CA1153272A - Method for breaking petroleum emulsions and the like using micellar solutions of thin film spreading agents comprising polyepoxide condensates of resinous polyalkylene oxide adducts and polyether polyols - Google Patents

Abstract

ABSTRACT OF THE INVENTION
The invention relates to the use of a homogeneous, micellar solution of a water-insoluble thin film spreading agent comprising polyepoxide condensates of resinous polyalkylene oxide adducts and polyether polyols for the breaking of petroleum emulsions, and the like, the micellar solution comprising: (a) from between about 5% and about 75% by weight of said polyepoxide condensate;
(b) from between about 2% and about 30% by weight of a hydrotropic agent; (c) from between about 2% and about 30% by weight of an amphipathic agent; and (d) from between about 15% and about 90%
by weight of water.

Description

~:;L53272 1 B~CKG.~OUND OF TH~ INVENTION
__ ____ _ 1. FIE~]) OF THE INVENTION: The invention'relates to the use of a micellar so.lution of a thin film spreading agent,com-prising polyepoxide condensates of resinous polyalkylene oxide adducts and 'polyet~er polyols.for breaking or preventing petroleum emulsions. More specifically, a'll or a substantial part:of the organic solvents formérl.y required for preparation of liquid solutions of this.interf'acially ~active compound.
. 2. DESCRIPTION OF THE PRIOR ART: One of the principal uses ~10 of the present composition is in the breaking of petroleum emulsions ` to permit the separation thereof into two bulk phases. Much of the~crude petroleum~oil procluced throughout ~th~e world is accompan-ied~by~some:wat,er or~brine which~originates in~or adjacent to the geol;o~gical:formation from:~which' the oll is pro~dùced. The amount l$,',~ o:~aqueous~phase accompany~ing~the oi~l:may.vary from a trace to a very~;làrge~percentage~,of the total' fluid p:roduc:ed. Due to the :-,n`,atur~al~occurrence in-most:petroleu.m of :oil-soluble~or dispers.ible `' ~ idg~;~ag~ts~ much~o~f:the~aqueous~phase~ produced~with oil ~, ~ lèd~:the~r ~ ~ orming.stable~water-in-oil emulsions,~ .
~he L~iter~ture 'Gon~a~in.s~numerous~references to s~uch emulsions, esul,:~ting~:~rom::~the:ir'~occùrrence~ ;and tXe methods employ~ed~:~to~br~eak:them:and separate~salable ~etroleum. See, for "exa~pl~e~ "The'~'rechnology~of. Re~olvin~ Pet~oleum Emulsions`' by L~
nso'n~and~:. W~ S'~ el, p. ~535 et seq~i ~Colloid ChemLs ry 9 ~ ~VoL-VI~, ~ by ~ o~è Ale~ander, R,hein~old Publishing Corp., New "a ~ ~" ~ érf~acia~l Films~.,A~ff~ecting~the~Stability of Em s~;~ ~ s",'~'¢~s,;~M.~.~ Blair, Jr.~in~Chemistry and .,;InJus ~;y:(Lo~d,o,n),~ et~se :~( 60).
'y de ~ ~s' er;~' é:~to~` e water-~soluble~'soa~ps,~Twit~chell~reagents~, and~sulonated glycerides.
'Thes~è~pr'oduc't's'~wer~e:~readily~co~pounded with~water to form easily 1::

' ~lS3~72 l pulnlable l;(lu;ds and w(fre c!~nvellifallt.ly applied by ~lmping into flow linfes at t:he well head or by washillfg down the casing annulus with ~a~er to commingle with well fluids prior to their'flow to the surface. These products, however, were effective only at relat1vely high concentrations and their use adf1ed subs~antially to the cost of production.
Some ti.me ago, it ~as discovered that certain lightly sul-fonated oils, acetylated caster oils and various polyesters, all of which were ;nso~.uble in ~ater but soluble i.n alcohols and aromatic hydrocarbons, were much more effective in breakin.g .
:~ emulsions. Accordingly,'essentially all commercial'demulsifier.
~ affevelop~ent has led to production of agents which are insoluble f~ in ~oth water and petroleum oils-~lnd have other properties.to be descr1bed below which cause~-tlem to~spr~ad aL oi1-water inter-15~ ~aces to form~;very th1n,~mobile ~11ms which displace any emulsify-ing agent pr.esent in~the~ o'il to:allow coalescence of dispersed ; wat~er droplets. '~Genera11y,~ such~interfacially:active compounds are~hereafter~-refefrred':to a~s Thin~Film Spread'ing Agents', or '`T~SA's"
In.~:the~past, these:~have~.had' to~b~e compounded'w1th and dissolved in~ al~ohol~s~or:~highly aromat1c hydrocarbon so~lvents in order to roduc~e:re~adil;y~applied~:liquid~:f^ompcfsitions. A~wide variety of su~ch c~ompo;sitions are required ~o trea~ the many di~erent emul-~ s~icns~;enc~untered throu ~f~Ut the world..f~
Wh~i1e:pré~sent:~TFSA;compos~i~tions:are hi~,hly effective, bf~ing, p.erhaps~ up~to.'fLfty~to-a~hun~dred~tLmes more eff~ctive per unit vo1ume~ than ~he ;ori~lna~ water-:soluble demulsiflers, they suffer .~ s~er`~ous:~pra~ct1~eal~de~1c~1encLes:~:because o~ their solubility.charac-te~ist;i~cfi~ .FQ'r~é'xample,~alc~oho1s and the aromatic hydroc.arbons, which~are required~-~for~pP'epara~tion:of~liquid, pumpable compositions, 3~0~ are~qulte~expen~si~e,~todqy~approaching in cost~that of the active .demul:sifier 'in~edient its~elf~. Further, such:solvents are flam-.:.~,.~: : :
,~, . . . - ., .
~f ~ ~ "
:. ,1 . .

' ~15327Z

1 m~ble ~nd ~ s clc~;~te s.~fet~l plo~le~ns ;~ en~ ol-e ex~-ense in ' shipping, s~or;ng and use. The low flash point fl~mmability can - be improved by using high boiling aromatic solvents, but these ~re incrcasin~ly rare, e~pensive an~ dan~el-ous from the standpoint of carcinogenicity and ~erm~to]ogical effects.
Still urther, present'demulsifiers cannot generally be used-in a subterranean oil or gas well, in~ection we'll, or the'like, since they cannot be washed down with either water ~or brine) or a portiort of the produced oil, and, being viscous liquids which are required in very small amounts, they cannot be reliably and .
continuously delivered several thousand feet down at the fluid level in a typical well withoùt use o~ elab~orate and expensive delivery means.
' ; O~her appllcations;of l'FSA compositLons woul~ be acilita~ed 15~ ~ if they were readily soluble or dispersible in~water. For example, much~heavy', vlscous~oil~ls~produced in the United State's by steam inJe~ction~procedur~es.~Typically, wet' steam is inject`ed into the ol~l produc~ing~;str~ata~for several~weeks in order to heat'the oil, lower~ t~s vlsco~s~ity~and~increa~se~r~eservoir energy. Steam injec-~ io~ is~then stopped~and~oil~i~s~fl~owed~or pumped from the bore-hole which~was~used for~'~st~eam in~ection. Much of the water resulting from~condensation of~the steam is also pioduced w~h the~o~il in emulsi~fied form. ~Since emulsions are more viscou~
th'an~the~external~phase~at~the~same tempera~ure~, and thus create increased~resistànce to~low~,~ productivity~of the steamed wells c~an'be~impra~èd by ~nj`èc'tin~a~`~waL~or-soluble demulslfier into the ~''~ wet~st;eam during the~steam inject~ion period ~o`prevent emulsion or~ ion,~S ,~ o~ex Ie,~ .S~.~Patent 3,39;6,~92, dated April , 1966,~to~F.~;D.~ Mu~g;ee.; At~pres~est, the requirement o~ water 3~0~ solubilit~y~sériously limits~the~choice of d~emulsifiers for use in ste~am or~water~injection to the~relatively;inefficient compositions ~ " ~ . :- ` . .
~ j . . .
, ~ ~ ' , .

115327'2 As disclosed in my co-pending Canadian applications, Serial Number 353,251, filed June 3/80 and entitled "Metho~ o~ Recovering Petroleum From A Subterranean Reservoir Incorporating A Polyether Polyol", Serial Number 353,232, filed June 3, 1980, and entitled "Method of Recovering Petroleum From A Subterranean Reservoir Incorporating Resinous Polyalkylene Oxide Adducts", Serial Number 353,258, filed June 3, 1980, and entitled "Method of Recovering Petroleum From A Subterranean Reservoir Incorporting An Acylated Polyether Polyol", and Serial Number 353,233, iled June 3, 1980, and entitled "Method of Recovering Petroleum From A
Subterranean Reservoir Incorporating Polyepoxide Condensates Of Resinous Polyalkylene Oxide Adducts And Polyether Polyols", TFSA's are useful in processes.for enhanced recovery of petroleum.
U~sed in such pro~cess~es ~involving displacement of residual oil by 15 ~ ~ ;aqueous~solut~ions,:polymer solutlons and other a~ueous systems, ;these~agents~act to increase ~the amount of oil recovered. Such act~on posslb~ly~arises from their ability to further water wetting of reservolr~rock~ e~ssen ~the~vls~cosity of~the oil-water: inter-'faciai ~l,ayèr~ ~and~promote' ~coalescence~of~dispersed droplets~ of ér~ water~or~oil~in~the~other~phase~
By`use~o~the present~aq éous micellar~solutioDs~, the intro-duc~tion~of~TFSA ~1nto~aqueous~disp1acement or flooding~ flUid5 iS
gr~e:atly f!acilî~ated. ~ In~ ad~d~ition, the present micellar solutions, ;.per:,~se, ~or in:~:cQmbinaticn with other components, can be used as cbe ~l o d L~ gent ~ or~ as ~ pretreating ha~k or ~lue ahcad of O~:her~ appli~Gati~ons~for-the~pr~e~sent:::TFSA~:micellar solutiQns in-ude~heir u5e as~ loecùlatio~aids ~for~finely ground hematite and :wag~e ~ ~orè~S durine;the~de$1 ~ ing~step~o~ore ~eneficiation, as ao~ additiYes~fo~ ~impr~ovlne~the~ail;~re~-oval and detergent action: o~

cl~eaning~composit~ions~and~detergents designed~ for use :on polar ~ ~-l ~ m.~terials, for ~lle im~rovc~n(l~t o~ solvcnt ext~-acLic~n processes such'as tbose used in extraction of antib;otic pl-cd~lcts from aqueoùs fermentation broths with'organic solvents, for the improve-ment o~ efficiency and phase separation in the purification and concentration of metals by solvcnt extraction with organic solu-tions of metal colnplex-foL~ing agents, and as assistants to improve the wetting and dying of natural and synthetic fibers and for otller pL-occsses~normally involving the in.te~-f~ce'be~een suraces of differing polarity or wetting characteristics.
10 - ` ` ' ' ' : SUMMARY OF THE INVENT~ON
. A primary object of'the present invent~.on is to provide aqueous, li~uid compositlons of these TFSA's having new and` '.
' useful characLer'istic$ which sllow~production o: petroleum emulslon ~reak:ers~and emulslon preventing,compositions free or .rel~atively~free o~f~h:ighly flammable~-and env1ronmentally objection-able:aromatic~hy'drocarbonsi compositions h'aving a comparatively low c;ost; compos1ti~ons~which;'are soluble~or~dispersible`in wster and~whi~ch,`~the'refore,~;can~often:be:`appli~ed by:more efec'tive ;me'tbod`s~than ~can exlsting~products; compositions which'can be used in enhancsd~recover~ opera~ions SllCh as ste~m fl~odin~ ~nd ag;ueous medium :flooding where`presqnt produc~s.cannot.be readily app~ ed~;~and;co~position6 which~can be'compounded with water-sD1ubl~e~reagent~s:of~o~ther ~yp:es~;, such`as corrosion inhibitors, wstting:~a;gents~, s~cale~ hibitors,~biocides, acids,~etc., to prov1dé~'multi~purpose~compoun:d's~for:~use:ln solvm~'many oil well:
coTnp1etLon,:pràduction~ transportation and refining problems.
.In~ac:cor~:ance~wi~h,the~pres~e-n~t ~invent1on, thes'e'a'ims are ac~c~mplished by means~of amphipa~hic agent~s wh'i'ch'are''capable of 30~ orming mi~cellar~solut~ions~and wh'ich'by th~is mechanism or other unde~ined actions,: coTnbined:with'~'thos'e`of a secon`d es'sential 6- ` :
.

