(13)
20
so that varies w i t h t h e r a d i u s , R. ( M o r e details are g i v e n i n refs. 13 a n d 31.) T h e Y o u n g - L a p l a c e e q u a t i o n forms t h e basis f o r some i m p o r t a n t m e t h ods f o r m e a s u r i n g surface a n d i n t e r f a c i a l tensions, s u c h as t h e p e n d a n t , sessile, a n d s p i n n i n g d r o p m e t h o d s a n d t h e m a x i m u m b u b b l e pressure m e t h o d (27-30). I n p r i m a r y o i l r e c o v e r y f r o m u n d e r g r o u n d reservoirs, the c a p i l l a r y forces d e s c r i b e d b y this e q u a t i o n are r e s p o n s i b l e f o r h o l d i n g back m u c h o f t h e o i l (residual o i l ) i n parts o f t h e p o r e s t r u c t u r e i n t h e r o c k o r sand. A n y secondary o r e n h a n c e d (tertiary) o i l r e c o v e r y process strategies are i n t e n d e d to o v e r c o m e these same forces (32). I n t h e example i n v o l v i n g m i c r o e m u l s i o n s i n e n h a n c e d o i l r e c o v e r y (discussed u n d e r t h e h e a d i n g " M i c r o e m u l s i o n s " ) , the Y o u n g - L a p l a c e e q u a t i o n was u s e d , w i t h o u t i n t r o d u c t i o n , to d e m o n s t r a t e h o w l o w e r i n g i n t e r f a c i a l t e n s i o n c a n facilitate e m u l sification a n d i n c r e m e n t a l o i l recovery. I n that e x a m p l e r , t h e p o r e radius, was u s e d i n p l a c e o f R i n t h e Y o u n g - L a p l a c e e q u a t i o n , a n d t h e contact angle was i n c l u d e d . Contact Angles and Wetting. W h e n a d r o p l e t o f o i l i n w a t e r comes i n t o contact w i t h a s o l i d surface, t h e o i l m a y f o r m a b e a d o n t h e surface, o r i t m a y s p r e a d a n d f o r m a film. A l i q u i d h a v i n g a s t r o n g affinity for t h e s o l i d w i l l seek to m a x i m i z e its contact (interfacial area) a n d f o r m a film. A l i q u i d w i t h m u c h w e a k e r affinity m a y f o r m i n t o a b e a d . T h e affinity is t e r m e d t h e w e t t a b i l i t y . B e c a u s e there c a n b e degrees o f s p r e a d i n g , another q u a n t i t y is n e e d e d . T h e contact angle, , i n a n o i l - w a t e r - s o l i d system is d e f i n e d as t h e angle, m e a s u r e d t h r o u g h t h e aqueous phase, that is f o r m e d at the j u n c t i o n o f the three phases. W h e r e a s i n t e r f a c i a l t e n s i o n is d e f i n e d f o r t h e b o u n d a r y b e t w e e n t w o phases, t h e contact angle is d e f i n e d f o r a three-phase j u n c t i o n . I f t h e i n t e r f a c i a l forces a c t i n g a l o n g t h e p e r i m e t e r o f t h e d r o p l e t are r e p r e s e n t e d b y t h e i n t e r f a c i a l tensions, t h e n a n e q u i l i b r i u m force balance c a n b e w r i t t e n as
7w/o cos = 7s/ - 7SAV
0
( 14)
w h e r e t h e subscripts refer to w a t e r ( W ) , o i l ( O ) , a n d s o l i d (S). E q u a t i o n 14 is Y o u n g ' s e q u a t i o n . T h e s o l i d is c o m p l e t e l y w a t e r - w e t t e d i f = 0 a n d o n l y p a r t i a l l y w e t t e d o t h e r w i s e . E q u a t i o n 14 is f r e q u e n t l y u s e d to d e s c r i b e w e t t i n g p h e n o m e n a , so two p r a c t i c a l points are i m p o r t a n t . I n t h e o r y c o m p l e t e n o n w e t t i n g b y w a t e r w o u l d m e a n that = 180, b u t this contact angle is n o t seen i n p r a c t i c e . A l s o , values o f < 90 are o f t e n c o n s i d e r e d to r e p r e s e n t " w a t e r - w e t t i n g " , a n d values o f > 90 are c o n s i d e r e d to represent " n o n w a t e r - w e t t i n g " . T h i s assignment is r a t h e r a r b i t r a r y because i t is b a s e d o n c o r r e l a t i o n w i t h v i s u a l appearance o f d r o p l e t s o n surfaces. T h e s e considerations c o m e i n t o p l a y i n o i l r e c o v e r y schemes a p p l i e d to reservoirs o f m i x e d w e t t a b i l i t y o r w h e r e t h e r o c k is p r e d o m i n a n t l y o i l w e t t i n g . A n o t h e r example is t h e case o f t h e s o - c a l l e d P i c k e r i n g e m u l s i o n s ,
1.
SCHRAMM
Basic Principles
21
e m u l s i o n s s t a b i l i z e d b y fine p a r t i c l e s . A film o f c l o s e - p a c k e d particles has c o n s i d e r a b l e m e c h a n i c a l strength, w h i c h c o n t r i b u t e s to t h e stability o f a n e m u l s i o n . T h e most stable e m u l s i o n s o c c u r w h e n t h e contact angle is close to 90, so that t h e particles w i l l c o l l e c t at t h e interface. C o m b i n i n g Y o u n g ' s e q u a t i o n w i t h t h e o r i e n t e d w e d g e t h e o r y (see later, " E m u l s i f y i n g A g e n t s " ) allows some p r e d i c t i o n s to b e m a d e . I f the contact angle f o r a fine p a r t i c l e at the O / W interface is < 90, t h e n most o f t h e p a r t i c l e w i l l reside i n t h e aqueous phase. I n this case a n O / W e m u l s i o n is i n d i c a t e d . C o n v e r s e l y , i f > 90, t h e n t h e p a r t i c l e w i l l b e m o s t l y i n t h e o i l phase, a n d W / O is p r e d i c t e d .
Adsorption
at Interfaces:
Surface Activity.
Surfactants.
S o m e c o m p o u n d s , l i k e s h o r t - c h a i n fatty acids, c a n b e p a r t l y s o l u b l e i n b o t h w a t e r a n d o i l . T h i s d u a l s o l u b i l i t y is because s u c h m o l e c u l e s are a m p h i p h i l i c or a m p h i p a t h i c ; that is, they have one part that has a n affinity f o r t h e o i l (the n o n p o l a r h y d r o c a r b o n c h a i n ) , a n d o n e part that has a n affinity f o r t h e w a t e r (the p o l a r g r o u p ) . T h e e n e r g e t i c a l l y most favorable o r i e n t a t i o n f o r these m o l e c u l e s is at t h e o i l - w a t e r interface, so that each p a r t o f the m o l e c u l e c a n reside i n t h e solvent f o r w h i c h i t has the greatest affinity (see F i g u r e 8).
Figure 8. Surfactant associations in an O/W emulsion. The size of the surfac tant molecules compared to the oil droplets has been exaggerated for the purposes of illustration.
22
T h e s e m o l e c u l e s that f o r m o r i e n t e d monolayers at interfaces s h o w surface activity a n d are t e r m e d surfactants. A s t h e r e w i l l b e a balance b e t w e e n a d s o r p t i o n a n d d e s o r p t i o n (due to t h e r m a l m o t i o n s ) , the i n t e r f a c i a l c o n d i t i o n r e q u i r e s some t i m e to establish. B e c a u s e o f this t i m e r e q u i r e d , surface activity s h o u l d b e c o n s i d e r e d a d y n a m i c p h e n o m e n o n . T h i s fact can b e seen b y m e a s u r i n g surface t e n s i o n versus t i m e f o r a freshly f o r m e d surface. A c o n s e q u e n c e o f surfactant a d s o r p t i o n at an interface is that it p r o v i d e s an e x p a n d i n g force acting against the n o r m a l i n t e r f a c i a l t e n s i o n . I f is this e x p a n d i n g pressure (surface pressure), t h e n 7 = 7 i - . T h u s , surfactants t e n d to l o w e r i n t e r f a c i a l t e n s i o n ; i f a l o w e n o u g h value o f 7 is r e a c h e d , e m u l s i f i c a t i o n c a n take p l a c e because o n l y a s m a l l increase i n surface free energy is r e q u i r e d , f o r e x a m p l e , w h e n ~ 7 i t i a i - I f s o l u t e - s o l v e n t forces are greater t h a n s o l v e n t - s o l v e n t forces o n the o t h e r h a n d , t h e n m o l e c u l a r m i g r a t i o n away f r o m the interface can o c c u r a n d cause i n c r e a s e d surface t e n s i o n (e.g., N a C l [aq]).
i n i t i a i n
G i b b s has t h e r m o d y n a m i c a l l y d e s c r i b e d the l o w e r i n g o f surface free e n e r g y that results f r o m surfactant a d s o r p t i o n . T h e g e n e r a l G i b b s adsorp t i o n e q u a t i o n f o r a b i n a r y , i s o t h e r m a l system c o n t a i n i n g excess electrolyte is T = - (1 /RT)
s s
(dy/d
In C )
s 2 s
(15)
w h e r e F is the surface excess o f surfactant (mol/cm ), C is the s o l u t i o n c o n c e n t r a t i o n o f the surfactant ( M ) , a n d 7 m a y be e i t h e r surface o r i n t e r f a c i a l t e n s i o n ( m N / m ) . T h i s e q u a t i o n c a n b e a p p l i e d to d i l u t e surfactant s o l u tions i n w h i c h the surface c u r v a t u r e is not great a n d w h e r e the a d s o r b e d film c a n b e c o n s i d e r e d a m o n o l a y e r . T h e p a c k i n g density o f surfactant i n a m o n o l a y e r at the interface c a n b e c a l c u l a t e d as f o l l o w s . T h e surface excess i n a t i g h t l y p a c k e d m o n o l a y e r c a n be c a l c u l a t e d f r o m the slope o f the l i n e a r p o r t i o n o f a p l o t o f surface t e n s i o n versus the l o g a r i t h m o f s o l u t i o n c o n c e n t r a t i o n (see F i g u r e 9). F r o m this slope, the area p e r a d s o r b e d m o l e c u l e (a ) c a n be c a l c u l a t e d f r o m
s
= 1/(2 .)

(16) examples are given by
where
is A v o g a d r o ' s n u m b e r .
Numerous
R o s e n (33). Surface Films. I n s o l u b l e p o l a r m o l e c u l e s (e.g., l o n g - c h a i n fatty ac ids) e x h i b i t an extreme k i n d o f a d s o r p t i o n at l i q u i d surfaces. T h a t is, t h e y can b e m a d e to c o n c e n t r a t e i n one m o l e c u l a r layer at the surface. T h e s e i n t e r f a c i a l films o f t e n p r o v i d e the s t a b i l i z i n g i n f l u e n c e i n e m u l s i o n s because they c a n b o t h l o w e r i n t e r f a c i a l t e n s i o n a n d increase the i n t e r f a c i a l viscosity. I n c r e a s i n g i n t e r f a c i a l viscosity p r o v i d e s a m e c h a n i c a l resistance to coales c e n c e . S u c h systems also l e n d themselves to the study o f size, shape, a n d
1.
SCHRAMM
Basic Principles
23
CMC
Surfactant Monomers
Surfactant Micelles
Log Concentration
Figure 9. The association behavior of surfactants in solution, showing the critical micelle concentration (CMC). o r i e n t a t i o n o f m o l e c u l e s at an interface. H a v i n g an a d s o r b e d layer lowers the surface t e n s i o n (to y) b y the surface pressure = 7 i - 7, as already n o t e d . I n a surface balance ( p i o n e e r e d b y L a n g m u i r a n d others) versus t h e available area o f surface (A) c a n b e d e t e r m i n e d d i r e c t l y . A n o t h e r a p p r o a c h is to measure t h e l o w e r e d surface tension ( W i l h e l m y plate) a n d calculate . F o r v e r y l o w film pressures, an i d e a l gas l a w analogy,
i n i t i a
TTA = nRT = nN kT
A A
(17)
allows c a l c u l a t i o n o f the effective area p e r m o l e c u l e (A/nN ) i n the m o n o layer; here is t h e n u m b e r o f moles, R is t h e gas constant, is absolute t e m p e r a t u r e , a n d k is the B o l t z m a n n constant. Classification of Surfactants, Surfactants are classified a c c o r d i n g to the nature o f the p o l a r ( h y d r o p h i l i c ) part o f the m o l e c u l e , as i l l u s t r a t e d i n T a b l e I I I . I n - d e p t h discussions o f surfactant structure a n d c h e m i s t r y c a n b e f o u n d i n references 3 3 - 3 5 . I n aqueous s o l u t i o n , d i l u t e concentrations o f surfactant act m u c h as n o r m a l electrolytes, b u t at h i g h e r concentrations v e r y d i f f e r e n t b e h a v i o r results. T h i s b e h a v i o r (illustrated i n F i g u r e s 8 a n d 9) was e x p l a i n e d b y M c B a i n i n terms o f o r g a n i z e d aggregates c a l l e d m i c e l l e s i n w h i c h the l i p o p h i l i c parts o f the surfactants associate i n the i n t e r i o r o f the aggregate a n d leave h y d r o p h i l i c parts to face t h e aqueous m e d i u m . ( D e t a i l s are g i v e n i n refs. 16 a n d 31.) T h e c o n c e n t r a t i o n at w h i c h m i c e l l e f o r m a t i o n b e c o m e s
Table III. Surfactant Classifications ^