~lS3272 ~

component which will be referred to as a hydrotropic agent, are able to form homogeneous aqueous solutions containing a rela-tively wide range of concentrations of TFSA.

DESCRIPTION OF THE PREFERRED EMBODIMENTS
The TFSA compositions of the present invention can be broadly categorized by the following general characteristics:
1. Solubility in water and isooctane at about 25C
is less than about 1% by volume;

2. Solubility parameter at about 25C is in the range : 10 of from between about 6.8 to about 8.5, with a .majority in the range of from between 7.0 and about 7.9; and ~ ~

3. ~ Spread~at the~interface between white,~reflned mineràl oil and~distil:led water to form films having a calculated th1~cknoss no~'gréater than:about 20 Angs~tr~ms;~*~a~ preadlng~pressure of about 16:dynes A'~co~posL~1On~h~ving~ the properties are gen~rally po ~ ~:or~s ~ poly~ers~having~mo1ecular~ lghts ~
f~om: ~ ~,000~:to,,about~100~000 and having~str w tures ~`
ing~a`mul ~ lcity~;of~distr~ibutèd~hydrophilic and hydro-pho'pic~moietle~.arranged~:ln lineàr or::planar array~which make t~ m'~ùrfacè aat:~'ve and~lead~to~:thq;ir~àdsQxptlon at oil-water ~ :
ajcies,~:t,o~o ~ ~ve' ~: f lm9~
ke~moJY~c ~ nly~ ~ u~ntered~9u~rface-aati~ve~compounda, ~re~:ejnt~ ~ :,.~ pears~ to~be~:~incàpable of~forming a miaelle :oil~Q~w4ter~ di9trib ~ d and;alte~rnating ~;

of~ r~,and~,nonpolar or~hydrophilicand hydrop~obic oup~ in ~the. ~ ~ e~ ~ ~y~`p ~ ents the-kind of organiza-'30::~ t:ion;~requlr~ed~f ~-~mi¢eLle~:~formatlon~'and thus impairs dispersion ,'' ~ : : : :
.,.. ,, . . . .,, ... . : . . .

~lS;3Z7Z

or so}ution in either water or low polarity organic solvents.
The TFSA's useful in the present invention have the :~
previously recited properties: .

~: , ~ .

.

5~3;27Z

1 1. 'l`l~e ~so]ul~ y in ~ter .lnd in i~;~)oc~ e aL ,~l)o~t 25~C ~s less_than_.ll,)out 1% ~y_~olu~ne.
Solubility tests may be run by placing a 1 ml sample (or the weight of solid product calculated to have a volume of 1 ml) in a ~raduated cylinder of the type which may,be closed with a ground glass stopper.
Tnerea~ter place 99 ml of wa~er in the-cylinder, close, , place in a 25C water bath lmtil ~he~mal equili~rium is reached, and remove from the bath and sllalce vigorously ~ , for one minute. Return the sample to the'bath for five minutes and then repeat the shaking procedure. Finally, retu~n~the sample to the~bath and,~allow it to stand uietly for one~hour.,~-iThe'~cyli'nder contents should be ; carefully~examin~ed~a~d any~cloudine~ss or opacity of the ,5~ iqu~d~ph~ase or~the~appearance o'~any sediment or ~ :-undissolved material~in~the cylind~er noted, thus indlcating;that th~e~sampl~e satisf'ied~the requirement ~"~ for~Lnsol ~ lity~in~wa~er~
I oo' t nQ:~ sol~ b: it~ ~is~ deter~ined~ Si ilarly by ~substitutin~ this~hydrocarbon ~o~ the~wat,er u~sed '-The-Sol~bilit:y~Parameter`(S.P.~) at~about 25C is fro~
` ;between~ ab~ut 6. g and~ about 8 . 5, . inclusive.
Me~hod8~0~ dete~ ination o ~s~ubLll y parame~er are"d~sel~os ~in~Joel~`~H~ ;Hildebrand,;`'The Solubility o~
Nonel'~ ~ lyte5",~,Thi~d Edit~ion,~p~s. 425 et seq~ How-,~ ever~, a ~ ified;~proc~edure, sufficiently accurate for qualific-at :on~o~ a~u ~ f ~`:TFSA cQmposition may be ut~iliz d..~ ~ pQne :t~ f~a are~general1y~inso1uble i~ hy~drocarbon (non-hydrogen-b~onding)~solvents~ having~a :lower solubi1ity parameter ,, ~, ~, - :
r f '~

llS3Z~7Z

than themselves. Therefore, the present composition should be insoluble in a hydrocarbon solvent of a solubility parameter of about 6.8. Since the solu-bility parameter of mixtures of solvents is an additive function of volume percentage of components in the mixture, test solutions of the desired solu-bility parameters may be easily prepared by blending, for example, benzene (S.P. 9.15) and isooctane (S.P. 6.85) or perfluoro-n-heptane (S.P~ 5.7).
A mixture of about 72 parts of benzene with about 28 parts of isooctane will provide a solvent having a solubility parameter of about 8.5 at room temperature (about 25C). Perfluoro-n-heptane has a solubiIity parameter of about 5.7 at 25C, so a.:. ..
mixture o:f 68 parts of this solvent with 32 parts of benzene provides a solvent with a solubility parameter of about 6.8, or isooctane.of a solubility parameter 6.85 may be~ used.
When 5~ ml of the TFSA are mixed with 95 ml of 2:0~ an 8.5 solu~ility parameter solvent at room tempera-: ture,~a clear solution should result. When 5 ml of : TFSA is mixed with a 6.85 solubility parameter ; solvent, a aloudy mixture or one showing phase separation should result. Solvent mixtuxes have a solubllity parameter between about 7.0 and about 7.9 may be prepared as described above and utilized ln a ~imilar test procedure.
: : Ih interpreiing the solubility parameter and , ~ , other tests, it:should be reaognized that the TFSA
30~ : ~ consists not of a single material or compound but .~ a cogeneric mixture of products containing a range of products of molecular weights distributed around _ g _ ~ . ~ ''" . ; '" ' ` ~

llS3Z~2 the average molecular weight and even containing small amounts of the starting compounds employed in the synthesis. As a result, in running solubility and solubility parameter tests, very slight appear-ances of cloudiness or lack of absolute clarity should not be interpreted as a pass or a failure to pass the criteria. The intent of the test is to ensure that the bulk of the cogeneric mixture, i.e., 75% or more, meets the requirement. When the result is in doubt, the solubility tests may be run in centrifuge tubes allowing subsequent rapid phase separation by centrifugi.ng, after which the separat-ed non-solvent phase can be removed, any solvent contain`ed in it can be evaporated, and the actual weight or volume of separated phase can be determined.
3. T~he T~SA should spread at the i*terface between distilled water and refined mineral oil'to form films with thickneJs no qreater than about 20 Anqstroms (0.0020 micrometerj at a film Pressure of about 16 : Yne~s~per cm (0.0i6 Newton per meter).
Sult~ble methods of determining film pressure are disclosed~in N. K. Adam, "Physics and Chemistry of 9urfaces", Third Edition, Oxford University Press, ' Lo~don, 1941, pgs. 20 et seq, and C. N. ~lair, Jr., "Interfacial Films Affecting ~he Stability of Petro-leum~Emulsions", ChemistrY and Industry ~London), 1960, pgs.~538 et seq. Film thickness is calculated on the assumption that all of the TFSA remains on the area of interface between oil and water on which the pr~duct or its solution in a volatile solvent has been placed. Sinoe spreading pressure is numerically equal to the change in interfacial tension resulting :

-~3L53272 from spreading of a film, it is conveniently determined by making interfacial tension measurements before and after adding a known amount of TFSA to an interface of known area.
Alternatively, one may utilize an interfacial fllm balance of the Langmuir type such as that described by J. H. Brooks and B. A. Pethica, Trans-actions of the Faraday Society (1964), p. 20 et seq, or other methods which have been qualified for such interfacial spreading pressure determinations.
In determining the interfacial spreading pres-sure of the TFSA products, I prefer to use as the oil phase a fairly available and reproducible oil such as a clear, refined mineral oil. Such oils are derived from petroleum and have been treated with sulfuric acid and other agents to remove non-hydrocarbon and aromatic constituents. Typical of such oils is "Nujol'l,~distributed by Plough, Inc.
This oil;ranges in density from about 0.85 to 0.89 20~ ~ and usually has~ a solubility parameter between , ~ , about 6.9~and about 7.5.. Numerous similar oils of greater or smaller density and viscosity are ~ commonly available from chemical supply houses and' }~ pharmacies.

Ji~ Other essentially aliphatic or naphthenic ~ hydrooàrbons of~low volatillty are equally usabie 3~ and will yield similar values of spreading pressure.
~ Suita~tle hydrocarbon oils appear in commercial 3~ tradè a3 refined "white oils", "textile lubricants", "paraffin oil",~ and the like. Frequently, they may aoi~tain very small quantities of alpha-tocopherol : , : :
;. .

, llS3Z72 (Vitamin E) or similar antioxidants which are oil-soluble and do not interfere with the spreading measurements.

::

, ~
~ :
`:~

,:
' - lla -~, .

, ' ~lS3272 .
ile t:he exist:cnce of In;cellcs clnd o~ oily or aql-eous nicellclr s~lu~:i.ons havc bcen known .ror some tirne (see, e.g., "Surface Activity", Moilliet, Collie and Bl.ack, D. Van Nostrand &
Co., New York (1961) ) Rnd are probably involved i.n many operations involviIlg det:erj~,ency wh~rc cither oi.ly (nolll-ol~r) or e;~ hy (highly polar) soil particles are to be relnoved, their utility in cooperation' with hydrotropic agents for the present purpos~es is - an une~pected and unpI-edictable ~iscovery.
In U.S. Patent No~ 2,356,205, issued August 22, 1944, to , 10 Chas. M. Blair, Jr. ~ Sears ~ehman, Jr., a wide-variety of '.: . . . :
::~ micellar solutions designed to dissolve'petroleum oils~ bitumen, wax, and other relatively nonpolar compounas'are'described for 3~
3 ~ purposes of cleanin~g bii formation ~faces and for ef~ecti'ng en- .
,~.
' hanced recovery of petroleum:by solution thereof. At this early ~' 15 . date, however, the use of micellar~principles was not contem-3~ plated for the~preparation.of solut:ions of t.he relatively hijgh olecular weight~de~ulsifiers. : ~ ~ -;However,~some~of~the prLncipIes disclosed in the'above p~a:tent:,~omltting~the~:maln~ ob]ectLve~'therein of dissolvin~'rela-: tively large amounts~of hydroc~arbons~, chlorinated hydrocarbons, . and the~like,~ are applicable to;~preparation of the present com-'~ posit~ions.
The four necessary component;s:of the micellar soluticns o~
3~ TFgA~are~
5~ : A micelle-~o~min~phip,s~ c ~ent, Such m~y be : anionic,~ cationic~, or~nonîonic and, lf anio,nic or 7`' ~ cation:ic:,~mày~;be~either~ In~salt form or as the free ; 'acid.or fr;ee~base~or mixtures thereof, 2.~ d--_E~c ~ent ~T~is is a small to medium mole-3~ cular;~welght~semi-polar compound containing oxygen. -nitr~ogen or sulur and:capable o~ forming'hydrogen ,., ~ ~ . . .