3 2 1 6 + 2 + 4 +
Class
Examples
Structures
Anionic CH (CH ) CO<XNa CH3(CH )iiS0 ~Na CH (CH ) C6H S03~Na

3 2 11 4 3 2 +
N a starate N a dodecyl sulfate N a dodecyl benzene sulfonate
Cationic
3 2 15 + 3
Laurylamine hydrochloride Cetyl trimethylammonium bromide CH (CH )iiNH3 Cr CH (CH ) N (CH )3Br2n+ 2 m
Nonionic
9 6 4
Polyoxyethylene alcohol Alkylphenol ethoxylate

n 2 3
CH i(OCH2CH ) OH C Hi9-C H -(OCH CH ) OH

2 2 n
Zwitterionic C H
n 2 n +
C H CONH(CH ) N (CH )2CH COO"

2 3 + 3 2
In Emulsions; Schramm, L.; Advances in Chemistry; American Chemical Society: Washington, DC, 1992. iCONH(CH ) N (CH ) CH CH(OH)CH S0 2 3 + 3 2 2 2 3
Lauramidopropyl betaine Cocoamido-2-hydroxypropyl sulfobetaine
1.
SCHRAMM
Basic Principles
25
significant is c a l l e d the c r i t i c a l m i c e l l e c o n c e n t r a t i o n ( C M C ) . T h e C M C is a p r o p e r t y o f the surfactant a n d several o t h e r factors, because m i c e l l i z a t i o n is o p p o s e d b y t h e r m a l a n d electrostatic forces. A l o w C M C is f a v o r e d b y i n c r e a s i n g the m o l e c u l a r mass o f the l i p o p h i l i c p a r t o f the m o l e c u l e , l o w e r i n g the t e m p e r a t u r e (usually), a n d a d d i n g e l e c t r o l y t e . Surfactant m o l e c u l a r weights range f r o m a f e w h u n d r e d u p to several t h o u s a n d . S o m e t y p i c a l C M C values f o r l o w electrolyte concentrations at r o o m t e m p e r a t u r e are Surfactant Class Nonionic Anionic Amphoteric Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 CMC (M) KH-IO" KH-IO" KH-IQ
4 2
- 1
T h e s o l u b i l i t i e s o f m i c e l l e - f o r m i n g surfactants show a s t r o n g increase above a c e r t a i n t e m p e r a t u r e , t e r m e d the K r a f f t p o i n t ( T ) . T h i s increase i n s o l u b i l i t y is e x p l a i n e d b y the fact that the single surfactant m o l e c u l e s have l i m i t e d s o l u b i l i t y , whereas the m i c e l l e s are v e r y s o l u b l e . R e f e r r i n g to F i g u r e 10, b e l o w the K r a f f t p o i n t the s o l u b i l i t y o f the surfactant is too l o w for m i c e l l i z a t i o n , a n d s o l u b i l i t y alone d e t e r m i n e s the surfactant m o n o m e r c o n c e n t r a t i o n . A s t e m p e r a t u r e increases, the s o l u b i l i t y increases u n t i l at T the C M C is r e a c h e d . A t this t e m p e r a t u r e a relatively large a m o u n t o f surfactant c a n be d i s p e r s e d i n m i c e l l e s , a n d s o l u b i l i t y increases greatly. A b o v e the
K K
Figure 10. The solubility-micellization behavior of surfactants in solution, showing the Krafft point.
26
K r a f f t p o i n t , m a x i m u m r e d u c t i o n i n surface o r i n t e r f a c i a l t e n s i o n occurs at the C M C because n o w the C M C d e t e r m i n e s the surfactant m o n o m e r c o n centration.
C o h e s i o n , A d h e s i o n , a n d Spreading.
T w o phases A a n d may
have a n interface b e t w e e n t h e m , A B . C o h e s i o n , a d h e s i o n , a n d s p r e a d i n g can be d e n n e d f o r the changes s h o w n i n F i g u r e 11 ( i n v o l v i n g always u n i t surface area). T h e w o r k o f c o h e s i o n represents the energy r e q u i r e d to increase i n t e r f a c i a l area b y two square u n i t s . T h u s the energy r e q u i r e d to disperse o i l i n t o finer a n d finer droplets, to make a n e m u l s i o n , increases as the i n t e r f a -
Figure 11. Cohesion, adhesion, and spreading. All indicated changes are per unit area, AG is the Gibbs free energy change, and the subscripts denote oil (O), water (W) and air (A).
1.
SCHRAMM
Basic
Principles
27
c i a l t e n s i o n b e t w e e n t h e droplets increases. T h e w o r k o f a d h e s i o n is t h e energy i n v o l v e d w h e n t w o surfaces, i n i t i a l l y i n contact w i t h each other, are separated to each contact a t h i r d phase. T h e w o r k o f a d h e s i o n relates t o , f o r e x a m p l e , surface e n e r g y changes i n v o l v e d w h e n a n o i l d r o p l e t i n i t i a l l y i n contact w i t h a s o l i d p a r t i c l e b e c o m e s released i n t o water. S p r e a d i n g occurs w h e n , f o r e x a m p l e , e m u l s i f i e d o i l droplets r e a c h t h e a i r - w a t e r interface a n d spread over the surface. T h i s s p r e a d i n g is a m e c h a n i s m f o r d e m u l s i f i c a t i o n ; a negative s p r e a d i n g coefficient s h o u l d thus t e n d to c o n t r i b u t e to e m u l s i o n stability. S p r e a d i n g is also a m e c h a n i s m f o r d e f o a m i n g b y e m u l s i o n s (36). P e t r o l e u m e m u l s i o n s have b e e n u s e d to p r e v e n t t h e f o r m a t i o n o f foams, o r destroy foams already generated, i n various i n d u s t r i a l processes (37).
Stability of Emulsions
M e a n i n g o f Stability. M o s t e m u l s i o n s are not t h e r m o d y n a m i c a l l y stable. R a t h e r t h e y possess some degree o f k i n e t i c stability, a n d i t is i m p o r tant t o d i s t i n g u i s h t h e degree o f change a n d t h e t i m e scale. A s m e n t i o n e d p r e v i o u s l y , coalescence a n d aggregation are processes i n w h i c h p a r t i c l e s , d r o p l e t s , o r b u b b l e s are b r o u g h t together w i t h (coalescence) o r w i t h o u t (aggregation) large changes i n surface area. T h u s , t h e r e c a n b e d i f f e r e n t k i n d s o f k i n e t i c stability. T h i s d i s c u s s i o n o f c o l l o i d stability w i l l explore t h e reasons w h y c o l l o i d a l dispersions c a n have d i f f e r e n t degrees o f k i n e t i c s t a b i l ity a n d h o w these are i n f l u e n c e d , a n d c a n t h e r e f o r e b e m o d i f i e d , b y s o l u t i o n a n d surface p r o p e r t i e s . T h e d i s c u s s i o n is c a r r i e d f u r t h e r , a n d i n m o r e d e t a i l , i n C h a p t e r 2. E n c o u n t e r s b e t w e e n particles i n a d i s p e r s i o n c a n o c c u r f r e q u e n t l y b e cause o f B r o w n i a n m o t i o n , s e d i m e n t a t i o n , o r s t i r r i n g . T h e stability o f t h e d i s p e r s i o n d e p e n d s u p o n h o w t h e particles interact w h e n these e n c o u n t e r s h a p p e n . T h e m a i n cause o f r e p u l s i v e forces is t h e electrostatic r e p u l s i o n b e t w e e n l i k e - c h a r g e d objects. T h e m a i n attractive forces are t h e v a n d e r W a a l s forces b e t w e e n objects. Electrostatic F o r c e s . Charged Interfaces. M o s t substances ac q u i r e a surface e l e c t r i c charge w h e n b r o u g h t i n t o contact w i t h a p o l a r m e d i u m s u c h as water. F o r e m u l s i o n s , t h e o r i g i n o f t h e charge c a n b e i o n i z a t i o n , as w h e n surface a c i d f u n c t i o n a l i t i e s i o n i z e w h e n o i l droplets are d i s p e r s e d i n t o a n aqueous s o l u t i o n , o r the o r i g i n c a n b e a d s o r p t i o n , as w h e n surfactant ions o r c h a r g e d particles adsorb o n t o a n o i l d r o p l e t surface. S o l i d particles c a n have a d d i t i o n a l m e c h a n i s m s o f c h a r g i n g . O n e is t h e u n e q u a l d i s s o l u t i o n o f cations a n d anions that m a k e u p t h e crystal s t r u c t u r e ( i n t h e salt type m i n e r a l s , f o r example). A n o t h e r is t h e d i f f u s i o n o f c o u n t e r i o n s away f r o m t h e surface o f a s o l i d w h o s e i n t e r n a l crystal structure carries a n o p p o site charge because o f i s o m o r p h i c s u b s t i t u t i o n ( i n clays, f o r example). T h e
28
surface charge influences t h e d i s t r i b u t i o n o f n e a r b y ions i n t h e p o l a r m e d i u m . Ions o f opposite charge (counterions) are attracted to t h e surface, b u t those o f l i k e charge (co-ions) are r e p e l l e d . A n e l e c t r i c d o u b l e layer, w h i c h is diffuse because o f m i x i n g c a u s e d b y t h e r m a l m o t i o n , is thus f o r m e d . I n a p r a c t i c a l p e t r o l e u m e m u l s i o n s i t u a t i o n , t h e d e g r e e o f surface c h a r g i n g is m o r e c o m p l i c a t e d . A n example is t h e b i t u m e n - w a t e r interface, w h i c h b e c o m e s negatively c h a r g e d i n alkaline aqueous solutions as a result o f t h e i o n i z a t i o n o f surface c a r b o x y l i c a c i d groups b e l o n g i n g t o n a t u r a l surfactants present i n t h e b i t u m e n . T h e degree o f negative c h a r g i n g is v e r y i m p o r t a n t to the success o f b i t u m e n r e c o v e r y processes f r o m i n situ o i l sands a n d also separation processes f r o m surface o i l sands, s u c h as t h e h o t - w a t e r flotation process (38-42). T h e degree o f negative charge at t h e interface d e p e n d s o n the H a n d i o n i c strength o f the s o l u t i o n (38, 39) a n d also o n the c o n c e n t r a t i o n o f n a t u r a l surfactant m o n o m e r s present i n t h e aqueous phase (40, 41). W i t h b i t u m e n , as w i t h o t h e r heavy c r u d e oils, m o r e t h a n o n e k i n d o f surfac tant m a y b e p r o d u c e d (42), a n d t h e s o l u t i o n concentrations o f the surfactants d e p e n d also o n r e a c t i o n c o n d i t i o n s (temperature, etc.) a n d o n the extent o f c o m p e t i n g reactions s u c h as t h e a d s o r p t i o n o f t h e surfactants o n t o s o l i d (clay) particles that are present (43, 44). Electric Double Layer. T h e e l e c t r i c d o u b l e layer ( E D L ) consists o f the c h a r g e d surface a n d a n e u t r a l i z i n g excess o f c o u n t e r i o n s over co-ions, d i s t r i b u t e d near t h e surface (see F i g u r e 12). T h e E D L c a n b e v i e w e d as b e i n g c o m p o s e d o f t w o layers: a n i n n e r layer that m a y i n c l u d e a d s o r b e d ions a d i f f u s e layer i n w h i c h ions are d i s t r i b u t e d a c c o r d i n g to t h e i n f l u e n c e o f e l e c t r i c a l forces a n d t h e r m a l m o t i o n G o u y a n d C h a p m a n p r o p o s e d a s i m p l e quantitative m o d e l f o r t h e diffuse d o u b l e layer, a s s u m i n g , a m o n g other things, a n i n f i n i t e , flat, u n i f o r m l y c h a r g e d surface a n d p o i n t - c h a r g e ions. ( F u r t h e r details are g i v e n i n refs. 14, 3 1 , a n d 45.) T a k i n g t h e surface p o t e n t i a l to b e , t h e p o t e n t i a l at a distance f r o m t h e surface is a p p r o x i m a t e l y = exp (-)
0
( 18)
T h e surface charge density is g i v e n as = , w h e r e e is the p e r m i t t i v i t y a n d is n o t c o n d u c t i v i t y b u t a special v a r i a b l e d e f i n e d i n e q u a t i o n 19; thus, d e p e n d s o n surface charge density a n d t h e s o l u t i o n i o n i c c o m p o s i t i o n ( t h r o u g h ). T h e variable l/ is c a l l e d t h e d o u b l e - l a y e r thickness, a n d f o r w a t e r at 25 C i t is g i v e n b y = 3.288V/ (nm" )
1
(19)
1.
SCHRAMM
Basic Principles
29
Figure 12. Simplified illustrations of the electrical double layer around a negatively charged colloidal emulsion droplet. The left view shows the change in charge density around the droplet. The right view shows the distribution of ions around the charged droplet. (Courtesy of L. A. Ravina, Zeta-Meter, Inc., Long Island City, NY.) w h e r e I is the i o n i c strength, g i v e n b y I = (1/2) <<% , i n w h i c h c are t h e
2 {
i n d i v i d u a l i o n c o n c e n t r a t i o n s a n d z are t h e respective i o n - c h a r g e n u m b e r s .
{
F o r a 1 - 1 electrolyte, 1/K=lnmfor/ = 1 0 M
1
1/K = 10 n m f o r / = " M
3
(20)
I n fact a n i n n e r layer exists because ions are not r e a l l y p o i n t charges a n d an i o n c a n a p p r o a c h a surface o n l y to t h e extent a l l o w e d b y its h y d r a t i o n s p h e r e . T h e S t e r n m o d e l specifically i n c o r p o r a t e s a layer o f s p e c i f i c a l l y a d s o r b e d ions b o u n d e d b y a p l a n e , t h e S t e r n p l a n e (see F i g u r e 13 a n d refs. 14, 3 1 , a n d 45). I n this case t h e p o t e n t i a l changes f r o m at t h e surface, t o () at t h e S t e r n p l a n e , t o = 0 i n b u l k s o l u t i o n . Electrokinetic Phenomena. E l e c t r o k i n e t i c m o t i o n occurs w h e n t h e
m o b i l e part o f the e l e c t r i c d o u b l e layer is s h e a r e d away f r o m t h e i n n e r l a y e r
30
Figure 13. Simplified illustration of the surface and zeta potentials for a charged emulsion droplet dispersed in high and low electrolyte concentration aqueous solutions. (Courtesy of L. A. Ravina, Zeta-Meter, Inc., Long Island City, NY.)
(charged surface). T h e f o u r types o f e l e c t r o k i n e t i c m e a s u r e m e n t s are elec trophoresis, electro-osmosis, s t r e a m i n g p o t e n t i a l , a n d s e d i m e n t a t i o n p o t e n tial, o f w h i c h electrophoresis finds the most use i n i n d u s t r i a l p r a c t i c e . G o o d d e s c r i p t i o n s o f p r a c t i c a l e x p e r i m e n t a l t e c h n i q u e s i n electrophoresis a n d t h e i r l i m i t a t i o n s c a n be f o u n d i n references 4 6 - 4 8 . I n electrophoresis an e l e c t r i c field is a p p l i e d to a sample a n d causes c h a r g e d droplets o r particles a n d any attached m a t e r i a l o r l i q u i d to m o v e t o w a r d the o p p o s i t e l y c h a r g e d e l e c t r o d e . T h u s the results c a n be i n t e r p r e t e d o n l y i n terms o f charge density ( ) or p o t e n t i a l () at the p l a n e o f shear. T h e latter is also k n o w n as the zeta p o t e n t i a l . B e c a u s e the exact l o c a t i o n o f the shear p l a n e is g e n e r a l l y not k n o w n , the zeta p o t e n t i a l is u s u a l l y taken to be a p p r o x i m a t e l y e q u a l to the p o t e n t i a l at the S t e r n p l a n e ( F i g u r e 13):
= ()
(21)
w h e r e is the distance f r o m the d r o p l e t surface to the S t e r n p l a n e . I n m i c r o e l e c t r o p h o r e s i s the d i s p e r s e d droplets are v i e w e d u n d e r a m i c r o s c o p e , a n d t h e i r e l e c t r o p h o r e t i c v e l o c i t y is m e a s u r e d at a l o c a t i o n i n the sample c e l l w h e r e the e l e c t r i c field gradient is k n o w n . T h i s m e a s u r e m e n t m u s t b e d o n e at c a r e f u l l y selected planes w i t h i n the c e l l because the c e l l walls b e c o m e c h a r g e d as w e l l a n d cause e l e c t r o - o s m o t i c flow o f the b u l k l i q u i d i n s i d e the cell. T h e e l e c t r o p h o r e t i c m o b i l i t y , , is d e f i n e d as the e l e c t r o p h o r e t i c v e l o c i t y d i v i d e d b y the e l e c t r i c field gradient at the l o c a t i o n w h e r e t h e v e l o c i t y
1.
SCHRAMM
Basic Principles
31
was m e a s u r e d . It r e m a i n s t h e n to relate t h e e l e c t r o p h o r e t i c m o b i l i t y to t h e z e t a p o t e n t i a l ( ) . T w o s i m p l e relations c a n b e u s e d to calculate zeta p o t e n tials i n l i m i t i n g cases: H i i c k e l t h e o r y . F o r d r o p l e t s o f s m a l l radius (r) w i t h " t h i c k " e l e c t r i c d o u b l e layers, m e a n i n g that Kr < 1, i t is a s s u m e d that Stokes' l a w applies a n d t h e e l e c t r i c a l f o r c e is e q u a t e d to t h e f r i c t i o n a l resistance o f t h e d r o p l e t ,
= e/(1.5r/). = //.
S m o l u c h o w s k i t h e o r y . F o r large d r o p l e t s w i t h " t h i n " e l e c t r i c d o u b l e layers, m e a n i n g droplets f o r w h i c h > 100,
T h e s e theories are d i s c u s s e d i n m o r e d e t a i l i n r e f e r e n c e s 14 a n d 50. W i t h these relations zeta potentials c a n b e c a l c u l a t e d f o r m a n y p r a c t i c a l
systems. W i t h i n e a c h set o f l i m i t i n g c o n d i t i o n s t h e e l e c t r o p h o r e t i c m o b i l i t y is i n d e p e n d e n t o f p a r t i c l e size a n d shape as l o n g as t h e p o t e n t i a l is c o n stant. F o r i n t e r m e d i a t e values o f fcr, the H e n r y e q u a t i o n a n d m a n y o t h e r equations a p p l y (46, 47, 49). Repulsive Forces. I n t h e s i m p l e s t e x a m p l e o f c o l l o i d stability, e m u l created
s i o n d r o p l e t s w o u l d b e s t a b i l i z e d e n t i r e l y b y t h e r e p u l s i v e forces
w h e n t w o c h a r g e d surfaces a p p r o a c h each o t h e r a n d t h e i r e l e c t r i c d o u b l e layers o v e r l a p . T h e r e p u l s i v e energy, V , f o r s p h e r i c a l d r o p l e t s is g i v e n

R
a p p r o x i m a t e l y as V =
R
^ \ x p ( - K H )
n
(22)
w h e r e t h e spheres have radius r a n d are separated b y distance , is a constant (3.93 1 0

3 9
A~ s~ ), is the c o u n t e r i o n charge n u m b e r , a n d
2 2
exp [zeijj(S) / 2kT] - 1 exp[%?i/<S)/2fcT] + l Dispersion Forces,
v a n d e r W a a l s p o s t u l a t e d that n e u t r a l m o l e
cules exert forces o f attraction o n each o t h e r that are c a u s e d b y e l e c t r i c a l i n t e r a c t i o n s b e t w e e n t h r e e types o f d i p o l a r configurations. T h e attraction results f r o m t h e o r i e n t a t i o n o f d i p o l e s that m a y b e (1) t w o p e r m a n e n t d i p o l e s , (2) d i p o l e - i n d u c e d d i p o l e , o r (3) i n d u c e d d i p o l e - i n d u c e d d i p o l e . I n d u c e d d i p o l e - i n d u c e d d i p o l e forces b e t w e e n n o n p o l a r m o l e c u l e s are also c a l l e d L o n d o n d i s p e r s i o n forces. E x c e p t f o r q u i t e p o l a r materials, t h e L o n d o n d i s p e r s i o n forces are t h e m o r e significant o f t h e t h r e e . F o r m o l e c u l e s the force varies i n v e r s e l y w i t h t h e sixth p o w e r o f the i n t e r m o l e c u l a r d i s tance. F o r d i s p e r s e d d r o p l e t s (or p a r t i c l e s , etc.) t h e d i s p e r s i o n forces c a n b e a p p r o x i m a t e d b y a d d i n g t h e attractions b e t w e e n a l l i n t e r d r o p l e t pairs o f
32
m o l e c u l e s . W h e n a d d e d this w a y , the d i s p e r s i o n force b e t w e e n t w o d r o p l e t s decays less r a p i d l y as a f u n c t i o n o f separation distance t h a n is the case f o r i n d i v i d u a l m o l e c u l e s . F o r t w o spheres o f radius r i n a v a c u u m , separated b y distance H , the attractive e n e r g y V c a n b e a p p r o x i m a t e d b y
A
V
A
= -
12H
(24)
f o r H < 1 0 - 2 0 n m a n d H r . T h e constant A is k n o w n as the H a m a k e r constant a n d d e p e n d s o n the density a n d p o l a r i z a b i l i t y o f atoms i n the p a r t i c l e s . T y p i c a l l y 1 0 " J < A < 1 0 " J . W h e n the p a r t i c l e s are i n a m e d i u m o t h e r t h a n v a c u u m , the attraction is r e d u c e d . T h i s r e d u c e d attraction c a n be a c c o u n t e d f o r b y u s i n g an effective H a m a k e r constant
20 19
A=
( V , - ^ )
(25)
w h e r e the subscripts denote the m e d i u m (1) a n d particles (2). T h e effective H a m a k e r constant e q u a t i o n shows that the attraction b e t w e e n particles is weakest w h e n the particles a n d m e d i u m are most c h e m i cally s i m i l a r (A ~ A ) . T h e H a m a k e r constants are u s u a l l y not w e l l k n o w n a n d m u s t be a p p r o x i m a t e d .
1 2
D L V O Theory. Derjaguin and Landau, and independently Verwey a n d O v e r b e e k (45), d e v e l o p e d a quantitative t h e o r y f o r the stability o f l y o p h o b i c c o l l o i d s , n o w k n o w n as the D L V O theory. It was d e v e l o p e d i n an attempt to a c c o u n t f o r the o b s e r v a t i o n that c o l l o i d s coagulate q u i c k l y at h i g h electrolyte c o n c e n t r a t i o n s , slowly at l o w c o n c e n t r a t i o n s , a n d w i t h a v e r y n a r r o w electrolyte c o n c e n t r a t i o n range over w h i c h the t r a n s i t i o n f r o m one to the o t h e r o c c u r s . T h i s n a r r o w electrolyte c o n c e n t r a t i o n range defines the c r i t i c a l c o a g u l a t i o n c o n c e n t r a t i o n ( C C C ) . T h e D L V O t h e o r y accounts f o r the energy changes that take p l a c e w h e n t w o droplets (or particles) a p p r o a c h each other, a n d involves e s t i m a t i n g the energy o f attraction ( L o n d o n - v a n d e r W a a l s ) versus i n t e r p a r t i c l e distance a n d the energy o f r e p u l s i o n (electro static) versus distance. T h e s e , V a n d V , respectively, are t h e n a d d e d to gether to y i e l d the total i n t e r a c t i o n e n e r g y V . A t h i r d i m p o r t a n t force occurs at v e r y s m a l l separation distances w h e r e the a t o m i c e l e c t r o n c l o u d s o v e r l a p a n d causes a s t r o n g r e p u l s i o n , c a l l e d B o r n r e p u l s i o n . T h e t h e o r y has b e e n d e v e l o p e d f o r several s p e c i a l cases, i n c l u d i n g the i n t e r a c t i o n b e t w e e n t w o spheres, a n d refinements are constantly b e i n g m a d e .
A R
T h e value o f V decreases e x p o n e n t i a l l y w i t h i n c r e a s i n g separation dis tance a n d has a range about e q u a l to " , a n d V decreases i n v e r s e l y w i t h i n c r e a s i n g separation distance. F i g u r e 14 shows a single attractive e n e r g y c u r v e a n d t w o d i f f e r e n t r e p u l s i v e energy curves, r e p r e s e n t i n g t w o v e r y d i f f e r e n t levels o f electrolyte c o n c e n t r a t i o n . T h e figure shows the total i n t e r a c t i o n e n e r g y curves that result i n each case. E i t h e r the attractive v a n
R 1 A
1.
SCHRAMM
Basic Principles
33
d e r W a a l s forces or the r e p u l s i v e electric d o u b l e - l a y e r forces can p r e d o m i nate at d i f f e r e n t i n t e r d r o p l e t distances. W i t h a positive p o t e n t i a l e n e r g y m a x i m u m , a d i s p e r s i o n s h o u l d b e stable if V kT, that is, i f the energy is large c o m p a r e d to the t h e r m a l energy o f the particles (15&Tis c o n s i d e r e d i n s u r m o u n t a b l e ) . I n this case c o l l i d i n g d r o p l e t s s h o u l d r e b o u n d w i t h o u t contact, a n d the e m u l s i o n s h o u l d b e stable to ag gregation. If, o n the o t h e r h a n d , the p o t e n t i a l energy m a x i m u m is not v e r y great, V ~ kT, t h e n slow aggregation s h o u l d o c c u r . T h e h e i g h t o f the energy b a r r i e r d e p e n d s o n the surface p o t e n t i a l , () a n d o n the range o f the r e p u l s i v e forces, . F i g u r e 14 shows that an energy m i n i m u m c a n o c c u r at larger i n t e r p a r t i c l e distances. I f this energy m i n i m u m is reasonably d e e p c o m p a r e d to kT, t h e n a loose, easily r e v e r s i b l e aggregation s h o u l d o c c u r .
- 1
Practical G u i d e l i n e s . T h e D L V O calculations c a n b e c o m e q u i t e i n v o l v e d , r e q u i r i n g c o n s i d e r a b l e k n o w l e d g e about the systems o f interest. A l s o , t h e y present some p r o b l e m s . F o r e x a m p l e , some d i s t o r t i o n o f the s p h e r i c a l e m u l s i o n droplets w i l l o c c u r as they a p p r o a c h each o t h e r a n d b e g i n to seriously interact; these interactions cause a flattening. A l s o , o u r v i e w o f
Figure 14. The effect of different repulsive potential energy curves (1 and 2) on the total interaction energy for a given attractive energy curve. (Reproduced with permission from reference 16. Copyright 1981 Butterworth Heinemann Ltd.)
34
the v a l i d i t y o f the t h e o r y is c h a n g i n g as m o r e b e c o m e s k n o w n about t h e i n f l u e n c e o f a d d i t i o n a l forces s u c h as those d u e to surface h y d r a t i o n . T h e D L V O t h e o r y nevertheless f o r m s a v e r y u s e f u l starting p o i n t i n a t t e m p t i n g to u n d e r s t a n d c o m p l e x c o l l o i d a l systems s u c h as p e t r o l e u m e m u l s i o n s . E m p i r i c a l " r u l e s o f t h u m b " c a n b e u s e d to give a first estimate o f the d e g r e e o f c o l l o i d a l stability that a system is l i k e l y to have i f the zeta potentials o f t h e d r o p l e t s are k n o w n . Zeta Potential Criteria. M a n y types o f c o l l o i d s t e n d to adopt a nega tive surface charge w h e n d i s p e r s e d i n aqueous solutions h a v i n g i o n i c c o n centrations a n d p H t y p i c a l o f n a t u r a l waters. F o r s u c h systems o n e r u l e o f t h u m b stems f r o m observations that the c o l l o i d a l particles are q u i t e stable w h e n t h e zeta p o t e n t i a l is about -30 m V o r m o r e negative, a n d q u i t e unsta b l e because o f a g g l o m e r a t i o n w h e n the zeta p o t e n t i a l is b e t w e e n +5 a n d -5 m V . A n e x p a n d e d set o f g u i d e l i n e s , d e v e l o p e d f o r p a r t i c l e suspensions, is g i v e n i n r e f e r e n c e 48. S u c h c r i t e r i a are f r e q u e n t l y u s e d to d e t e r m i n e o p t i m a l dosages o f p o l y v a l e n t m e t a l electrolytes, s u c h as a l u m , u s e d to effect c o a g u l a t i o n i n treatment plants. F o r example, as stated earlier, i n o r d e r to separate b i t u m e n f r o m o i l sands, a significant negative charge must b e present at t h e o i l - w a t e r i n t e r face. T h i s negative charge is n e e d e d to a i d i n t h e release o f the b i t u m e n f r o m the sand matrix, a n d is also n e e d e d to p r e v e n t attachment o f the released a n d e m u l s i f i e d d r o p l e t s to c o d i s p e r s e d s o l i d particles s u c h as clays. I n fact, i n the flotation r e c o v e r y process f o r b i t u m e n the o p t i m a l p r o c e s s i n g c o n d i t i o n correlates w i t h m a x i m i z i n g the negative charge, o r zeta p o t e n t i a l , o n t h e droplets (41). O n - l i n e m e a s u r e m e n t s o f the e m u l s i f i e d b i t u m e n d r o p l e t zeta potentials c a n b e u s e d to m o n i t o r a n d c o n t r o l the c o n t i n u o u s o i l r e c o v e r y process, as i n d i c a t e d i n F i g u r e 15 (50). I n the F i g u r e 15 example, the m a x i m u m (negative) e m u l s i o n d r o p l e t zeta p o t e n t i a l a c h i e v e d was about -35 m V , w h i c h is consistent w i t h the " g o o d s t a b i l i t y " g u i d e l i n e just d e s c r i b e d . Schulze-Hardy Rule. T h e t r a n s i t i o n f r o m stable d i s p e r s i o n to ag gregation u s u a l l y occurs over a f a i r l y s m a l l range o f electrolyte c o n c e n t r a t i o n . T h i s c o n d i t i o n makes it possible to d e t e r m i n e aggregation c o n c e n t r a tions, o f t e n r e f e r r e d to as c r i t i c a l c o a g u l a t i o n concentrations ( C C C ) . T h e S c h u l z e - H a r d y r u l e s u m m a r i z e s t h e general t e n d e n c y o f the C C C to v a r y i n v e r s e l y w i t h the sixth p o w e r o f the c o u n t e r i o n charge n u m b e r (for i n d i f f e r ent electrolyte). F u r t h e r details a n d o r i g i n a l references are g i v e n i n refer ences 13 a n d 51. A p r e d i c t i o n f r o m D L V O t h e o r y c a n b e m a d e b y d e r i v i n g the c o n d i t i o n s u n d e r w h i c h V = 0 a n d dV/dH = 0. T h e result is
_9.75JBVfc rV
5
eN Az
2 A 2
(26)
Figure 15. Flot of oil recoveries versus process aid addition level from the hot water flotation processing of an oil sand in a continuous pilot plant. Also shown is the correspondence with the zeta potentials, measured on-line, of emulsified bitumen droplets in the extraction solution. (Plotted from data in reference 50.)
s h o w i n g that f o r h i g h potentials (7 1), the C C C varies i n v e r s e l y w i t h z . A s an i l l u s t r a t i o n , f o r a h y p o t h e t i c a l e m u l s i o n , e q u a t i o n 26 p r e d i c t s a C C C o f 1.18 M i n solutions o f s o d i u m c h l o r i d e . T h e c r i t i c a l c o a g u l a t i o n c o n c e n t r a tions i n p o l y v a l e n t m e t a l c h l o r i d e s w o u l d t h e n decrease as f o l l o w s :