, 'i ~ .

llS3Z7Z

1 boncls. It is believed ~hat such a~nts cooperate in SOllle ln~llller ~it h ~:h~ n~ atl)ic ~ nt to form clc,lr or opalescent, stable compositions.
3 . W~ t. er.

4. 'rFSA, having the propertics' reclted aboYe.
In addition to t hese components, ~he micellar solutions may contain, but are not required to contain, salts~ hydrocarbons, or small amounts of other inorganic or organic material. Such' ~; constituents may be impurities, solvents, or by-products of ~10 syntheses used in fol~ing the hydrotropic a~ent, or may be addi-io~s~found useful in iorming~ the composition o~f this invention.
As~an~example~of~the l~atter,'small~amounts of lnor~anic s~lts-;
such as~NaCl, Na2504~,;KN03;,~CaC1~2;~and the l~ikè~,' are~sometimes ~~
`hélp~ful~in promoting~homogeneity~with~a minimum~o amphipathic ~15~ and~'hydrotropic~agent;s~ They may`~also'yield-compositions of .
lower~freezlng~poin~t,~a pr~op~erty` seful~w n~'the eomposit on is~
'e~plo ~ ~in ~cold'~clim~ate`s~ Simila~rly,~et ~ le ~glycol,~met , acetic~acid~ or~siinil~ar~org~anlo~compounds~ma~y be~incor~
p~ra~ed~into the composi~ o ,~ ~improve p~ysical~properti s ~ing~ ~o~in`t~ vls~os`ity~A~an'd~dens~i~ty,~or to i~prove ~stability.
" As~stated above,~;the~micel~le-forming amphipathic agents ich`'may~b'e'used~in preparin~ the'aqueous solutlQns ~erein cnt ~ ated~may be ~eithe~ ~cation-activej~ ~ni~on-active, or of the rol~ytl'c type.~ p~athic~a~ents gen~erally have~pres~ent a~ one~ra~d~i¢~a~'containing;about~10 or; more car~o atoms and net-m~-re~``than a~out ~ cà ~ on~atom -p ~molecu q~.~ This amphipa~hic~'e ts-` mpl yed~ the~pres ~ t~invention as a gmpone~ of~ e~ve~icle~or~solv~nt~ or~dispersant employed in the pres~ent~composi~ns~ T ~hydrophobic portions of these a ents may~be~alipha~ic,~alicyclic~ ;alkylali~cyclie~, aromatic, arylalky~, or~àlkylaromati~c. $he'pr~ef~rred~'type~of agents are those in -` ~lS;3Z'~;~

which the molecule contains a long, uninterrupted carbon chain containing from 10 to 22 carbon atoms in length. Examples of suitable anion-active amphipathic agents include the common soaps, as well as materials such as sodium cetyl sulfate, ammonium lauryl sulfonate, ammonium di-isopropyl naphthalene sulfonate, sodium oleyl glyceryl sulfate, mahogany and green sulfonates from petroleum or petroleum fractions or extracts, sodium stearamidoethyl sulfonate, dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate, sodium naphthenate, and the like.
!0 Other suitable sulfonates are disclosed and taught in U.S.
Patent No. 2,278,171, issued February 17, 1942, to De Groote and Keiser.
Suitable cation-active compounds include cetyl pyridinium chloride, stearamidoethyl pyridinium chloride, trimethyl-hepta-decyl ammonium chloride, dimethyl-pentadecyl sulfonium bromide, octadecylamine acetate, and 2-heptadecyl-3-diethylene diamino-imidazoline diacetate.
Suitable nonelecfrolytic amphipathic agents include the oleic acid estér of nonaethylene glycol, the steric acid ester o polyglyceroli oxyethylated alkylphenols, and long chain ~; alcohol ethers of polyethylene glycols.
It is of course, well known that amphipathic compounds are readily and commercially available, or can be readily prepared to exhibit the oharacteristics of more than one of the above mentioned types. Such compounds are disclosed in U.S. Patent ,~ ~
No. 2,262,743, dated November Il, 1941, to De Groote, Keiser ;~ and Blair. For convenience, in such instances where asurface-active ~iaterial may show the characteristics of more than one of thè above described types, it is understood that it ~0 may be classifiéd under either or both types.

,................... . . . .

115~3Z7~

The mutual solvent or hydrotropic agents of the solution utilized in the present invention are characterizable as compounds LO

': :

, :` :

- 14a -'' ~"7~

5~Z72 1 Of a hydl-ophobic l~y(:lroc~rboll.residue of colnparatively low molecular weight combine~ with a hydrophilic ~roup of low molecular weight and are free from surface-active properties. The'hydrophobic resic~ue may'contain fr~m 2 to 12 carbon atoms and may be alkyl, alicyclic, aromatic, or alkyl substituted alicyclic or aromatic, or may be the'hydrocarbon portion of a heterocyclic or hydro-carbon subst~ tèd heterocyclic group. The llydrocarbon residue may have br~nched or normal chain structure, but no branch may '" have a lèngth of.more than 7 car~o,n atoms from the point of .
attachment to the hydrophiiic residue, co~mting a'benzene or cyclohexyl group as being equivalent in length`to an aliphatic chain of three carbon~atoms.' Whére the hydrocarbon residue con-sists of not more-than~4 carbon atoms, structures:of .the noEmal pr~lmary alkyl~type~are pre~ferre'd.'. Where'the residue~is made up ~ 15 ~ ~of mo;re than fou'r carbon atoms,~ then~structures of secondary and ;~,~ ;,:; , :;~tertiary~types;~ar~e a~so~good~'wher~è~the~s'èc~nd~aDd~third~branches may~b~e,~me~thyl or:-~eth ~;gr~up~s ~b `~ ` T~is~hy~drophobic~hydrocarbon residu~e'is~combined~either d~rsctiy or~in~dir~ectly~with~:a~hy~drophi~lici~group~of one of the following.groups~
a)~ A hyd~oxyl~group which may be alcoholic~ phenolic, or carbo~ylic;;~
(b)~'~ An~aldehyde~group;~
",~ (:c)~,A~carboxy amide group;
(d)~ n~amine~sa~lt,group:; : ' ' (e) An~amine~rQup, and (f~ n,~alkali~phenoLate~group~
h,,~ ~.,"indir~e~edly~c~ombined with one of these ~roups" is meant that~:the',hydroc~arbon residue~is co~bined as,by etherification, ;:~ es~terification,~ar~amidiflc:at:ion, or ~he like~ with'another ;organic residue~whicb:~conta,ins~not ~ore than four carbon atoms ., - - . . ~ , .
,., ~ , : ;

~ 15327Z
and also one or more of the hydrophilic groups named above, provided that after said combination, at least one of the hydro-phile groups remains free. Specific examples illustrating this class of compounds are: Ethyl alcohol, n~amyl alcohol, alpha-terpineol, p-cresol, cyclohexanol, n-butyraldehyde, benzalde-hyde, n-butyric acid, glycol mono-butyrate, propyl lactate, mono n-butyl amine hydrochloride, n-propionamid, ethylene glycol mono n-butyl amine hydrochloride, n-propionamide, ethylene glycol mono n-butyl ether, pyridine, methylated pyridine, piperidine, or methylated piperidines.
The solubilizer (mutual solvent ox hydrotropic compound above described) is essentially a semi-polar liquid in the sense that any liquid whose polar character is no greater than that of ethyl alcohol and which shows at least some tendency to dissolve in water, or have water dissolved in it, is proper-ly designated as semi-polar.
The solubilizer or semi-polar liquid indicated may be illustrated by the formula X - Z, in which X is a radical hav-ing 2 to 12 carbon atoms and which may be alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl, or alicyclic-alkyl in nature, and may, furthermore, include heterocyclic compounds and substituted heterocyclic compounds. There is the added limitation that the longest carbon atom chain must be less than eight carbon atoms, and that, in such characteriza-tion, cyclic carbon atoms must be counted as one-hal~. Z
represents:
H O U
- OH: - N / - C / : - CN / : - COOH or - O~e where U and V are hydrogen or a hydrocarbon substituent and Me is an alkalie metal;

~ .

llS~Z~7;~

N
if X is a cyclic tertiary amine nucleus;

~0 , .
~ -:

;:

'1; .
i.- . ..

. .

- 16a ~

" , NH ~3~S~Z7~ 1 if X is a cyclic secondary amine'nucleus.
' The scmi-polar liquid also'may be indica~ed by the following for1nula: ~X -Y - R - (Z)n Here X and Z have their previous significance, R is -C1~2 , ~ C2H4-, - C3Hs =; C3H6 or --C2H4-- C2~4 and n is either one or two as t~e choice of R demands. Y is one of the following: .

N, ;' - N - C-; - C- 0~;~ O- ~; ~0 - ; -S
In general, these hydrotropic agents are li.quids having di-elec~tric constant values~ between about 6 and about 26, and have at~1east~one polar:group contai.nlng Dne or Inore a~oms of oxygenr 5: : and/or n1trogen.~It is~si~gnifi:cant,.p~erhaps,-that all of the so~1ub11iæ~ers are~of:types~kn~own~to be able to~form hydrogen The choice:'of~so:lu~ilizer~:or:common~solvent and its:pro-in;~the~m~ixture:~d'epends~somewhat-:upon~;~the amphipathic agent:used,~:the:~amount~and:kind: of~TFSA used,~and the.pr~oportion : ~ :water~"u.se~d,~and~is~best~.determined by preparing experimental mixtu:res:~on a.small scale, In 90~e'case:9,: it is~desirable to include in the-solution ;smal1~amoùnts;~of~a~cid,~'~alkali~ or inorganic sal'ts, as it has been ' , ~ d~-that~the~presen~ce~of~the~s`e electrolytes o:~ten gives solutions n'g~gr:èate ~sta iIity~and;~a wider ~ange~
wa~er~and~orgàn c~mate l~.:.Exc~ess~a~cid,~:when used, will usually q~n solu.t-'i~ons~con:~aining.~a~'cation~-ac~iv:e~or nonelectrolytic 7e:tting~:agen:t,~ but~; nat~exclusively sa. Excess alkali,: when used, wnl~:usually~be~'in a~solutiDn oontaining~anion-active wetting ag~ents,~ ~but;, again, ~not exclu:sively~

:, ~: : ~`,' ' ' ' . ' .

32t7Z

l - The polye~her polyol ol: IlSA utilized in this invention is generally an organic polymer or semi-polymer wi`th an average molecular weight above about 800 and below about 30,000 and has a st.ructure which will allow orientation on polar surfaces with much or most of the elements of the molecule in a thin p.lane. To be effectively adsorbed at oil-water or oil-rock interfaces and subsequently to be desorbed at water-rock interfaces, the TFSA
must ~enerally contain cons~ituents wllich givc'i~ a highly dis-tributed hydrophi'le and hydrophobe character, and witho'ut such concentrations of eithe`r hydrophilic or hydrophobic groups as to produce water soIubility or oil solubility, in the ordinary macroscopic sense. The TFSA also appears to differ from formerly used surfactants'in that the effects on oil-water' interfacial tensions as a function of concen'tration are limited. While .
spreading'efficiently at such interfaces to fo.rm thin.films with spreading pressures up to about 3'5 to 40 dynes per cm, addition or larger amounts of TFSA have relatively little''effect on inter-facial tension.' Also,'the`'present TFSA constituent of the micellar solution in contrast to formerly used surfactants, has relatively '20 ~ ~:little or no tendency to stabilize;either oil-in-water or water-in-oil emulsions when present in normal use amounts.
~`' UsuaIly the TFSA .constituents applicable to the practice of ~: the i~vention are or~anic molecules con~aining carbon', hy~ro~en and oxygen, although in some instances they may also contain '25~ sulfur, nitrogen, silicon, chlorine, phosphorous or other elements.
; - :Small:amounts of:inorganic materia'l such as alkalies, acids or salts may appeàr in:the'compo5itions as'neutralizing agents-, catalyst residues or otherwise,' The critical requiremen'ts ~or : the TFSA compositions ~are'not s`o'much`compositional as structural and physical. 'They must be'made'up of hydrophi'Ii'c '~polar~ moieties, usually on'es' capable'of forming~hydrogen bon'ds, .s'uch'.'as hydroxyl, .
~ .
. -18- -;