6
Dissolved Salt NaCl CaCl

AICI3
2
1 2 3
CCC (mol/L) 1.18 0.018 0.0016
Broad Influence on Stability. I n g e n e r a l , w h e n e l e c t r i c a l surface charge is a n i m p o r t a n t d e t e r m i n a n t o f stability, i t is easier to f o r m u l a t e a v e r y stable O / W e m u l s i o n t h a n a W / O e m u l s i o n because the e l e c t r i c d o u b l e - l a y e r thickness is m u c h greater i n w a t e r t h a n i n o i l . (This c o n d i t i o n is sometimes i n c o r r e c t l y stated i n terms o f greater charge b e i n g present o n droplets i n an O / W e m u l s i o n ) . T h i s is not to say that W / O e m u l s i o n s cannot b e s t a b i l i z e d , h o w e v e r . M a n y reasonably stable o i l - f i e l d W / O e m u l s i o n s are s t a b i l i z e d b y a n o t h e r m e c h a n i s m : t h e p r o t e c t i v e action o f viscoelastic, p o s s i b l y r i g i d , films f o r m e d o n the droplets b y m a c r o m o l e c u l e s o r s o l i d particles.
36
EMULSIONS IN THE PETROLEUM INDUSTRY
K i n e t i c s . T h u s far this c h a p t e r has m o s t l y b e e n c o n c e r n e d w i t h an u n d e r s t a n d i n g o f the d i r e c t i o n i n w h i c h reactions w i l l p r o c e e d . H o w e v e r , f r o m an e n g i n e e r i n g p o i n t o f v i e w , it is j u s t as i m p o r t a n t to k n o w the rates at w h i c h s u c h reactions w i l l p r o c e e d . T w o p r i n c i p a l factors d e t e r m i n e the rate o f aggregation o f droplets i n an e m u l s i o n : the f r e q u e n c y o f d r o p l e t e n c o u n ters a n d the p r o b a b i l i t y that the t h e r m a l e n e r g y o f the d r o p l e t s is sufficient to o v e r c o m e the p o t e n t i a l energy b a r r i e r to aggregation. T h e rate o f ag gregation c a n b e g i v e n as -(dn/dt) = k n w h e r e k is the rate constant a n d is the n u m b e r o f droplets p e r u n i t v o l u m e at t i m e t. F o r - n at t = 0,
2 2 2 0
1/n = k t + l / n
2 2
(27)
D u r i n g the process o f aggregation, k m a y not r e m a i n constant. I f the energy b a r r i e r to aggregation is r e m o v e d (e.g., b y a d d i n g excess electrolyte) t h e n aggregation is d i f f u s i o n c o n t r o l l e d ; o n l y B r o w n i a n m o t i o n o f i n d e p e n d e n t droplets o r particles is present. F o r a m o n o d i s p e r s e suspen s i o n o f spheres, S m o l u c h o w s k i d e v e l o p e d an e q u a t i o n for this " r a p i d c o a g u lation" (28)
1 + 8<nDrn t
0
w h e r e r is the radius, a n d the d i f f u s i o n coefficient D = kT/(6ir^). Nowk = 4kT/(3ri), w h e r e k is the rate constant f o r d i f f u s i o n - c o n t r o l l e d aggregation. W h e n t h e r e is an energy b a r r i e r to aggregation, o n l y a f r a c t i o n IfW o f encounters l e a d to attachment. T h e variable W is the stability ratio, W = k lk . U s i n g W gives " s l o w c o a g u l a t i o n " ( h i n d e r e d ) t i m e s . I n this case, the i n t e r a c t i o n energy a n d h y d r o d y n a m i c viscous d r a g forces must b e c o n s i d e r e d (16).
2 2 2 2
F i n a l l y , particles c a n also b e b r o u g h t i n t o i n t e r a c t i o n distances b y stir r i n g or s e d i m e n t a t i o n so that the relative m o t i o n s o f t w o adjacent regions o f fluid, each c a r r y i n g particles, c a n cause p a r t i c l e e n c o u n t e r s . C o a g u l a t i o n d u e to s u c h i n f l u e n c e is c a l l e d " o r t h o k i n e t i c c o a g u l a t i o n " as d i s t i n g u i s h e d f r o m the B r o w n i a n i n d u c e d " p e r i k i n e t i c c o a g u l a t i o n " . T h e t h e o r y for o r t h o k i n e t i c c o a g u l a t i o n is m u c h m o r e c o m p l i c a t e d t h a n that f o r p e r i k i n e t i c a n d is not discussed h e r e . H o w e v e r , shear can also cause d i s p e r s i o n i f the e n e r g y i n t r o d u c e d allows the i n t e r a c t i o n energy b a r r i e r to b e o v e r c o m e . Stability to C o a l e s c e n c e . U p to this p o i n t , stability to aggregation has b e e n c o n s i d e r e d . H o w e v e r , o n c e aggregation has t a k e n p l a c e i n an e m u l s i o n , there r e m a i n s the q u e s t i o n o f stability to coalescence. U s u a l l y e m u l s i o n s m a d e b y m i x i n g t o g e t h e r two p u r e l i q u i d s are not v e r y stable. T o increase the stability, an a d d i t i o n a l c o m p o n e n t is u s u a l l y n e e d e d , a n d it f o r m s a film a r o u n d the d i s p e r s e d droplets to p r o v i d e a b a r r i e r to b o t h
1.
SCHRAMM
Basic Principles
37
aggregation a n d coalescence. A l t h o u g h n u m e r o u s agents a n d m e c h a n i s m s are effective, the a d d i t i o n a l c o m p o n e n t is f r e q u e n t l y a surfactant. S t a b i l i t y to coalescence involves the m e c h a n i c a l p r o p e r t i e s o f the i n t e r f a c i a l films. M e c h a n i c a l p r o p e r t i e s w i l l b e c o n s i d e r e d f u r t h e r i n the next section. C o n s i d e r i n g stability to b o t h aggregation a n d c o a l e s c e n c e , the factors f a v o r i n g e m u l s i o n stability c a n be s u m m a r i z e d as f o l l o w s : L o w i n t e r f a c i a l tensionlow i n t e r f a c i a l free energy makes it easier to m a i n t a i n large i n t e r f a c i a l area. M e c h a n i c a l l y strong filmthis acts as a b a r r i e r to coalescence and m a y b e e n h a n c e d b y a d s o r p t i o n o f fine solids o r o f closep a c k e d surfactant m o l e c u l e s . Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 E l e c t r i c d o u b l e - l a y e r repulsionthis r e p u l s i o n acts to p r e v e n t collisions a n d aggregation. S m a l l v o l u m e o f d i s p e r s e d phasethis reduces the f r e q u e n c y o f collisions a n d aggregation. H i g h e r v o l u m e s are possible (for c l o s e - p a c k e d spheres the dispersed-phase v o l u m e f r a c t i o n w o u l d b e 0.74), b u t i n p r a c t i c e the f r a c t i o n can even b e h i g h e r . S m a l l d r o p l e t size, i f the droplets are electrostatically o r sterically i n t e r a c t i n g . H i g h viscositythis slows the rates o f c r e a m i n g a n d coales cence. A n assessment o f e m u l s i o n stability involves the d e t e r m i n a t i o n o f the t i m e v a r i a t i o n o f some e m u l s i o n p r o p e r t y s u c h as those d e s c r i b e d i n the e a r l i e r section " P h y s i c a l C h a r a c t e r i s t i c s o f E m u l s i o n s " . T h e classical m e t h ods are w e l l d e s c r i b e d i n r e f e r e n c e 9. S o m e n e w e r approaches i n c l u d e the use o f p u l s e n u c l e a r m a g n e t i c resonance spectroscopy o r d i f f e r e n t i a l scan n i n g c a l o r i m e t r y (52).
Emulsifying Agents. O n e g e n e r a l t h e o r y o f e m u l s i o n type states that i f an e m u l s i f y i n g agent is p r e f e r e n t i a l l y w e t t e d b y one o f the phases, t h e n m o r e o f the agent c a n be a c c o m m o d a t e d at the interface i f that i n t e r face is convex t o w a r d that phase; that is, i f that phase is the c o n t i n u o u s phase. T h i s t h e o r y w o r k s for b o t h solids a n d soaps as e m u l s i f y i n g agents. F o r surfactant m o l e c u l e s it is r e f e r r e d to as B a n c r o f t ' s r u l e ; the l i q u i d i n w h i c h the surfactant is most s o l u b l e b e c o m e s the c o n t i n u o u s phase. V e r y o f t e n , mixtures o f e m u l s i f y i n g agents are m o r e effective t h a n single c o m p o n e n t s . S o m e m i x e d emulsifiers m a y f o r m a c o m p l e x at the interface a n d thus y i e l d l o w i n t e r f a c i a l t e n s i o n a n d a strong i n t e r f a c i a l film.
A s e c o n d g e n e r a l r u l e specifies that soaps o f m o n o v a l e n t m e t a l cations t e n d to p r o d u c e O / W e m u l s i o n s , b u t those o f p o l y v a l e n t m e t a l cations w i l l
38