1 carbonyl, ~ster, e~her, sul~l)ni.um, all~ino, alTITl)o~ Tn, phospho or similar hydrogen bonding groups, connected by or to hydrophobic groups, such as alkylene, al~yl, cycloaklyl, aryl, arylene, aralkyl, polyalkylene, polyalkylyne, combinations of such groups and such groups containing relatively non-polar substituents,' such as hydrocarbon, chlorine, ~luorine and the like. Sometimes the hydrophobic mOieTies are larger and contain more atoms than the polar groups in the molecule, havi.ng a mi.nimum'or two ca~bon . atoms in each group and up to as many as 36 carbon atoms, although the actual ratio of sizes depends greatly on the'structure of the hydrophilic moiety. .Most commonLy, the hydrop~lobic groups will contain 14 to:22 carbon atoms and will have'linear or sheet-like `~ conformations allowlng'for rela~tively flat orientation on surfaces.`
Polar moieties~other.~than~hydrogen bonding ones are not. .
: excluded from these'~compositions and, indeed, may.be del~iberately included in some ;structur~es to improve adsorption and interfacial s~preading~tendencies~ F~or example,' quaternary ammon'lum groups, whi~le~ incapable~of~ forming~hydrogen bonds, can improve'spreading and~Lnterfac'iaL~adsorption~in~some applications by way of their 2;0 ~ h;l~ly~ionized form~wh'ich:imparts cationic character to the mole-~ cules in which they occur an~d, via coulombic repulsion effects,t`~ can improve spreading in a film.
Generally, the~TFSA~constitu~nts will contain at least two each~of~the~required~hydrophilic (polar)~ and hydrophobic moieties ~5~ per moleculè~and~;commonly~will~contain~many~ more of~each. The ef~fective produc~ts,; however, must have'the three'properties described ~above. ~
Whi:le,'~as~point~ed out~above,' the effective TFSA may be'de-;rived ~rom::a`wi~de~:var~iety~.of chemical.reactants and may contain 30~ numerous~diferent-~groups~or moiet;es, I have`found .that partic-ularly effect~.products ar~e~'tho~se~'w.h`ic.h:`are`describe'd as a ~ ~ ~ -12-~, -, . .

~ I llS327Z
l polyepoxide con~ensate o~ at least one o~: (l) a.T)olyalkylene oxide ~dduct of a fusible, water~-insoluble or~anic aromatic . hydrocarbon solvent-soluble synthetic resin, wherein said resin . has from betwcen about 4 to aho~1t lS phenolic~groups and is an alkyl or cycloaliphatic substituted phenol-aldehyde condensate of an ortho- or para-su~stituted phenol and an aldehyde, said con-- densate resin being thereafter ~urther condensed with an alkyleneoxide containing less than about five carbon atoms in an amount equal to at least one mol.e of alkylene oxide per phenolic moiety .
~10 of said resin; and (2) a polyether~polyol having the formula:
[o(A)iN~n ":~ NRl L (.A) k~]~ m wh:erein~
`~15 ~A~1s an~alkylene oxide~group5, -C,iH2iO~
~ is~oxygen;
i is ~a ~ po~sitive~ integer;no~greater~:than~about~la;
sitive~'integer nolgreater~: than~ about~LOQ
~int~eger~no~greater Lhan about~100j ~ :

is o~e~:of~ ~hydrog~en:, ~a monoualent~hydrocarbon ~roup containin~
1ess: than ~ aboùt ~::Cll , or [~ H].7 :
a positive~ integer~no gr ter~than~about~100; ~
a~h~n moié~y~:o~f~a~polyoL,~ a~pri~ary~or secondary a ~ imar~y~or~ econ ~ y~po~1 a e,: a prima y or 5econd~:~y~-a~ino,~alcohoI;,~or~,hydr~ogen;~and ~
n~is~;`no-~g~eater~ ~ ~bout~: : is;~other t d~one~Q-f~ ~ ~n~' -ze `~`-: d e othe`r-is~unity ~ en R
s~ ~ rQgen~ Th~se~:p:o~lyepQxlde~cQndensates must conform to . ~: Xhe~p ~ icai~;p ~ erty~p-arameters set forth;above,`
The~polyal ~ lene~.oxide`a~dducts~are broadl~described in U.S.
:Pa;tént~2,499~,~365,~en~it1ed '~'Chem`ica~l Manufàcture", date~ March 7, 1~5327~

1950, to DeGroote, et al. These compositions also include materials wherein less than one or two alkylene oxide units may be reacted with each reactive structural group of the starting resin.
The most common resin is an alkyl or cycloaliphatic sub-stituted phenol-aldehyde resin prepared by condensing an ortho-or para-substituted phenol with an aldehyde, most commonly with formaldehyde or a formaldehyde progenitor such as paraformal-dehyde or trioxane, under mildly alkaline or acidic conditions to form a fusible and xylene-soluble polymer of low or moderate molecular weight and which typically will contain from between about 4 to about 12 phenolic groups. ~his resin is then conden-sed, usually with an alkaline catalyst, with an alkylene oxide or a mixture of alkylene oxides.
Alkylene oxides suitable for use in preparing the composi-tions used in the present process include ethylene oxide, propylene oxide, butylene oxide, 2-3-epoxy-2-methyl butane, trimethylene oxide, tetrahydrofuran, glycidol, and similar oxides containing less than about 10 carbon atoms. Because of their reactivity and relatively low cost, the preferred alkyl-ene oxides for preparing effective TFSAIs are the 1,2-alkylene oxides (oxiranes) exemplified by ethylene oxide, propylene oxide and butylene oxide. In tha preparation of many TFSAIs, more than one alkylene oxide may be employed either as mixtures of oxides or sequentially to form block additions of individual alkylene oxide groups.
To be suitable for use in the present process, addition .
and condensation of oxide must not be carried to the point of producing water-soluble products. Where ethylene oxide alone is condensed with the resin, the amount added preferably will be between one and five moles per phenolic moiety in the resin. The actual amount will vary with the size of the alkyl ~5~2.7Z

or cycloalkylene group attached to the phenol ring as well as, apparently, with the composition and properties of the oil, aqueous phase and rock formation encountered in the method.
Where propylene or butylene oxides or mixtures of one or both of these with ethylene oxide are condensed with the pheno-lic-resin intermediate, generally a greater amount of such oxides may be reacted without leading to extremely polar, water-insoluble products. In contract, the amount of epichloro-hydrin or glycerol chlorohydrin which can be condensed without producing agents not meeting the solubility and interfacial spreading criteria defined above is usually somewhat lower.
On a solvent-free weight basis, the amount of alkylene oxide or mixture of oxides condensed with the resin will fall within the range of about one part oxides to about 10 parts of resin and up to from between about l-to-5 and about 3-to-1.
The final product should contain at least about one mole of alkylene oxides per phenolic moiety of the resin.
Compositions incorporated within the scope of the formula set forth above for the polyether polyol contain an average of about 1~ or more hydroxyl groups per molecule and are generally composed of a cogeneric mixture of products obtained by con-densing al~ylene oxides with smaller molecules containing two or more reactive hydrogens as part of hydroxyl or amino groups.
Representative of these compositions is polypropylene glycol, having an average molecular weight of about 1,200, to which about 20~ by weight of ethylene oxide has been added.
Such a p~lyether glycol is theoretically abtainable by condens-ing about 20 moles of propylene oxide with about one mole of water, followed by addition of about six moles of ethylene oxide. Alternatively, one may condense about 20 moles of propylene oxide with a previously prepared polyethylene glycol of about 240 average molecular weight.

X

l~S~27;~
.
1 Other suitable clihydric ~lcohols may be obtained by condens-ing lkylene oxides or mixtures of oxides or in successive steps (blocks) with diflmctional (with respect to oxide addition~ com-p~unds, such as ethylene glycol, methyl amineJ propylene glycol, hexamethylene glycol, ethyl ethanolamine, analine,' resorcinol, hydroquinone and the like.
Trihydric ether alcohols may be prepared by condensation of ethylene, propylene or butylene oxides with, for example, glycerin, ammonia, triethanolamine, diethanolamine, ethyl ethylene diamine or similar smaller molecules containing three hydrogens capable of reacting with alkylene oxides. Similarly, polyether alcohols with a multiplicity of hydroxyl groups may be'obtained by con-de'nsing alkylene oxides with multireactive starting compbunds~
such as pentaerythritol, glycerol, N-monobutyl ethylene diamine, trishydroxymethylaminomethane, ethylene diamine, dieth.ylenetri-amine,' diglycerol,.hexamethylene'diam'ine, decylamine and cyclo-hexylamine. DeGroote, in U.S. Patent No. 2,67~,511, describes a number of amino derived polyols which he'subsequently esterfies.
Product 15-200., manufactured and sold by thè Dow Chemical Company, ~ and derived by oxyalkylation of glycerol with'a mixture of ethylene and propylene oxides, is an example of a commercially ~ available'polyol of the kind contemplated herein.
:~ Generally, these compositions will have'average molecular weights of 15,000 or less and will be'derived from reactive' , ~ :
~ hydrogen compounds having 18 or fewer carbon atoms and lQ or fewer reactive~hydrogens.
Other general descriptions of suitable polyether poly~ls : coming within the scope'of the structure'detailed above,` along '(~ with methods for carrying QUt the'actual manufacturing steps, are ~ , . . .
disclosed in "High Polymers, Vol X~II, Polyethers,".edited by N. G. Gaylor'd, John Wiley & Sons, New York, 1~.63.' ' : . :

* Trademark ~L53272 Suitable polyepoxide for condensation with the compounds set forth above include, particularly, the diglycidyl ether of dihydroxyphenyl-methylmethane and the lower polymers thereof, which may be formed as cogeneric mixtures and which have the general formula:

/ \ I
H C - CH-CH - C_O_C6H4 - C(CH3)2 C6H4 2 2 o -o-c6H4-c(cH3) ~ C6H4 CH2 2 wherein n is zero or a positive integer of less than about 6.
Other polyepoxides containing two or more oxirane or epoxy groups, such as diisobutenyl dioxide, polyepoxypolyglycerols~
epoxidized linseed oil, epoxidized polybutadiene or the like, may also be employed.
The compositions suitable for practicing the present invention are prepared by reacting formaldehyde or a substance which breaks down to formaldehyde under the reaction condi-tions, e.g., paraformaldehyde and trioxane, and a difunctional, with respect to reaction with formaldehyde, alkyl phenol, often ~ a~crude~mixture of alkyl phenols for economic reasons, by heat-ing the reactantq between about 100 and about 125C in the presence of a small amount of an acid catalyst 9uch as sulfamic acid or muriatic acid or, alternativ@ly,in the presence o~ an alkallne catalyst such as sQdium hydroxide or sodium methylate and~,~ preferably, under substantially anhydrous conditions, eXaepting the~water produced during the reaction. The aqueous distillate which~begins~to form is collected and removed from the reaction mixture. After several hours of heating at tem-:
peratures slightly above the boiling point of water, the mass becomes viscous and is permitted to cool to about 100 - 10SC.

At this point, an aromatic hydrocarbon fraction such as xylene ` may be added, and heating is resumed.

,`'`, ~ . .

1~5;~27Z
, 1 Furtlller aqueous distillate l,e~ins ~o form, an~ heating is continued forlan ad~itional number of h~urs until at least about one mole of aqueous distillate per mole of the.formaldehycle has been distilled off. Xylene or other hydrocarbon w~ich may be'distilled S with the water is ret-urned to the reaction mass. The temperature at' the end of the reaction reaches about 180 - 250C. The product is permitted to cooi to yield.the phenol-formaldehyde . condensation product in ~he aroma~ic solvent.
: The molecular weight of these int~r~ediate concdensation products cannot be ascertained wit~h certainty, but it is estimated ~ . ~ that the resins employed hereln'should contain from between about ; ~ ' 4 to about'15, pre~ferably from about 4 to about 6, phenolic ' 'nuclei per resin:molecule.' The'solubility of the condensation product in hydrocarbon solvent would indicate that the`resin.is a ~:15 linear or sheet-like poLymer,~ thu's distinguishing it from the mor~e c:ommon phenol~-formaldehyde res'ins of the~insoluble:'cross-~
.linked~type.
Having: prepared~the~intermediate'phenol-formaldehyde pro~ucts, 'thè~'next~step i5 the QxyaLkylat~ion of the condensation`products .:with~alkylene~oxi:de~.~;Th:i~s~ls a'chieved by mixing the`intermediate phenol-ormaldehyde.condenæation product as is or contained in he aromatic's~lvent with`a small amount o a suitable ca~alyst, usually potassium~hydroxide:or sodium metllylate, in an autoclave.
The~con~ènsation product~is heated above~100C, and ethylene S ~ ;oxide, propyl~ne;oxide, b~yl~e~e.~oxide`or mixtures of two or all :three~o~f these~ox~ides,~::elther-.as a~mix'ture or by sequential addi-tion~of:~fir~st eit,her~o~e~'or'another ~o the oxides is char~ed into the Autoclave~un~t`il'~.ne~'press'ure'îs`in the vicinity o 75 - 100 30~ The:`reaction mixtur~e;is gràdually heated:until an exothermic: reactlon begins.~ The'exteroal heating is then re~oved, and , , ` : .. ~ . . . ..

~15 ~27Z
alkylene oxide or oxide mixture is added at such a rate that the temperature is maintained between about 130 - 160C in a pressure range of'30 - 100 psi. After all of the alkylene oxide has been added, the temperature is maintained for an additional 10 to 20 minutes to assure substantially complete reaction of the alkylene oxide. The resulting product is the alkylene oxide adduct of an alkyl phenol-formaldehyde condensa-tion product, in which the weight ratio of the oxide to the condensation product (on a solvent-free basis) is between about ~10 l-to-10 and about 10-to-1, preferably between about 1-to-5 and about 3-to-1, and containing at least about one mole of alkyl-ene oxide per phenolic moiety of the resin.
As to the limit~s of the various~constituents of the micel-l~ar solutions containing TFSA, the following will serve as a guide, the percéntages being by weight:
Percent TFSA~;¢onstituents ~about 5 to about 75 HydrotropiG Agent ~ ~ about 2 to about 30 s~ Amphipathia~Agent ~ about 2 to about 30 ~-20~ Water~ about lS to about 9Q
Although the~ex4ct~funation of the electrolytes previously re~er~red~to is not~aompletely understood, the e~oct, ln part, may~be~due~to the abillty~to blnd~water, i.e., to beaome hydr4ted.~ his~uggests~;that certain other materials which are h ~ ~ ~ rophi ~in charaater~and clearly differentiated ~from t~hé'~class'es~f~non-polar solvents and semi-polar solubilizers `may~be'the~functional~'equivaLent;~of an;electrolyte. Substances of this~cla90~which 0rd~inarily~do not~dissociate include 3~ glyGero~ ethylen~e~glycol~diglycerol~sugar~ glucose, sorbitol, ~ 30~ mannitol,~and~the~lik~e~

: ~: :: , -~ - 26 -X-`:
,'s ~ .
.. . .

1 ~lso, a~ st~ted al~ove, t:hese solutions ~ay contair other organic constit~lents such as hydl-ocarbons. These frequently are used as thinning agents, aze~ropic distillation aids or reflux temperature controllers in the manufacture of~the TFSA constituent ' and may be left therein when the present micellar solutlons are prepared. To the extent that such compounds are prcs'ent they appear to compete somewhat with the TFSA constit~lent for micel'le space,' thus limiting, to isome extent, the maximum amount of TFSA
constituent which can be'brought into homogcneous solution.
' Selection of an effective TFSA composition for a given pet-, roleum emulsion and determi~ation of the amount required is , usually made'by so-called "bottle~tests", conducted', in a typical situation, as follows: ' ' ' ' ' -: , ~
A sample of fresh'emulsion is obtained and 100 mL portions are poured into'each of several 180 ml screw top'prescription or similar~graduated~'bottl'es~ Di~lute'solutions (1%'or 2%~ of'various TFSA c~onstituents~are~'prepared~in lsopropyl~alcahol. By means of a;~graduated pipett~e,~a small~volume of a TFSA solution is a'dded ~ t~o~a~bottle. A~sim;lar~volume~'of each"composition is added to I ~ ~ other~bottles~con;tain~ing emulsion. The'bottles are'then closed and~transferred to a'water bath held at the same temperature as that empIoyed in the field trea~ing'plan~. iA~ter reac~ing ~
temperature,' the~bottles are'shaken briskly for several minutes.
~ After the~shakin~period, the'bottles are placed uprig~t in g`~ the water bath~and al~lowed~to stand~quietly." Periodically, the volume'of the;separat~ed;water layer is recorde~ alon~ with obser-vations on the~ sharpness ~o;~the oil-water interface', appearance of the oil and~clarity af the water phase.~
A~ter~the~standing~perLod, which may range from 30'minutes ~30~ to several hoùrs,~depending upon'~the'temperature,' the'~isco`sity of the~emulsion~and;the~amount of~TFSA compositions-used, small . . . . . . .

, . . .
,J

~532~;Z
samples of the oil are removed by pipette or syringe andcentri-fuged to determine the amount of free and emulsified water left in the oil. The pipette or syringe used to remove the test samples should be fitted through a stopper or other device which acts as a position guide to insure that all bottles are sampled at the same fluid level.
The combined information on residual water and emulsion, speed of the water separation and interface appearance provides the basis for selection of the generally most effective TFSA
L0 constituent. Where none of the results are satisfactory, the tests should be repeated using higher concentrations of TFSA
constituents and, conversely, where all results are good and similar, the tests should be repeated at lower concentrations until good discrimination is possible.
In practicing the process for resolving petroleum emulsions of the water-in-oil type with the present micellar solution, such solution is brought into contact with or caused to act upon the emulsion to be treated, in any of the various methods or apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.
One type of procedure is to accumulate a volume of emulsi-fied oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this pro-cedure, the emulsion is admixed with the micellar TFSA solution, for example, by agitating the tank of emulsion and slowly dripping the micellar TFSA solution into the emulsion. In some cases, mixing is achieved by heating the emulsion while drip-ping in the micellar TFSA solution, depending upon the convec-tion currents in the emulsion to produce satisfactory admixture.
In a third modification of this 532~

typ~ o~ Lre~ ent, a circul~.in~ UIllp ~iLh(lraws ~ sion from, e.g., ~he bot~om of the tank and reint:rod~lccs it il-tO the top of the tank, the micellar T~SA solution being added, for example, at the suction side of said clrculating pump.
In a second type of treating procedure, the micellar TFSA
solution is in'troduced into tl-e well fluids at the wellhead, or at some po;nt between the ~el;lllead al-d the final oil s~orage tanlc, by mCatlS oE an ~djustal-lc pro~ort~:i.ollillg ll)ecll.lllislll ~r ~ or-tioni.ng pump. Ordinarily, the flow of fluids through the subsequent lines and fitti.ngs suffices to produce the desired degree of mixlng of micell.ar TFSA solution and cmulsion, al~hough, in some instances, additional mixing devices may be introduced into the . .
flow system. In this`general procedure, the system may include various mechani.cal devices--for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemically treated emulsion. Ileating devices may like'wise be incorporated in any of the treating procedures described herein.
A third type'of application (down-the-'hole?' of-micellar TFSA
solution to emulsion is to introduce the micel'lar solution either ,i , .
periodically or continuously 'in diluted form into the'well and to allow it to come to the surface with the well f].ui(ls, and then to flow the chc~ical'-containing emulsion through any desirable ~ ' surface equipment, such as employed in the other treating proced-`~ ' ures. This particular t`ype o application is especially useful ,~ 25 when ~he micel'lar solution is used in connection with ac;dification , ' : of calcareous oil-bearing s~rata, especially if dissolved in ~he acid employed for acidification.
In all cases, it will be apparent from'the foregoing descrip-tion,~the broad process consists simply in introducing a relatively small proportion of micellar TFSA solution into a relatively '' large proportion of emulsion, admi~ing the' chemical and emulsion .
- 2 !~! -1~5 ~Z~2 l e;~her L11ro~.1gh nat:1lral ~low, or ~11rough ~r~ci,~ r~ a~1s, ~ith or'without the application of hea~, and allowing the' mixture'to stand quiescent until the undesirable water content of the emulsion-separates and settles from the mass.
5 . ' Besides their utîlity for'breaklng petroleum emulsions, the present micellar TFSA solutions, as'mentioned earlier, may be ' used to prevent emulsion formation in steam flooding, in secondary waterfl.ooding, in aci.dizing ~f oil-~-rod-1c;.llg ol111ati.o1ls, a1ld t:he ' like.
lO . Petroleum oils, even after demulsification, m~y contain ~: substantial amounts of inorgan'ic salts, either~in soIid form or as small remaining brlne droplets.. For thLS reason, most petroleum ~ oils are'desalted prior to refining. The'des'alting step is ': effected by ad:dlng and mixing with the~'oil a few volume'pe.rcentages ~ of resh water to~: contact the~brine~'and salt. ~In the'absence of demuls:ifier, su~ch~'added water~would also~become~emulsiied with-out~effecting its~ w~shing~action. The pres:ent:micellar solutions may~:be~added to the~fresh~'water~to prevent its~emulsification and to~:ald~in phase~ se;paration~ and':removal of salt by~the'desalting 2p~ proce:s~s. 'Alternatively, if desired~,~they may be add.ed to the'oil phase as.are present aromati.c solvent compositions, Most petroleum oil, alon~.with its~accompanying brinès and gases, is corposive~to:steel and other metallic structur:es with wh:ic~h~:it~comes in:contact~; We:l'l.~tubing, casing, flow lines, sepàrators and`lease;tanks~are often.seriously~attacked by well 1ui.d~s,~especially'where~acidic~ga~ses such as H2S'or C02 are pro~duced:with the liquids,~bu~t~also ln systems free of such gas~es, ~ ~
It has:b~een known~for~50me:time,' and as exemplified in U.S.
Patent.2,466,~517,'.issued April 5,~lg49, to Chas, M. Blair and Wm.
F.: Gross, that such'co'rrosive'at:tack of crude oil fluids can ~e ~' ' . .
', ::~ ' ' ~ S;~Z7~

l - m;.t:ig~ted or ~lrevcnted by ad~lition to the ~luids of small amoun~s of organic inhibitors. Efectivè inhibitors compositions for this use are usually semi-polar, surf~ce active compounds con- '' taining a nonpolar hydrocarbon moiety attache~ to one or more polar groups containing nitrogen, oxygen or sulfur or combinations of such elements. Gener~lly thes'e';.nhi~itors or their salts are soluble in oil and/or water (brlne~ and ~rcc1uent:ly a1pear ~o be able to ~orm micelles in one or both of tlicse'phascs. Typical inhibitors i.nclude'amines such as octyl amine, dodecyl amine, dioctodecyl amine, butyl naphthyl amine, d1cyclohexyl arnine,' ~: benzyl dimethyldodecyl ammonium chloride, hexadecylaminopropyl amine, decyloxypropyl amine, mixed amines prepared by hydrogenation ' . of nitrile' derivatives of tal1 oil fatty acids, soya acid este-rs' of monoethanol amine,' 2-und'ecyl, l-amino.ethyl'imidazoline and a ::~15 wide variety of cationic nitrogen compounds of semi-polar char-~ acter. ALso effect1ve~in some applications are nonyl succinic :s~ acid,~d1ocylnaphthalene~:'sulfonic 'acid, trimeric'and dimeric fatty acids, propargyl~alcohol, mercaptobenzothiozo~le:, 2, 4, 6-trimethyl-~ 3j`~5-trithiaane,' hex~a~ecyldimethyl`benzimidazolium bromide, 2-;~ ~2~0 .~ t~hiobutyl-N-tetrodec~ylpyridinium chl'orid'e, tetrahydronaph,thylthio-: mbrpholine~ and the llke.
'~ : ' In contrast to the TFSA, corrosion inhibitors appear'~o funct1on by orming on~the~metal surface strongly adherent, hick,~closely~packed~fil~s which prevent;or lessen contact of 2~ corrosive~lui~ds~;snd gases with''the~:metal~and interfere with ioniç~and electron t~ransfer react1ons:involved~ in the'corrosion process.
3 - ~
Corrosion~inhibitors are'quite commonIy introduced down the cas1ng ~annul-us o;f oil- wells wher~e'they commingle'with the well 30~ 1u;ds before~ their.trave1 up the'we`11 tubing and thus can ef~ec-tively prevent corro'sion of wel'l equipm~nt. Where'corrosive' , i ~ .
~ - ' -31-, , .