t e n d to p r o d u c e W / O e m u l s i o n s . F i g u r e 16 illustrates the c o n c e p t . I n t h e example s h o w n , the c a l c i u m ions each c o o r d i n a t e to t w o surfactant m o l e cules that are a l i g n e d w i t h t h e i r p o l a r groups near the m e t a l i o n . T h i s c o o r d i n a t i o n forces t h e h y d r o c a r b o n tails i n t o a w e d g e l i k e o r i e n t a t i o n . T h e h y d r o c a r b o n tails i n a c l o s e - p a c k e d i n t e r f a c i a l layer are most easily a c c o m m o d a t e d i f the o i l phase is t h e c o n t i n u o u s phase. T h u s , the o r i e n t e d - w e d g e t h e o r y p r e d i c t s that t h e c a l c i u m soap w i l l p r o d u c e a W / O e m u l s i o n . F o r t h e s o d i u m soap, t h e c h a r g e d p o l a r groups o f the surfactant t e n d to r e p e l e a c h o t h e r m o r e strongly. T h i s fact, together w i t h the single c a t i o n - s u r f a c t a n t c o o r d i n a t i o n , makes i t most favorable f o r t h e p o l a r groups to b e i n t h e c o n t i n u o u s phase, a n d an O / W e m u l s i o n results. A n analogous r u l e to the o r i e n t e d - w e d g e a n d B a n c r o f t theories states that t h e l i q u i d that p r e f e r e n t i a l l y wets t h e s o l i d particles w i l l t e n d to f o r m the c o n t i n u o u s phase. T h u s i f t h e r e is a l o w contact angle ( m e a s u r e d t h r o u g h the w a t e r phase), t h e n a n O / W e m u l s i o n s h o u l d f o r m . E x c e p t i o n s o c c u r f o r each o f these rules, a n d s o m e t i m e s o n e w i l l w o r k w h e r e t h e others d o n o t . They do remain useful for making initial predictions. A n e m p i r i c a l scale d e v e l o p e d f o r c a t e g o r i z i n g s i n g l e - c o m p o n e n t o r m i x e d (usually n o n i o n i c ) e m u l s i f y i n g agents, u s i n g this p r i n c i p l e , is t h e h y d r o p h i l e - l i p o p h i l e balance o r H L B scale. T h i s d i m e n s i o n l e s s scale ranges f r o m 0 to 2 0 ; a l o w H L B (<9) refers to a l i p o p h i l i c surfactant (oil-soluble) and a h i g h H L B (>11) to a h y d r o p h i l i c (water-soluble) surfactant. I n g e n -
Figure 16. The oriented-wedge theory of emulsion type.
1.
SCHRAMM
Basic
Principles
39
e r a l , W / O emulsifiers exhibit H L B values i n t h e range o f 3 - 8 , a n d O / W emulsifiers have H L B values o f about 8 - 1 8 . E m p i r i c a l tables o f H L B values r e q u i r e d to make e m u l s i o n s o u t o f various materials have b e e n p u b l i s h e d (53). I f the value is n o t k n o w n , t h e n laboratory e m u l s i f i c a t i o n tests are r e q u i r e d , u s i n g a series o f e m u l s i f y i n g agents o f k n o w n H L B values. F o r example, to make a 1 5 % O / W e m u l s i o n o f a p a r a f f m i c m i n e r a l o i l , a set o f e m u l s i o n tests is p e r f o r m e d w i t h a series o f b l e n d s o f emulsifiers A ( H L B 4.7) a n d ( H L B 14.9): Emulsifier Blend HLB 4.7 6 8 10 12 14 14.9 Emulsion Test no emulsion no emulsion moderate emulsion stable emulsion moderate emulsion no emulsion no emulsion
100% A 87% A + 13% 68% A + 32% 48% A + 52% 28% A + 72% 6% A + 94% 100%
In this case a n H L B o f 10 is r e q u i r e d to make the O / W m i n e r a l o i l e m u l s i o n . V a r i o u s c o m p i l a t i o n s a n d equations f o r d e t e r m i n i n g e m u l s i f i e r H L B values have b e e n p u b l i s h e d (J5, 53, 54). F o r e x a m p l e , i n p o l y o x y e t h y l e n e alcohols, C H ( O C H C H ) O H , a class o f n o n i o n i c surfactants, the H L B c a n b e c a l c u l a t e d f r o m H L B = E/5, w h e r e is the p e r c e n t a g e b y mass o f ethylene oxide i n the m o l e c u l e . E x p e r i m e n t a l l y , t h e u n k n o w n H L B o f an e m u l s i f i e r c a n b e d e t e r m i n e d b y m i x i n g it w i t h an e m u l s i f i e r o f k n o w n H L B and a n o i l f o r w h i c h t h e H L B r e q u i r e d f o r e m u l s i f i c a t i o n is k n o w n . A series o f tests s u c h as just i l l u s t r a t e d i n t h e example c a n b e u s e d t o d e t e r m i n e the u n k n o w n H L B . F r o m the p r e v i o u s d e f i n i t i o n o f s p r e a d i n g i t m i g h t s e e m that i f an o i l does n o t s p r e a d o n w a t e r , t h e n i t s h o u l d b e e m u l s i f i e d i n i t , a n d v i c e versa. Ross et a l . (55) d i d , i n fact, find a c o r r e l a t i o n b e t w e e n H L B a n d the s p r e a d i n g coefficients o f o i l a n d water. T h e y f o u n d that f o r a g i v e n type o f e m u l s i o n , b o t h l o w i n t e r f a c i a l t e n s i o n a n d a negative v a l u e o f t h e a p p r o p r i ate s p r e a d i n g coefficient are necessary.
n 2 n + 1 2 2 m
A l i m i t a t i o n o f the H L B system is that o t h e r factors are i m p o r t a n t as w e l l . A l s o , t h e H L B is an i n d i c a t o r o f the e m u l s i f y i n g characteristics o f a n e m u l s i f i e r b u t n o t the efficiency o f an e m u l s i f i e r . T h u s , a l t h o u g h a l l e m u l s i fiers h a v i n g a h i g h H L B w i l l t e n d to p r o m o t e O / W e m u l s i o n s , the e f f i c i e n c y w i t h w h i c h those emulsifiers act w i l l vary c o n s i d e r a b l y f o r any g i v e n system. F o r example, usually mixtures o f surfactants w o r k b e t t e r t h a n p u r e c o m p o u n d s o f the same H L B . Just as solubilities o f e m u l s i f y i n g agents vary w i t h t e m p e r a t u r e , so does the H L B , especially f o r the n o n i o n i c surfactants. A surfactant m a y thus stabilize O / W e m u l s i o n s at l o w t e m p e r a t u r e b u t W / O e m u l s i o n s at some h i g h e r t e m p e r a t u r e . T h e t r a n s i t i o n t e m p e r a t u r e , that at w h i c h the surfactant
40
changes f r o m s t a b i l i z i n g O / W to W / O e m u l s i o n s , is k n o w n as the phase i n v e r s i o n t e m p e r a t u r e ( P I T ) . A t the P I T , the h y d r o p h i l i c a n d o l e o p h i l i c natures o f the surfactant are essentially the same (another t e r m f o r this is the H L B t e m p e r a t u r e ) . A s a p r a c t i c a l matter, e m u l s i f y i n g agents are c h o s e n so that t h e i r P I T is far f r o m the expected storage a n d use temperatures o f the d e s i r e d e m u l s i o n s . I n one m e t h o d (56) an e m u l s i f i e r w i t h a P I T o f about 50 C h i g h e r t h a n the s t o r a g e - u s e t e m p e r a t u r e is selected. T h e e m u l s i o n is t h e n p r e p a r e d at the P I T w h e r e v e r y s m a l l d r o p l e t sizes are most easily c r e a t e d . N e x t , the e m u l s i o n is r a p i d l y c o o l e d to the d e s i r e d use t e m p e r a t u r e , at w h i c h n o w the coalescence rate w i l l be slow, a n d a stable e m u l s i o n results. Protective Agents a n d Sensitization. T h e stability o f a d i s p e r s i o n c a n be e n h a n c e d (protection) o r r e d u c e d (sensitization) b y the a d d i t i o n o f m a t e r i a l that adsorbs o n t o p a r t i c l e surfaces. P r o t e c t i v e agents c a n act i n several ways. T h e y c a n increase d o u b l e - l a y e r r e p u l s i o n i f t h e y have i o n i z a b l e g r o u p s . T h e a d s o r b e d layers c a n l o w e r the effective H a m a k e r constant. A n a d s o r b e d film m a y necessitate d e s o r p t i o n b e f o r e particles can a p p r o a c h closely e n o u g h f o r v a n d e r W a a l s forces to cause attraction. I f the a d s o r b e d m a t e r i a l extends out significantly f r o m the p a r t i c l e surface, t h e n an e n t r o p y decrease c a n a c c o m p a n y p a r t i c l e a p p r o a c h (steric stabilization). F i n a l l y , the a d s o r b e d m a t e r i a l may f o r m s u c h a r i g i d film that it poses a m e c h a n i c a l b a r r i e r to d r o p l e t coalescence. O i l - f i e l d W / O e m u l s i o n s m a y be s t a b i l i z e d b y the p r e s e n c e o f a p r o t e c tive film a r o u n d the w a t e r d r o p l e t s . S u c h a film c a n be f o r m e d f r o m the asphaltene a n d r e s i n fractions o f the c r u d e o i l . W h e n d r o p l e t s a p p r o a c h each o t h e r d u r i n g the process o f aggregation, the rate o f o i l film drainage w i l l be d e t e r m i n e d i n i t i a l l y b y the b u l k o i l viscosity, b u t w i t h i n a c e r t a i n distance o f a p p r o a c h the i n t e r f a c i a l viscosity b e c o m e s i m p o r t a n t . A h i g h i n t e r f a c i a l viscosity w i l l significantly r e t a r d the final stage o f film drainage a n d p r o m o t e k i n e t i c e m u l s i o n stability. I f the films are viscoelastic, t h e n a m e c h a n i c a l b a r r i e r to coalescence w i l l be p r o v i d e d , y i e l d i n g a h i g h degree o f e m u l s i o n stability. M o r e d e t a i l e d d e s c r i p t i o n s are g i v e n i n references 26, 57, a n d 58. S e n s i t i z i n g agents can be p r o t e c t i v e agents that are a d d e d i n s m a l l e r amounts t h a n w o u l d be u s e d n o r m a l l y . S e n s i t i z i n g agents have several p o s s i b l e m e c h a n i s m s o f action. I f the additive is o p p o s i t e l y c h a r g e d to the dis p e r s e d particles, t h e n d e c r e a s e d d o u b l e - l a y e r r e p u l s i o n w i l l result. I n some k i n d s o f p r o t e c t i n g a d s o r p t i o n , a b i l a y e r is f o r m e d w i t h the o u t e r layer h a v i n g l y o p h i l i c groups exposed o u t w a r d s . A d d i t i o n o f e n o u g h a d d i t i v e to f o r m o n l y the single layer w i l l have l y o p h o b i c groups o r i e n t e d o u t w a r d w i t h a s e n s i t i z i n g effect. I f the additive is o f l o n g c h a i n l e n g t h , sometimes a b r i d g i n g b e t w e e n particles occurs a n d i n d u c e s aggregation (at h i g h e r c o n centrations p r o t e c t i v e a c t i o n takes over because the p o t e n t i a l b r i d g i n g sites become covered).
1.
SCHRAMM
Basic Principles
41
Creaming, Inversion, and Demulsification