~15~27Z

1 a~ack occurs at the surface, th,e inhibitor may be introduced at or near the well head, allowing ~t to adsorb on the flow lines and surface equipment to insure protection., Addi~ion of inhibitor a,t either downhole~or surface locations 5 'm,ay be combined conveniently with demulsifier addition since the latter is also frequently introduced in one of these locations.
` Inhibitors such as those ~entioned above, ~ay ~enerally be incorporated illtO the TFSA micellar so1uti.o1ls, repl.acing a :~ portion of or in addition to the TFSA~ constituent. Also, since many of these inhibitors are themselves micelle-forming amphi-: pathic:agents, they m:ay be included in the mi,cel'lar solution as such, :replacing o~ther amphi.pathic~agents which might be`otherwise ' . utilized. vombining:the m1ceIlar solùtion~with corrosion inhibitor , perm,its more~economic chemical treatment by reducing inventory to 15 ~ one;compound,~requ1ring~onl~y~one'chem~1ca1;injection~system ratherthan two~and~ess~ening~;~the~1abor and~supervis1on requir~ed'.
Still another~:impor.tant:effect of us~ing the'miceIlar solution of-`TFSA~ànd~corrosion'~inh:ib~itor results from the prevention of ;emu1sification by th~e~.inhibit~or. 'Frequently,~:it has been found 20,~ ;that inhLb:itor~in the'amount`:r~eq~lired for eifective protectLon causes~the for~ation of very rera~tive emulsions o wa~er and ;hydrocarbon, .especia11y~,in~:systems containln~ light, no~mally nonému1sifying~hydrocarbons~such as~distil1ate, c~sing head gaso1ine, kerosene,~diese1~fuel and~various refinery fractions.
5~ Inhibi.tor~s:~a~e~co~monly'~:used in~refiner~y systems where .emulsifica-t~ion is hlgh1y~;object~i~nab~1e~and~where: the compositions ~ould be designed~to:in;c1ùde~an ef~ect~ive:~'emu1siQn preventative miceIlar ,solution~o~ TF~A.~
Inhibitor use may range''from~a few to~se;veral hundred parts 30~ per:~mi11~1on';~based~on ~he Qil ~to~b~e~:~'treated, depending upon`thè
;',sev~erity of CQ~rrOSiO~. ~ For'a: given oil iel'd or` ~roup of wells, ,., ~:

~lS~272 1 t:~sts will normally be run to detelmi.ne ~he requirement for micellar solution of TFSA and for inhibitor and a composition incorporating these components in approximately the'desired ratio will be prepared. In some'ins~ances, tXe req.uirement for micellar splution of TFSA in ~he bes~ concentration may result in use of corrosion inhibiLor, cmployed as micelle-former, in some excess over that required for inhibition. This will not affect the utility of the` micellar solution and will provide a comfortable ' excess of inhibition which can be helpful during the periods when higher corrosivity may be encountered.
Examples of micellar solutions employing TFSA with inhibitor in water disperslble,~ micel'lar solutions are given below.
Selection of the prdper' corrosion inhibitor for a given : , . .
system or oii is usually made by conducting laboratory tests under conditions simulating those encountered in the well or flowline, Such ~t~es~t~s are exempliied by that described in Item No.~lK155~, "Proposed~;S~andardized Laboratory Procedure for Screening Corrosion Inhibi~tors for Oil and Gas Wells`', publ'ished by the W~ational Associ~ation of Corroslon Engineers, Houston, Texas.

EXAMPLES OF THIN FILM SPREADING ~GaNTS
i ':~;
` EXAMPLE I~
RESINOUS~POLYALKYLENE~OXIDE ADDUCT'PRECURS`ER
25~ Referencé- is made to U~S~. Patent No~ 2,~99,365, to M. De Groote, issued~March'7, 19SO,~whlch describes generally the manu- -fac~ture of demu;lslfiers~by the ~xyalkylation o fusible, or~anic : solvent~-solubl:e,~ alkylphenol ~resins. The'procedur'e of Example '74a~of this pat~ent was ollowed to prepare'a fusible,' xylene' 30~ ' soluble'p-dodecylphenol resLn in xylene solution. The`aci'd catalyst was neutralized, water~was removed by azetropic dis-: -` :
., ~ ~ .... . .
. . .

I ` ~153Z7Z
1 tillation of some zylene and 0.5% by weight of sodium methylate catalyst was added. Using the procedure of Example'lb of the I
cited patent, 25% by weight of ethylene oxide, based on the final batch weight, was added and reacted with the resin.
EXAMPLE IB . - ' FINAL PRODUCT PREPARATION
Reference is made to U.S. Patent No. 3,383,325 to V. L.
Seale, et al, dated May 14, 1968, which described demulsifiers prepared by condensing polyet'her polyols and oxyalkylated alkyl-phenol resins with'diglycidyl ethe`rs of bis-phenol'compounds.
One'hundred parts of~the:product of Example 1, in co-pending S~erial No'.'''361~38'1~ fl1ed 'September'30, 1980, entitled Micellar Solutions~Of~Thin Film~Sprea'ding:Agents~Comprising A
~ Po:lyethe'r~Polyol", was:~reacted~with'l5 parts of the diglycidyl ethqr;:of~bis:-phenol:~A,~followed:by reacting:~with'80 parts of the ` d~:uct of~ ~ ~ e~IA,~-above?'~:~ l ln accordance with'the~procedure of~the Se`al~e~ et;aL~ pat ~ t~,~ Example~D8~ Addition.:of the~final ofi 5O2~extract was~omitted,~ Th~is~product meets the`
i~eria~fDr:~thin~il~sprcading~gent. ~ ~ :

The~'proc~d~re~employçd~in~Example~'4~a of U.S.' Pa~cnt ~,429,365.
,'~l~s:~sue~d~March.7,~ 19g0',~:~was~ followed~to produc~ an ed ndet ~ _ 1 IA ~v 1~000 ~ r~ ~ f ~ ~le:~ oxlde, ~S0 Ibs. of propyleDc`oxide ~LSt~ Z~
~ . .

.
l ' After coTnpl~tion of the oxide addition, the telnperature was adjusted to 140C and 70 lbs. of diemthyl, diglycidyl hydantoin dissolved in 250 lbs. of xylene was slowly introduced with rapid stirring. A~er colnpletion o~ the cpoxy hyda~toin addition, s,tirring and heating ~t 1`40C was continued until the batch viscosity at 100C was between 1,500 and 2,000 centlpoises.

EX~LE III
Thè proced~re of Example I was followed except that conden-sation with t.he oxylalkylated phenolic resin and final.addition . .
of S2 extr'act` were both :de.l'eted. ~ . .
The product was an effectlve :demulslfier meeting the'criteria described above, therefor. ~ h'is p~roduc~t wa~s~àlsa found to improve the percentage of oil recovery when ùsed as an additive'to`water :15 ~ us~ed in''experimental secondary~:waterflooding tests.

EXA~PLE IV :~
The~:proced~ure~'o~;Example'I is foll:owed,; except. that 12 parts .o~ iba-Geigy:Resin~XB2818,:an~a~1k~1ated dihydantoin containin~
thr:ee~epoxi~de groups, was~ substituted for:the l~:.parts of diglycidyl ether used~in Example I. ~Reaction was continued until ~he product exhibited a visc~sity af'abou~ 1,50~ centipoises at l~oQc. The f~nal:~product~met the~:'three~ cr~iteria for TFSA.

AU~L~ V
nto-~a~5~0D~g~al~ stainles~s:s.tee'l autoclave'equiljped with st~rrer~j steam j~ackèt~,:cool;ing coils;and appropriate inlet and '.
-o~t:let;:linès wa:s~intro:duce~d~l,:OO.O~lbs. af co~mercial polypropylene : glyeol~with~a*erage molec~ular~weigh~t of 4,.000.~ Sixteen pounds of .~ 30~ a~50%~:aqueQus~solution~of~potass;ium hy'droxide'was then added to the'g~lycol. St'eam:was:admitted to the'jacket ànd the` contents wer'e'stirred whi'le't~e~'t:emperature'was'br:ought to about 125C~

, ,, ~, .. .

~15~27Z
1 A slow stream of nitr~gen was bl~wn through the vessel c~ntents during the heating period to effect removal of water.
Mitrogen sparging was stopped when a sample of the glyol showed a water content below 0.1%.
At this point, commercial,epox;dized soyabean oil containing an average of three epoxy groups per glyceride molecule was added at a slow continuous rate while the temperature was increased to 145C. Addition was stopped after 90 lbs. of epoxidized soyabean oil had been introduced. Stirring and heating at 145C was continued until the reaction mixture had a viscosity within the range of 1,200 to 1,400 centipoises when measured at 100C.

EXAMPLES 'OF MICELLAR SOLUYIONS INCORPORATING TFSA''s EXAMPLE A
Wt. %
Product of Example II 38 Isopropanol 16 Dodecylbenzene sulfonic acid 16 20 ~ Diethylene triamine 4 Water 26 Thig product is an effective'e~ulsion breakex for e~ulsions ~i' produced in the Glendive fiel'd of Montana and is particularly useful as a synergistic component when combined with'other aqueous Z5~ ~ TFSA compositions such as described in my co-pending application Serial No~'' 361,788' , filed October 8, 1980 , entitled "Micellar Solutions Of Thin Film Spreàding Agents Comprising i: :
Polyepoxide'Condensates Of Resinous Polyalkylene Oxide'Adducts And Polyether Polyols".

~1~3;~7~

, 1 - F,X~MPLE B
__ ................. . .
Wt. %
Pr~duct of Ex'ample III 25 Xylene - 8 Sodium salt of p-nonylphenoxy- j pentaethoxy sulfuric acid 15 Isopropallol ' 31 Methanol , 6 ' Water 15 This is a solùtion of very low pour point which is suitable - for use as a demulsifier in oil fiel'ds where ambient temperatures are wel'l below freezing.
.

l~ EXAMPLE C
wt. %
`, 15 , Product o Example'III 31.3 'i~ Isoprop,anol 3I.2 l .
hmmonium, nonylp~enox-yethoxy~sul~ate 15.6 Sodium- acetPte O . 2 Water ~ , 21.7 ' ~ ' Among procedures which'have'been found useul in selecting e~fective micellar TFSA solutions for this use, one involves a determination of oil displacement eficiency from prepared oil-containing rock cores-in e~uipment described below. A tube of 2 ~ glass or transparent poiymethacrylate ester, having an inside diamcter of ab~out 3,5 cm (l~ in.~ and a len~th of about 45 cm (18 ,), lS fitted~with i~nl'et connectlons and appropriate'valves at each~end. The tube is mounted vertically on a rack in an'air bath equlpped with a'fan, heater and thermostat which allows selection and maintenance'of te'mperatures in th'e range of between ,~ 30 ~ : ~
~' ~ about 25 - 1309,C. ' ~ ' ,, ~ :: .
. "
',,'` ' -37-.~,, . . ' .
`, .
,.:, . . .
, .... . .