C r e a m i n g . D r o p l e t s i n a n e m u l s i o n w i l l have s o m e t e n d e n c y to rise o r settle a c c o r d i n g to Stokes' l a w . A n u n c h a r g e d s p h e r i c a l d r o p l e t i n a fluid w i l l s e d i m e n t i f its density is greater t h a n that o f the fluid. T h e d r i v i n g f o r c e is that o f gravity; t h e resisting f o r c e is viscous a n d is a p p r o x i m a t e l y p r o p o r t i o n a l to the d r o p l e t velocity. A f t e r a short p e r i o d o f t i m e the p a r t i c l e reaches t e r m i n a l (constant) v e l o c i t y , dx/dt, w h e n t h e t w o forces are m a t c h e d . T h u s dx_2r (p -p )g
8 2 1 ( 2 g )
dt
2
9
x
w h e r e r is t h e p a r t i c l e radius, p is t h e d r o p l e t density, p is t h e external fluid density, g is t h e gravitational constant, a n d is t h e b u l k viscosity. I f t h e d r o p l e t has a l o w e r density t h a n t h e external phase, t h e n i t rises i n s t e a d (negative s e d i m e n t a t i o n ) . E m u l s i o n droplets are n o t r i g i d spheres, so they may d e f o r m i n shear flow. A l s o , w i t h the p r e s e n c e o f e m u l s i f y i n g agents at the interface, t h e droplets w i l l n o t b e n o n i n t e r a c t i n g , as is a s s u m e d i n t h e theory. T h u s , Stokes' l a w w i l l n o t strictly a p p l y a n d may u n d e r e s t i m a t e o r e v e n overestimate t h e real t e r m i n a l velocity. T h e process i n w h i c h e m u l s i o n droplets rise o r settle w i t h o u t significant coalescence is c a l l e d c r e a m i n g ( F i g u r e 17). T h i s process is n o t e m u l s i o n b r e a k i n g , b u t p r o d u c e s two separate layers o f e m u l s i o n that have d i f f e r e n t d r o p l e t concentrations a n d are usually d i s t i n g u i s h a b l e f r o m each o t h e r b y c o l o r o r opacity. T h e t e r m c o m e s f r o m t h e f a m i l i a r separation o f c r e a m f r o m raw m i l k . A c c o r d i n g to Stokes' law, c r e a m i n g w i l l o c c u r faster w h e n t h e r e is a larger density d i f f e r e n c e a n d w h e n t h e droplets are larger. T h e rate o f separation can b e e n h a n c e d b y r e p l a c i n g t h e gravitational d r i v i n g force b y a c e n t r i f u g a l field. C e n t r i f u g a l force, l i k e gravity, is p r o p o r t i o n a l to t h e mass, b u t t h e p r o p o r t i o n a l i t y constant is n o t g b u t , w h e r e is t h e angular v e l o c i t y (equal to 2 x revolutions p e r second) a n d is t h e distance o f t h e p a r t i c l e f r o m the axis o f r o t a t i o n . T h e d r i v i n g force f o r s e d i m e n t a t i o n b e comes (p - ) . B e c a u s e is s u b s t i t u t e d f o r g, o n e speaks o f m u l t i p l e s o f g, o r " g s " , i n a c e n t r i f u g e . T h e c e n t r i f u g a l acceleration i n a c e n t r i f u g e is not r e a l l y a constant t h r o u g h o u t t h e system b u t varies w i t h x. T h e actual distance f r o m t o p to b o t t o m o f a s e d i m e n t i n g c o l u m n is usually s m a l l c o m p a r e d to t h e distance f r o m t h e c e n t e r o f r e v o l u t i o n , so t h e average accelera t i o n is u s e d . T h e t e r m i n a l v e l o c i t y t h e n b e c o m e s
2 2 2 2
dx _ 2 r ( p - Pi)
2 2 2
dt
T h e p r o b l e m o f deaerated b i t u m i n o u s f r o t h p r o d u c e d f r o m t h e h o t w a t e r flotation o f b i t u m e n f r o m o i l sands c a n serve as a n i l l u s t r a t i o n . T h i s
42
Figure 17. Creaming, aggregation, and coalescence in an O/W emulsion.
f r o t h is a W / O e m u l s i o n f r o m w h i c h t h e w a t e r must b e r e m o v e d p r i o r to u p g r a d i n g a n d r e f i n i n g . A t process t e m p e r a t u r e (80 C) t h e e m u l s i o n viscos ity is s i m i l a r to that o f t h e b i t u m e n , b u t t h e density, because o f e n t r a i n e d solids, is h i g h e r . T a k i n g = 5 0 0 mPa-s (59) a n d p = 1.04 g/mL, t h e rate o f rise o f 2 0 - d i a m e t e r w a t e r droplets u n d e r gravitational force w i l l b e v e r y slow. A c c o r d i n g to e q u a t i o n 2 9 :
x
rlr = -3.05xl0" di
cm/s
ek = 96 cm/year u p w a r d dt I n a c o m m e r c i a l o i l sands p l a n t , a c e n t r i f u g e process is u s e d to s p e e d u p the separation. T h e c o n t i n u o u s centrifuges c a n operate at 2500 x g , t h e
1.
SCHRAMM
Basic Principles
43
droplets h a v i n g to travel 9 c m to reach the p r o d u c t stream. W i t h the centrif u g a l force a d d e d , a c c o r d i n g to e q u a t i o n 30, the d r o p l e t v e l o c i t y w o u l d become dx
.di.
= 2500
x dt
3
dx
l d I
= 7.63 X 1 0 "
cm/s o u t w a r d
T h i s result is 2500 x faster t h a n w i t h gravity alone, b u t the r e s i d e n c e t i m e i n the c e n t r i f u g e w o u l d have to be about 20 m i n , a n d this l e n g t h o f t i m e is not p r a c t i c a l . T o s p e e d u p the separation, n a p h t h a is a d d e d to the l e v e l o f 2 5 % . T h e n a p h t h a lowers the viscosity to about 4.5 mPa-s (59) a n d lowers the density o f the c o n t i n u o u s phase to 0.88 g/mL. N o w the w a t e r d r o p l e t s w o u l d s e d i m e n t rather than rise u n d e r gravitational force, a n d a l t h o u g h the e m u l s i o n density is m u c h r e d u c e d , the absolute value o f the density d i f f e r e n c e changes v e r y l i t t l e : = - 0 . 0 7 g/mL o r i g i n a l l y , a n d b e c o m e s = +0.09 g/mL! T h e o v e r a l l effect is to l o w e r the viscosity b y about 2 orders o f m a g n i t u d e . T h e d r o p l e t v e l o c i t y n o w b e c o m e s ( c k / d i ) = 1.1 cm/s, w h i c h yields a satisfactory residence t i m e o f about 8 s.
n
I n general, f o r g i v e n l i q u i d densities, c r e a m i n g w i l l o c c u r m o r e s l o w l y the greater the e l e c t r i c a l charge o n the droplets a n d the h i g h e r the e m u l s i o n viscosity. A l t h o u g h a d i s t i n c t process, c r e a m i n g does p r o m o t e coalescence b y i n c r e a s i n g the d r o p l e t c r o w d i n g a n d h e n c e the p r o b a b i l i t y o f d r o p l e t droplet collisions. Inversion. I n v e r s i o n refers to the process i n w h i c h an e m u l s i o n s u d d e n l y changes f o r m , f r o m O / W to W / O , or v i c e versa. T h i s process was e n c o u n t e r e d i n the example o f c h a n g i n g e m u l s i o n viscosity g i v e n i n the e a r l i e r section, " P h y s i c a l C h a r a c t e r i s t i c s o f E m u l s i o n s " , subsection " B u l k V i s c o s i t y P r o p e r t i e s " ( F i g u r e 6). T h e m a x i m u m v o l u m e f r a c t i o n possible f o r an i n t e r n a l phase m a d e u p o f u n i f o r m , i n c o m p r e s s i b l e spheres is 74%. Although emulsions with a higher internal volume fraction do occur, usually i n v e r s i o n occurs w h e n the i n t e r n a l v o l u m e f r a c t i o n exceeds some value reasonably close to = 0.74. O t h e r factors have a b e a r i n g as w e l l , o f course, i n c l u d i n g the nature a n d c o n c e n t r a t i o n o f emulsifiers a n d p h y s i c a l i n f l u ences s u c h as t e m p e r a t u r e or the a p p l i c a t i o n o f m e c h a n i c a l shear. T h e exact m e c h a n i s m o f i n v e r s i o n r e m a i n s u n c l e a r , a l t h o u g h o b v i o u s l y some processes o f c o a l e s c e n c e a n d d i s p e r s i o n are i n v o l v e d . I n the r e g i o n o f the i n v e r s i o n p o i n t m u l t i p l e e m u l s i o n s m a y be e n c o u n t e r e d . T h e process is also not always exactly r e v e r s i b l e . T h a t is, hysteresis m a y o c c u r i f the i n v e r s i o n p o i n t is a p p r o a c h e d f r o m d i f f e r e n t sides o f the c o m p o s i t i o n scale. F i g u r e 18 shows the i r r e v e r s i b l e i n v e r s i o n o f a d i l u t e d b i t u m e n - i n - w a t e r e m u l s i o n b r o u g h t about b y the a p p l i c a t i o n o f shear (60).
44
Low Shear
Moderate Shear
High Shear
\ O/W
Remains W/O Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001
\ ^ Inverts to W/O
-y
1 1 1
S /
Finer Droplets
Shear R t ae
Figure 18. Example of the shear-induced inversion of an emulsion of diluted bitumen in water. (Reproduced with permission from Syncrude Canada Limited.
Demulsification
(Emulsion Breaking).
T h e stability o f a n
e m u l s i o n is o f t e n a p r o b l e m . D e m u l s i f i c a t i o n involves t w o steps. F i r s t , a g g l o m e r a t i o n o r coagulation o f droplets m u s t o c c u r . T h e n , t h e agglomer ated droplets must coalesce. O n l y after these t w o steps c a n c o m p l e t e phase separation o c c u r . E i t h e r step c a n b e rate d e t e r m i n i n g for the d e m u l s i f i c a t i o n process. A t y p i c a l W / O p e t r o l e u m e m u l s i o n f r o m a p r o d u c t i o n w e l l m i g h t c o n t a i n 6 0 - 7 0 % water. S o m e o f this (free water) w i l l r e a d i l y settle out. T h e rest (bottom settlings*) r e q u i r e s s o m e k i n d o f specific e m u l s i o n treat ment. T h e first step i n systematic e m u l s i o n b r e a k i n g is t o c h a r a c t e r i z e t h e e m u l s i o n to be b r o k e n i n terms o f its nature (O/W o r W / O ) , the nature o f the two phases, a n d t h e sensitivity o f the emulsifiers. O n t h e basis o f s u c h a n evaluation, a c h e m i c a l a d d i t i o n c o u l d b e m a d e t o n e u t r a l i z e the effect o f the e m u l s i f i e r , f o l l o w e d b y m e c h a n i c a l means t o c o m p l e t e the phase separation. F o r example, b u t t e r results f r o m t h e c r e a m i n g , b r e a k i n g , a n d i n v e r s i o n o f e m u l s i f i e d droplets i n m i l k . It follows d i r e c t l y f r o m the p r e v i o u s considerations o f e m u l s i o n stability that i f an e m u l s i o n is s t a b i l i z e d b y e l e c t r i c a l r e p u l s i v e forces, t h e n d e m u l s i f i * Hence the field term "bottom settlings and water", or BS&W, used to characterize petroleum
samples. {See also the Glossary.)
1.
SCHRAMM
Basic Principles
45
c a t i o n c o u l d be b r o u g h t about b y o v e r c o m i n g o r r e d u c i n g these forces. I n this context the a d d i t i o n o f electrolyte to an O / W e m u l s i o n c o u l d b e u s e d to achieve the c r i t i c a l c o a g u l a t i o n c o n c e n t r a t i o n , i n a c c o r d w i t h the S c h u l z e H a r d y r u l e . S i m i l a r l y , d e m u l s i f y i n g agents, d e s i g n e d to r e d u c e e m u l s i o n stability b y d i s p l a c i n g o r d e s t r o y i n g the effectiveness o f p r o t e c t i v e agents, c a n b e a p p l i e d . A n example is antagonistic a c t i o n , that is, a d d i t i o n o f an O / W p r o m o t e r to b r e a k a W / O e m u l s i o n (see the e a r l i e r section " P r o t e c t i v e A g e n t s a n d Sensitization")- T h e s e considerations are d i s c u s s e d i n f u r t h e r d e t a i l i n C h a p t e r 9. A p a r t f r o m the a f o r e m e n t i o n e d c h e m i c a l treatments, a variety o f p h y s i cal m e t h o d s are u s e d i n e m u l s i o n b r e a k i n g . T h e s e p h y s i c a l m e t h o d s are a l l d e s i g n e d to accelerate c o a g u l a t i o n a n d coalescence. F o r example, o i l - f i e l d W / O e m u l s i o n s m a y b e t r e a t e d b y some o r a l l o f settling, h e a t i n g , e l e c t r i c a l d e h y d r a t i o n , c h e m i c a l treatment, c e n t r i f u g a t i o n , a n d filtration. T h e m e c h a n i c a l m e t h o d s , s u c h as c e n t r i f u g i n g or filtering, r e l y o n i n c r e a s i n g the c o l l i s i o n rate o f d r o p l e t s a n d a p p l y i n g an a d d i t i o n a l force that drives coales c e n c e . A n increase i n t e m p e r a t u r e w i l l increase t h e r m a l m o t i o n s to e n h a n c e the c o l l i s i o n rate, a n d also r e d u c e viscosities ( i n c l u d i n g i n t e r f a c i a l viscosity), and thus increase the l i k e l i h o o d o f coalescence. I n the extremes, v e r y h i g h temperatures w i l l cause d e h y d r a t i o n d u e to e v a p o r a t i o n , a n d f r e e z e - t h a w cycles w i l l break some e m u l s i o n s . E l e c t r i c a l m e t h o d s m a y i n v o l v e e l e c t r o phoresis o f o i l d r o p l e t s , c a u s i n g t h e m to c o l l i d e , to b r e a k O / W e m u l s i o n s . W i t h W / O e m u l s i o n s , the m e c h a n i s m involves d e f o r m a t i o n o f w a t e r d r o p lets, because W / O e m u l s i o n s are essentially n o n c o n d u c t i n g e m u l s i o n s . H e r e the e l e c t r i c field causes an increase i n the d r o p l e t area a n d disrupts the i n t e r f a c i a l film. I n c r e a s e d d r o p l e t contacts increase the coalescence rate a n d t h e r e b y break the e m u l s i o n . M o r e details o n the a p p l i c a t i o n o f these m e t h ods i n large-scale c o n t i n u o u s processes are g i v e n i n C h a p t e r 10.
List of Symbols
a A
s
area p e r a d s o r b e d m o l e c u l e available area o f surface .sp 0.2 H a m a k e r constant a constant (3.93 1 0 A~Y )
39 2 s
C
{
s o l u t i o n c o n c e n t r a t i o n o f the surfactant ( M ) i n d i v i d u a l i o n concentrations d i f f u s i o n coefficient t e r m i n a l (constant) v e l o c i t y (in c r e a m i n g ) e l e m e n t a r y e l e c t r o n i c charge gravitational constant distance separating s p h e r i c a l e m u l s i o n droplets i o n i c strength
c D x/dt e g H I
46 I I I
0
i n t e n s i t y o f i n c i d e n t l i g h t b e a m (in l i g h t - s c a t t e r i n g experiments) i n t e n s i t y o f l i g h t scattered (in l i g h t - s c a t t e r i n g experiments) intensity o f t r a n s m i t t e d b e a m o f l i g h t (in l i g h t - s c a t t e r i n g e x p e r i ments) B o l t z m a n n constant rate constant rate constant for d i f f u s i o n - c o n t r o l l e d aggregation l e n g t h o f p a t h t h r o u g h sample (in l i g h t - s c a t t e r i n g experiments) n u m b e r o f moles; n u m b e r o f d r o p l e t s p e r u n i t v o l u m e at t i m e t n u m b e r o f droplets p e r u n i t v o l u m e at t i m e t = 0
A
k k k I n
2
N N Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001
Avogadro's number capillary number p r e s s u r e , pressure i n phase A , pressure i n phase c a p i l l a r y pressure radius o f s m a l l d r o p l e t s p o r e radius radius o f s p h e r i c a l droplets also u s e d as the gas constant principal radii of curvature time absolute t e m p e r a t u r e t e m p e r a t u r e , t e r m e d the K r a f f t p o i n t , at w h i c h solubilities o f surfactants show a s t r o n g increase d u e to m i c e l l e f o r m a t i o n v e l o c i t y o f d i s p l a c i n g fluid total i n t e r a c t i o n energy attractive energy f o r s p h e r i c a l d r o p l e t s r e p u l s i v e energy f o r s p h e r i c a l d r o p l e t s stability ratio distance f r o m d r o p l e t at w h i c h i n t e n s i t y o f scattered l i g h t is taken (in l i g h t - s c a t t e r i n g e x p e r i m e n t ) c o u n t e r i o n charge n u m b e r individual ion-charge numbers
> PB F r r R
c p
R R t T
l K
V V V W z
Greek a , a , a 7
0 x 2
7 7 T
s
e m p i r i c a l constants i n equations d e s c r i b i n g e m u l s i o n viscosity o i l - w a t e r i n t e r f a c i a l t e n s i o n also u s e d as a t e r m i n the r e p u l s i v e energy expression for s p h e r i c a l d r o p l e t s shear rate surface t e n s i o n surface excess o f surfactant distance f r o m d r o p l e t surface to S t e r n p l a n e permittivity zeta p o t e n t i a l viscosity
e ]
1.
SCHRAMM
Basic Principles
47
i n t r i n s i c viscosity viscosity o f c o n t i n u o u s phase apparent viscosity d i f f e r e n t i a l viscosity r e d u c e d viscosity relative viscosity specific increase i n viscosity / Kc
VD
%ed %el
contact angle o f a n o i l - w a t e r interface i n contact w i t h a s o l i d surface d o u b l e - l a y e r thickness c o n d u c t i v i t y o f c o n t i n u o u s phase c o n d u c t i v i t y o f d i s p e r s e d phase conductivity o f emulsions w a v e l e n g t h o f l i g h t (in l i g h t - s c a t t e r i n g e x p e r i m e n t ) electrophoretic mobility e x p a n d i n g pressure (surface pressure) external fluid density d r o p l e t density charge density surface charge density turbidity shear stress y i e l d stress dispersed-phase v o l u m e f r a c t i o n potential surface p o t e n t i a l angular v e l o c i t y
Pi
2
Acknowledgments
I t h a n k E d d y Isaacs ( A l b e r t a R e s e a r c h C o u n c i l ) a n d K a r i n M a n n h a r d t (Pe t r o l e u m R e c o v e r y Institute) f o r v e r y h e l p f u l discussions a n d suggestions r e g a r d i n g the m a n u s c r i p t . V a l u a b l e suggestions o f f e r e d b y the external ref erees are also gratefully a c k n o w l e d g e d .
References
1. Martinez, A . R. In The Future of Heavy Crude and Tar Sands; Meyer, R. F . ; Wynn, J. C . ; Olson, J. C . , Eds.; U N I T A R : N e w York, 1982; pp xvii-xviii. 2. Danyluk, M.; Galbraith, B.; Omana, R. In The Future of Heavy Crude and Tar Sands; Meyer, R. F.; Wynn, J. C . ; Olson, J. C . , Eds.; U N I T A R : New York, 1982; pp 3-6.
American Chemical Society Library

1155 16th St., N.W. In Emulsions; D.C. 20036 Washington,Schramm, L.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1992.
48
3. Khayan, M . In The Future of Heavy Crude and Tar Sands; Meyer, R. F.; Wynn, J. C . ; Olson, J. C . , Eds.; U N I T A R : New York, 1982; pp 7-11. 4. Becher, P. Emulsions: Theory and Practice, 2nd E d . ; A C S Monograph Series 162; American Chemical Society: Washington, D C , 1966. 5. Sumner, C . G . Clayton's The Theory of Emulsions and Their Technical Treat ment, 5th E d . ; Blakiston: New York, 1954. 6. Encyclopedia of Emulsion Technology; Becher, P., E d . ; Dekker: N e w York, 1983; V o l . 1. 7. Encyclopedia of Emulsion Technology; Becher, P., E d . ; Dekker: N e w York, 1985; V o l . 2. 8. Encyclopedia of Emulsion Technology; Becher, P., E d . ; Dekker: N e w York, 1988; V o l . 3. 9. Lissant, . J. Demulsification: Industrial Applications; Surfactant Science Se ries 13; Dekker: N e w York, 1983; V o l . 13. 10. Micellization, Solubilization, and Microemulsions; Mittal, K . L . , E d . ; Plenum: New York, 1977; Vols. 1 and 2. 11. Macro- and Microemulsions; Shah, D . O., E d . ; A C S Symposium Series 272; American Chemical Society: Washington, D C , 1985. 12. Osipow, L . I. Surface Chemistry Theory and Industrial Applications; Reinhold: New York, 1962. 13. Ross, S.; Morrison, I. D . Colloidal Systems and Interfaces; Wiley: New York, 1988. 14. Colloid Science; Kruyt, H. R., E d . ; Elsevier: Amsterdam, Netherlands, 1952; V o l . 1. 15. Griffin, W . C . In Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed.; Interscience: New York, 1965; V o l . 8, pp 117-154. 16. Shaw, D . J. Introduction to Colloid and Surface Chemistry, 3rd ed.; Butterworths: London, 1981. 17. Microemulsions Theory and Practice; Prince, L . M., E d . ; Academic Press: New York, 1977. 18. Neogi, P. In Microemulsions: Structure and Dynamics; Friberg, S. E . ; Bothorel, P., Eds.; CRC Press: Boca Raton, FL, 1987; pp 197-212. 19. Poettmann, F . H . In Improved Oil Recovery; Interstate Compact Commission: Oklahoma City, O K , 1983; pp 173-250. 20. Bansal, V. K.; Shah, D . O. In Microemulsions: Theory and Practice; Prince, L . M., E d . ; Academic Press: New York, 1977; pp 149-173. 21. Schramm, L . L.; Novosad, J. J. Colloids Surf. 1990, 46, 21-43. 22. Whorlow, R. W . Rheological Techniques; Wiley: New York, 1980. 23. Van Wazer, J. R.; Lyons, J. W.; K i m , K. Y.; Colwell, R. E . Viscosity and Flow Measurement; Wiley: New York, 1963. 24. Fredrickson, A . G . Principles and Applications of Rheology; Prentice-Hall: E n glewood Cliffs, N J , 1964. 25. Schramm, L . L . J. Can. Pet. Technol. 1989, 28, 73-80. 26. Malhotra, A . K . ; Wasan, D . T. In Thin Liquid Films; Ivanov, I. B., E d . ; Surfac tant Science Series 29; Dekker: New York, 1988; pp 829-890. 27. Harkins, W . D . ; Alexander, A . E . In Physical Methods of Organic Chemistry; Weissberger, ., E d . ; Interscience: New York, 1959; pp 757-814. 28. Padday, J. F . In Surface and Colloid Science; Matijevic, E . , E d . ; WileyInterscience: N e w York, 1969; V o l . 1, pp 101-149. 29. Miller, C . .; Neogi, P. Interfacial Phenomena Equilibrium and Dynamic Ef fects; Dekker: N e w York, 1985.
1. 30.
SCHRAMM
Basic
Principles
49
31. 32. 33. 34. 35. 36. 37. Downloaded by 190.37.12.18 on April 8, 2012 | http://pubs.acs.org Publication Date: May 5, 1992 | doi: 10.1021/ba-1992-0231.ch001 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57.
58. 59. 60.
Cayias, J. L.; Schechter, R. S.; Wade, W . H. In Adsorption at Interfaces; Mittal, K. L . , E d . ; A C S Symposium Series 8; American Chemical Society: Washington, D C , 1975; pp 234-247. Adamson, A . W . Physical Chemistry of Surfaces, 4th E d . ; Wiley: N e w York, 1982. Lake, L . W . Enhanced Oil Recovery; Prentice-Hall: Englewood Cliffs, N J , 1989. Rosen, M . J. Surfactants and Interfacial Phenomena, 2nd ed.; Wiley: N e w York, 1989. Industrial Applications of Surfactants; Karsa, D . R., E d . ; Royal Society of Chemistry: London, 1987. Anionic Surfactants: Physical Chemistry of Surfactant Action; Lucassen-Reynders, E . H., E d . ; Dekker: New York, 1981. Ross, S. J. Phys. Colloid Chem. 1950, 54, 429-436. Currie, C . C . In Foams; Bikerman, J. J., E d . ; Reinhold: N e w York, 1953; pp 297-329. Takamura, K . Can. J. Chem. Eng. 1982, 60, 538-545. Takamura, K . ; Chow, R. S. J. Can. Pet. Technol. 1983, 22, 22-30. Schramm, L . L.; Smith, R. G.; Stone, J. A . AOSTRA J. Res. 1984, 1, 5-14. Schramm, L . L.; Smith, R. G . Colloids Surf. 1985, 14, 67-85. Schramm, L . L.; Smith, R. G . Can. J. Chem. Eng. 1987, 65, 799-811. Schramm, L . L.; Smith, R. G . AOSTRA J. Res. 1989, 5, 87-107. Smith, R. G . ; Schramm, L . L . Fuel Proc. Technol. 1989, 23, 215-231. Verwey, E . J. W . ; Overbeek, J. T h . G . Theory of the Stability of Lyophobic Colloids; Elsevier: New York, 1948. Hunter, R. J. Zeta Potential in Colloid Science; Academic Press: N e w York, 1981. James, A . M . In Surface and Colloid Science; Good, R. J.; Stromberg, R. R., Eds.; Plenum: New York, 1979; V o l . 11, pp 121-186. Riddick, T. M . Control of Stability Through Zeta Potential; Zeta Meter: N e w York, 1968. OBrien; White, L . R. J. Chem. Soc. Faraday 2 1978, 74, 1607-1626. Schramm, L . L . ; Smith, R. G. Canadian Patent 1,265,463, February 6, 1990. van Olphen, H . An Introduction to Clay Colloid Chemistry, 2nd E d . ; Wiley: New York, 1977. Cavallo, J. L.; Chang, D . L. Chem. Eng. Prog. 1990; 86, 54-59. The HLB System; I C I United States, Inc. (now I C I Americas, Inc.): Wilmington, D E , 1976. McCutcheons Emulsifiers and Detergents; M C Publishing C o . : G l e n Rock, N J , 1990; Vol. 1. Ross, S.; Chen, E . S.; Becher, P.; Ranauto, H . J. J. Phys. Chem. 1959, 63, 1681. Shinoda, K . ; Saito, H. J. Colloid Interface Sci. 1969, 30, 258-263. Cairns, R. J. R.; Grist, D . M.; Neustadter, E . L . In Theory and Practice of Emulsion Technology; Smith, A . L., E d . ; Academic Press: N e w York, 1976; pp 135-151. Jones, T. J.; Neustadter, E . L.; Whittingham, K . P. J. Can. Pet. Technol. 1978, 17, 100-108. Schramm, L . L.; Kwak, J. C . T. J. Can. Pet. Technol. 1988, 27, 26-35. Schramm, L . L . ; Hackman, L . P., unpublished results.
R E C E I V E D for review December 18, 1990. A C C E P T E D revised manuscript A p r i l 26, 1991.