`" 1153;~7Z ' l To ~elec~ n erfectivc ~nicellar '1`1'SA sollltiol- ror ~Ise in a given oil foL~ation, samples of the oil, of the producing rock formation and of the water ~o be used in the flooding operation were obtained. The formation rock is extracted with toluene to remove oil, is drled and is then ground in a ball mill to the point where a large percentage passes a 40 mesh sieve. The fraction between 60 and l00 mesh in size is ret'ained. The tube described above is removed from the alr bat1l, opene~ and, after insert'ion of a glass wool retainer at the lower end, is packed ' with the ~round formation rock. The tube is tapped gently from time-'to-time during filling to ensure close packing and is`visuaIly inspected to assure absence of voids.
The.tube'is then returned to the air bath,~connected to the inlet tubing, the temperature is adjusted to the oil formation temperature and water representative of that produced from the formation is admitted slowly through the bottom line from a callbrated reservo1r in an amount just sufficient to fill'the packed~rock~plug~in the''tube.~ ~This volume'is determined from the calibratlons~and is~ referred~to as the'"pore vol~me", being that ~2~ vo~lume o~f water j~ust sufficient'to'flll the por`es or interstices of~the paclced plug~rock.
The upper lin~ to ~he reservoir is then connected to a : :
cal~brated reservQir contalning the oil representing that ~rom the~f~ormation~to be f1Ooded~ By proper manipulation of valves, 5~ the line~is~fil1ed~with oll which is then slow~y pumped into the core from the~reservoir~ a~ter th'e lower valve'is opened to allow displacement of the ~ormation~water'.
As breakthrough~of oil at the'bottom is noted, pumping is stopped and the`~vgluune of oll introduced into~the' sand is deter-- 30 ~mined from the~'reservoir readings. ~This'is referred to as the ' volume'of'oil in place.'~ ~he'tube'o~ sand containing oil is then , ~ .

' .

1~3;~72 1 left in the air bath at the ~emperature of the formation for a period of three days to allow establishment of equilibrium between the ground fonnation rock and the oil with respect to adsorption of oil constituents on the rock and lowering of interfacial tension. The tlme allowed for,,equilibrium may be varied widely.
At higher temperatures, the time required ~o reach equilibrium is probably reduced. Usually, for comparative tests, three days are allowed'to age.'the oil-rock plug.. Results with 'this procedure closely simulate`work with actual cores of oil-bearing rock.
'~10 The:oil and wat'er samples used for test:purposes are prefer-ably taken under an inert gas such as h;gh purity-nitrogen, and , ' are maintained out of contact with'air during all miniuplat-ions .' : . . . .
in o.rder to prevent oxidation o the oi~ a~d concomitant intro-~
duction of spurlous polar, surrace-active constituents in the 5: oil. At this point, ,the;rock-oil: system simulates the original , oil~formatio~ before~ prLmary:~producti~on oil has.com enced-ànd well before~any~se~condary~waterflood o~peration.
The~'up'p~er:~inl'et~line~:'to~the~;'tube is now'connected to the s~ample~of:watèr:used~in~the floàding of the oil formation and, by ~, ~ means~,o~ a~:syringe pump or similar very small vblume positive di'splacement pump~,'the'water is~pumped into t~e sand body from : . the`t~ap~to.displace luids out of the~bottom tubin~:connection ::in~to~a~calibrated receivsr, ~The'pumping rate is-adjùsted to one , 9 mulsting~the~ratè~of~fl'ood~water advance in an actual operation, which~'is u~sually in:~a~r~ange of~1~to 50 c~ psr day. ' Pumping is ,ma~in:t:aine-di~st'~his r,ate~:until two pore volumes of`water have been pumpsd~thr~ough:,~'the~;`sand.~
The volumes~of~fluids colleeted in the'receiver are measured aDd~the~relative~amount of'~oil:and water displaced from the rock 30~ sàmple~'are~'det'ermined and:recorded. Of special interest is.the -volume'o'f~oil`di~splac~ed as~:a fraction of the original pore`volume.

"~ , _3~_ , . . -,. .
, .

~ 27 Z
l Tllis inforlllat:ion may be vie~!;?d as an indication of the approximateperc~nt,~e of oil originally in pla~e which is pro(l~lced by natural water drive following drilling of a well into the rock formation iollowed,by the primary phase of field production carried to the approximate economic limit.
Following this step, one to thrce additional pore volumes of water containing the TFSA micellar solution to'be tested are pumped s.lowly th.rough the plug and the volumes of a~ditional oil and water displaced are de'termined. Typically, where such an initial "slug" o micel~lar TFSA solution is in~roduced, it may be .~ ` . .
. contained in a volume of fluid rangi.ng from 1% to 100% of the pore volume,' bùt mos~t frequently it will be'in a slug volume-'of 10% to 50% of pore volume.' After this flnal~displacement step, the~produced.oil and 5~ . water are agaln~measured. By~comparlng the amount of:oil produced by~this additlonal~injection~of water~containing:, or preceded.by a~solutLon,~of~micellar~TFSA~sollltion:wlth~'the`'amount produced when~thé`~`same~vol ~ e~'of:water'~containLng~no TFSA solution is . ~:
ècted,~ one:~can:~e~aluate'the~effectiveness of~the partic~lar ..micellar:TFSA~so~lution;~us~ed~for enha'nclng~the recovery of additional oil:~over 'and above`~hat obtained:by~`ordinary waterfloodin~
Ge~erally, six or~more sand columns of the kind d~ac~ib~d : above:~are'mo~nted;in.the~hea~ed.air bath. Test~of a given miceIlar ''TFSA~solut~ion~ls~then~run in~t~riplicate, using.identical conditiQns conc~entrations,~s~imwltane;ously- with`~hrqe blank tests run similarly~but vithout -d~dition Oe mfcellar~TFSA solution to the The~:compo~si~ion~of Example'C~was~t~st~d by this.procedure ; with;~'t~e~'followi~g~conditions~
30~ :Oil ~ East Tex'as Fîel'd . API Gravity approximatel'y`40.'4' 4'0s' :"

.7 Z

ter -- ~lixed w~L~r u~d in rlc)od o~erations Ai~ th T~mperature -- 150F (Same as fo~m~ltioll temperature~
Oil was, displaced by p~nping two pore volumes of water into the sand. After measuring the'volumes of oil and water produced through the bottom'line,, a further 0-.2 pore volumes of water!
containing 3,500 ppm of the composition of Example C was injlcted followed by 2.8 ~olumes of water containing 200 ppm of the com-position of Example ,C. Measurement of ~.he vol~lmcs of oil and ' water produced were read after each 0.2 po,re vol~mes of water was : 10 injected. . '-.
~ , Results of this tes~ at the' points:'of 2,3 and 5 pore'volumes .: -of injected water are given in the table:bel~ow wh'erein averag~es o~f three duplicate'd:et'erminations are'pres'ented.
Oil:Recovery as %~of 5~ Oi'l''in Pl'ace' '~
Composition of Ratio of Increment : Example,C : of Oil Production : -Added to:Water After:Initial 2 Po:re Volumes ~P.V.) :No;¢hemical after Initial- P.V. Chemical/
of,Water'~Injected~ 'Addi't'ion:~' 2 P.~.' of Water No Chemical 3~ `43.2~ '46.2 2.0 : 5 ~ 46 . 0~ 50. 0: . L~ 68 .Use of~ the compo~sLtion of Example C in the amounts given ::: above resulted in the productlo~ of loa% more oil ~ram l~jection o~ one~,incremental~pore~,volume of water than~was~ produced by in~;ection~a~lone~:;a'nd`~ave~ 68% more~oll after three'inc,re-mental~;~pore.volumes:of~t~reat;èd:water inj~:ection~ .~
' Although the invention:~has been described in terms,of specified~embodi~ents.which~are'set forth in deta'il, it should be un.dèrq~tood:t~:at~sthis~is by illu~stration on.ly and that thè'inven-t~ion~.is~not~n:ec';e~ssar~ily ~limited~thereto, since'alternative ~ ;.emb~'dimen:ts~and oper~ating~teehniques wi'll become'apparent to 3:~ t~ho~e'skilled in:'the~'art in~view o'f the discl'osure.' 'Accordingly, modlf~ication .~are~ ontemplated whi'ch'can be made'without.departing ~: rom.~he spirit of the described inv~n~ion.

. J
J

Claims (109)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a micellar solution of a thin film spreading agent, said micellar solution comprising: (1) from between about 5% and about 75% by weight of a polyepoxide condensate of at least one of: (a) a polyalkylene oxide adduct of a fusible, water-insoluble organic aromatic hydrocarbon solvent-soluble synthetic resin, wherein said resin has from between about 4 to about 15 phenolic groups and is an alkyl or cycloaliphatic substituted phenol-aldehyde condensate of an ortho- or para-substituted phenol and an aldehyde, said condensate resin being thereafter further condensed with an alkylene oxide containing less than about five carbon atoms in an amount equal to at least one mole of alkylene oxide per phenolic moiety of said resin, the weight ratio of oxide to condensation product in a solvent-free state being between about 1-to-10 and about 10-to-1; and (b) a polyether polyol having the formula:

wherein:
A is an alkylene oxide group, -CiH2iO-;
O is oxygen;
i is a positive integer no greater than about 10;
j is a positive integer no greater than about 100;
k is a positive integer no greater than about 100;
N is nitrogen;
R1 is one of hydrogen, a monovalent hydrocarbon group containing less than about C11, or [ALH];
L is a positive integer no greater than about 100;
R is a hydrocarbon moiety of a polyol, a primary or secondary amine, a primary or secondary polyamine, a primary or secondary amino alcohol, or hydrogen; and m + n is no greater than about 4 when R is other than hydrogen and one of m and n is zero and the other is unity when R is hydrogen, said condensate, at about 25°C: (A) having a solubility in water and isooctane of less than about 1%, by bolume; (B) having a solubility parameter from between about 6.8 and about 8.5; and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm;
(2) from between about 2% and about 30% by weight of a hydrotropic agent having one of the formulas:
(A) X - Z
wherein X is an alkyl, alicyclic, aromatic alkylalicyclic, alkylaryl, arylalkyl, alicyclialkyl, heterocyclic or substituted heterocyclic radical having 2 to 13 carbon atoms; and wherein Z is one of: ??OH;
; ; ??COOH; and ??OCH3; and U and V are hydrogen or hydro-carbon substituents;
(B) -X-Y-R - (Z)n~
wherein:
Z is one of -OH; ; ; ; ??COOH; and ??OCH3;
X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic or substituted heterocyclic radical having 2 to 12 carbon atoms;
R is a member selected from the class consisting of, -CH2-, -C2H4-, -C3H5=, -C3H6, and ;
n is either a one or two integer, the integer dependent upon the selection of R; and U and V are hydrogen or hydrocarbon substituents, and Y is a member selected from the class consisting of:

, , , , -O-, and -S-;

(3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15% and about 90% by weight, water.

2. The method of Claim 1 wherein said alkylene oxide is present in said adduct in an amount from between about 1 and about 5 moles per phenolic moiety in said resin.

3. The method of Claim 1 wherein the polyepoxide is:

where n is zero or a positive integer of less than about 6.

4. A method for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a micellar solution of a thin film spreading agent, said micellar solution comprising: (1) from between about 5% and about 75% by weight of a polyepoxide condensate of resinous polyalkylene oxide adducts and polyether polyols, said condensate, at about 25°C:
(A) having a solubility in water and isooctane of less than 1%, by volume; (B) having a solubility parameter from between about 6.8 and about 8.5; and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm; (2) from between about 2% and about 30% by weight of a hydrotropic agent comprising a semi-polar hydrogen bond forming compound containing at least one of oxygen, nitrogen and sulfur and from between about 2 and about 12 carbon atoms;

(3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15% and about 90% by weight, water.

5. The method of Claim 1 or 4 wherein the hydrotropic agent is an alcohol.

6. The method of Claim 1 or 4 wherein the hydrotropic agent is an hydroxy ester of a polyol.

7. The method of Claim 1 or 4. wherein the hydrotropic agent is an aldehyde.

8. The method of Claim 1 or 4 wherein the hydrotropic agent is a semi-polar oxygen-containing compound capable of form-ing hydrogen bonds.