Chapter 1

Diunggah oleh

Informasi Dokumen

Deskripsi Asli:

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Chapter 1

Diunggah oleh

Hak Cipta:

Format Tersedia

1

3 Density Range (kg/m ), at 15.6 C

<934 934-1000 > 1000 >1000

Emulsions as Colloidal Systems

Physical Characteristics of Emulsions

Conductivity can be used to distinguish O/W f r o m

the d i s p e r s e d phase ( K ) is m u c h s m a l l e r t h a n that o f t h e c o n t i n u o u s phase

w h e r e is the dispersed-phase v o l u m e f r a c t i o n . If, o n t h e o t h e r h a n d , t h e c o n d u c t i v i t y o f t h e d i s p e r s e d phase (#c ) is m u c h greater t h a n that o f t h e

Bulk Viscosity Properties.

nRed = Tjsp/C nRei = / T o = viscosity of the pure solvent or dispersion | medium

Volume Fraction of Oil

Properties of the Interfaces

(16) examples are given by

Table III. Surfactant Classifications ^

Anionic CH (CH ) CO<XNa CH3(CH )iiS0 ~Na CH (CH ) C6H S03~Na

N a starate N a dodecyl sulfate N a dodecyl benzene sulfonate

Polyoxyethylene alcohol Alkylphenol ethoxylate

CH i(OCH2CH ) OH C Hi9-C H -(OCH CH ) OH

C H CONH(CH ) N (CH )2CH COO"

Lauramidopropyl betaine Cocoamido-2-hydroxypropyl sulfobetaine

K r a f f t p o i n t , m a x i m u m r e d u c t i o n i n surface o r i n t e r f a c i a l t e n s i o n occurs at the C M C because n o w the C M C d e t e r m i n e s the surfactant m o n o m e r c o n centration.

m o b i l e part o f the e l e c t r i c d o u b l e layer is s h e a r e d away f r o m t h e i n n e r l a y e r

S m o l u c h o w s k i t h e o r y . F o r large d r o p l e t s w i t h " t h i n " e l e c t r i c d o u b l e layers, m e a n i n g droplets f o r w h i c h > 100,

T h e s e theories are d i s c u s s e d i n m o r e d e t a i l i n r e f e r e n c e s 14 a n d 50. W i t h these relations zeta potentials c a n b e c a l c u l a t e d f o r m a n y p r a c t i c a l

w h e n t w o c h a r g e d surfaces a p p r o a c h each o t h e r a n d t h e i r e l e c t r i c d o u b l e layers o v e r l a p . T h e r e p u l s i v e energy, V , f o r s p h e r i c a l d r o p l e t s is g i v e n

w h e r e t h e spheres have radius r a n d are separated b y distance , is a constant (3.93 1 0

exp [zeijj(S) / 2kT] - 1 exp[%?i/<S)/2fcT] + l Dispersion Forces,

Dissolved Salt NaCl CaCl

CCC (mol/L) 1.18 0.018 0.0016

EMULSIONS IN THE PETROLEUM INDUSTRY

EMULSIONS IN THE PETROLEUM INDUSTRY

Figure 16. The oriented-wedge theory of emulsion type.

EMULSIONS IN THE PETROLEUM INDUSTRY

Creaming, Inversion, and Demulsification

T h e p r o b l e m o f deaerated b i t u m i n o u s f r o t h p r o d u c e d f r o m t h e h o t w a t e r flotation o f b i t u m e n f r o m o i l sands c a n serve as a n i l l u s t r a t i o n . T h i s

EMULSIONS IN THE PETROLEUM INDUSTRY

Figure 17. Creaming, aggregation, and coalescence in an O/W emulsion.

ek = 96 cm/year u p w a r d dt I n a c o m m e r c i a l o i l sands p l a n t , a c e n t r i f u g e process is u s e d to s p e e d u p the separation. T h e c o n t i n u o u s centrifuges c a n operate at 2500 x g , t h e

EMULSIONS IN THE PETROLEUM INDUSTRY

samples. {See also the Glossary.)

EMULSIONS IN THE PETROLEUM INDUSTRY

American Chemical Society Library

Advances in Chemistry; American Chemical Society: Washington, DC, 1992.

EMULSIONS IN THE PETROLEUM INDUSTRY

58. 59. 60.

R E C E I V E D for review December 18, 1990. A C C E P T E D revised manuscript A p r i l 26, 1991.

Anda mungkin juga menyukai