9. The method of Claim 1 or 4 wherein the hydrotropic agent is an amine.

10. The method of Claim 1 or 4 wherein the hydrotropic agent is a carboxy amide.

11. The method of Claim 1 or 4 wherein the hydrotropic agent is a phenolate.

12. The method of Claim 1 or 4 wherein the amphipathic agent is hydrophobic hydrocarbon residue-containing composition where the hydrocarbon is aliphatic, alkylalicyclic, aromatic, arylalkyl or alkylaromatic.

13. The method of Claim 1 or 4 wherein the amphipathic agent contains an uninterrupted chain of from between about 10 and about 22 carbons.

14. The method of Claim 1 or 4 wherein the amphipathic agent is an anion-active soap.

15. The method of Claim 1 or 4 wherein the amphipathic agent comprises sodium cetyl sulfate.

16. The method of Claim 1 or 4 wherein the amphipathic agent comprises ammonium lauryl sulfonate.

17. The method of Claim 1 or 4 wherein the amphipathic agent comprises ammonium di-isopropyl naphthalene sulfonate.

18. The method of Claim 1 or 4 wherein the amphipathic agent comprises sodium oleyl glyceryl sulfate.

19. The method of Claim 1 or 4 wherein the amphipathic agent comprises mahogany or green sulfonates of petroleum, petro-leum fractions, or petroleum extracts.

20. The method of Claim 1 or 4 wherein the amphipathic agent comprises sodium stearamidoethyl sulfonate.

21. The method of Claim 1 or 4 wherein the amphipathic agent comprises dodecylbenzene sulfonate.

22. The method of Claim 1 or 4 wherein the amphipathic agent comprises dioctyl sodium sulfo-succinate.

23. The method of Claim 1 or 4 wherein the amphipathic agent comprises sodium naphthenate.

24. The method of Claim 1 or 4 wherein the amphipathic agent comprises cetyl pyridinium chloride.

25. The method of Claim 1 or 4 wherein the amphipathic agent comprises stearamidoethyl pyridium chloride.

26. The method of Claim 1 or 4 wherein the amphipathic agent comprises trimethyl-heptadecyl ammonium chloride.

27. The method of Claim 1 or 4 wherein the amphipathic agent comprises dimethyl-pentadecyl sulfonium bromide.

28. The method of Claim 1 or 4 wherein the amphipathic agent comprises octadecylamine acetate.

29. The method of Claim 1 or 4 wherein the amphipathic agent comprises 2-heptadecyl-3-diethylene diamino-imidazoline diacetate.

30. The method of Claim 1 or 4 wherein the amphipathic agent comprises the oleic acid ester of non-aethylene glycol.

31. The method of Claim 1 or 4 wherein the amphipathic agent comprises the stearic acid ester of polyglycerol.

32. The method of Claim 1 or 4 wherein the amphipathic agent comprises an oxyethylated alkylphenol.

33. The method of Claim 1 or 4 wherein the amphipathic agent comprises an alcohol ether of a polyethylene glycol.

34. The method of Claim 1 or 4 wherein the amphipathic agent is anionic.

35. The method of Claim 1 or 4 wherein the amphipathic agent is cationic.

36. The method of Claim 1 or 4 wherein the amphipathic agent is nonionic.

37. The method of Claim 4 wherein the solubility parameter at about 25°C of the polyepoxide condensate is from between about 7.1 and about 7.9.

38. A method of recovering oil from an oil-bearing forma-tion into which a well bore extends, comprising the steps of: (I) generating steam at the surface, (II) supplying said steam to said oil-bearing formation by way of said well bore; (III) supplying a micellar solution of a thin film spreading agent to said oil-bearing formation to inhibit the production of oil-water emulsion as a result of the interaction of said steam with the oil and water in the formation said micellar solution comprising:
(1) from between about 5% and about 75% by weight of a polyepoxide condensate of resinous polyalkylene oxide adducts and polyether polyols, said condensate, at about 25°C: (A) having a solubility in water and isooctane of less than about 1%, by volume; (B) having a solubility parameter from between about 6.8 and about 8.5;
and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm; (2) from between about 2% and about 30%
by weight of a hydrotropic agent comprising a semi-polar hydrogen bond forming compound containing at least one of oxygen, nitrogen and sulfur and from between about 2 and about 12 carbon atoms;
(3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15%

and about 90% by weight, water; and (IV) recovering from said formation oil and water which was subjected to the action of said steam.

39. A method of breaking petroleum or bitumen emulsions of water comprising contacting the emulsion with a sufficient emulsion-breaking amount of a micellar solution of a thin film spreading agent, said micellar solution comprising: (1) from between about 5% and about 75% by weight of a polyepoxide condensate of resinous polyalkylene oxide adducts and polyether polyols, said condensate at about 25°C: (A) having a solubility in water and isooctane of less than about 1%, by volume; (B) having a solu-bility parameter from between about 6.8 and about 8.5; and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm; (2) from between about 2% and about 30% by weight of a hydrotropic agent comprising a semi-polar hydrogen bond forming compound containing at least one of oxygen, nitrogen and sulfur and from between about 2 and about 12 carbon atoms; (3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15% and about 90% by weight, water.

40. In the method of preventing the formation of emulsions of an aqueous phase and a petroleum oil or bitumen phase, the improve-ment comprising: contacting said petroleum oil or bitumen phase prior to or coincident with its contact with the aqueous phase with an effective emulsion preventing amount of a micellar solution of a thin film spreading agent, said micellar solution comprising:
(1) from between about 5% and about 75% by weight of a polyepoxide condensate of resinous polyalkylene oxide adducts and polyether polyols, said condensate, at about 25°C: (A) having a solubility in water and isooctane of less than about 1%, by volume; (B) having a solubility parameter from between about 6.8 and about 8.5; and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm; (2) from between-about 2% and about 30%
by weight of a hydrotropic agent comprising a semi-polar hydrogen bond forming compound containing at least one of oxygen, nitrogen and sulfur and from between about 2 and about 12 carbon atoms;
(3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15% and about 90% by weight, water.

41. In the method of breaking or preventing emulsions of water in bitumen during the recovery of bitumen or heavy oil from tar sands and subterranean deposits by steaming, flooding, and combinations thereof, the improvement comprising: contacting said bitumen or heavy oil with a micellar solution of a thin film spreading agent, said micellar solution comprising: (1) from between about 5% and about 75% by weight of a polyepoxide conden-sate of resinous polyalkylene oxide adducts and polyether polyols, said condensate, at about 25°C: (A) having a solubility in water and isooctane of less than about 1%, by volume, (B) having a solu-bility parameter from between about 6.8 and about 8.5; and (C) spreading at the interface between white, refined mineral oil and distilled water to form a film having a calculated thickness no greater than about 20 Angstroms, at a spreading pressure of about 16 dynes per cm; (2) from between about 2% and about 30% by weight of a hydrotropic agent comprising a semi-polar hydrogen bond forming compound containing at least one of oxygen, nitrogen and sulfur and from between about 2 and about 12 carbon atoms; (3) from between about 2% and about 30% by weight of an amphipathic agent having at least one radical having from between about 10 and about 64 carbon atoms per molecule; and (4) from between about 15% and about 90% by weight, water.

42. The method of Claim 38, 39 or 40 wherein said alkylene oxide is present in said adduct in an amount from between about 1 and about 5 moles per phenolic moiety in said resin.

43. The method of Claim 38, 39 or 40 wherein the poly-epoxide is:

where n is zero or a positive integer of less than about 6.

44. The method of Claim 38, 39 or 40 wherein the hydro-tropic agent is an alcohol.

45. The method of Claim 38, 39 or 40 wherein the hydro-tropic agent is an hydroxy ester of a polyol.

46. The method of Claim 38, 39 or 40 wherein the hydro-tropic agent is an aldehyde.

47. The method of Claim 38, 39 or 40 wherein the hydrotropic agent is a semi-polar oxygen-containing compound capable of forming hydrogen bonds.

48. The method of Claim 38, 39 or 40 wherein the hydrotropic agent is an amine.

49. The method of Claim 38, 39 or 40 wherein the hydrotropic agent is a carboxy amide.

50. The method of Claim 38, 39 or 40 wherein the hydrotropic agent is a phenolate.

51. The method of claim 38, 39 or 40 wherein the amphipathic agent is a hydrophobic hydrocarbon residue-containing composition wherein the hydrocarbon residue is aliphatic, alkylalicyclic, aromatic, arylalkyl or alkylaromatic.

52. The method of Claim 38, 39 or 40 wherein the amphipathic agent contains an uninterrupted chain of from between about 10 and about 22 carbons.

53. The method of Claim 38, 39 or 40 wherein the amphipathic agent is an anion-active soap.

54. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises sodium cetyl sulfate.

55. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises ammonium lauryl sulfonate.

56. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises ammonium di-isopropyl naphthalene sulfonate.

57. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises sodium oleyl glyceryl sulfate.

58. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises mahogany or green sulfonates of petroleum, petroleum fractions, or petroleum extracts.

59. The method of Claim 38,39 or 40 wherein the amphipathic agent comprises sodium stearamidoethyl sulfonate;`

60. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises dodecylbenzene sulfonate.

61. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises dioctyl sodium sulfo-succinate.

62. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises sodium naphthenate.

63. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises cetyl pyridinium chloride.

64. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises stearamidoethyl pyridium chloride.

65. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises trimethyl-heptadecyl ammonium chloride.

66. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises dimethyl-pentadecyl sulfonium bromide.

67. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises octadecylamine acetate.

68. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises 2-heptadecyl-3-diethylene nonaethylene imidazoline diacetate.

69. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises the oleic acid ester of glycol.

70. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises the steric acid ester of polyglycerol.

71. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises an oxyethylated alkylphenol.

72. The method of Claim 38, 39 or 40 wherein the amphipathic agent comprises an alcohol ether of a polyethylene glycol.

73. The method of Claim 38, 39 or 40 wherein the amphipathic agent is anionic.

74. The method of Claim 38, 39 or 40 wherein the amphipathic agent is cationic.

75. The method of Claim 38, 39 or 40 wherein amphipathic agent is nonionic.

76. The method of Claim 41 wherein the alkylene oxide is present in said adduct in an amount from between about 1 and about 5 moles per phenolic moiety in said resin.

77. The method of Claim 41 wherein the epoxide is:

wherein is zero or a positive integer of less than about 6.

78. The method of Claim 41 wherein the tropic agent is an alcohol.

79. The method of Claim 41 wherein the tropic agent is an hydroxy ester of a polyol.

80. The method of Claim 41 wherein the tropic agent is an aldehyde.

81. The method of Claim 41 wherein the hydrotropic agent is a semi-polar oxygen-containing compound capable of forming hydrogen bonds.

82. The method of Claim 41 wherein the hydrotropic agent is an amine.

83. The method of Claim 41 wherein the hydrotropic agent is a carboxy amide.

84. The method of Claim 41 wherein the hydrotropic agent is a phenolate.

85. The method of claim 41 wherein the amphipathic agent is a hydrophobic hydrocarbon residue-containing composition wherein the hydrocarbon residue is aliphatic, alkylalicyclic, aromatic, arylalkyl or alkylaromatic.

86. The method of Claim 41 wherein the amphipathic agent contains an uninterrupted chain of from between about 10 and about 22 carbons.

87. The method of Claim 41 wherein the amphipathic agent is an anion-active soap.

88. The method of claim 41 wherein the amphipathic agent comprises sodium cetyl sulfate.

89. The method of Claim 41 wherein the amphipathic agent comprises ammonium lauryl sulfonate.

90. The method of Claim 41 wherein the amphipathic agent comprises ammonium di-isopropyl naphthalene sulfonate.

91. The method of Claim 41 wherein the amphipathic agent comprises sodium oleyl glyceryl sulfate.

92. The method of Claim 41 wherein the amphipathic agent comprises mahogany or green sulfonates of petroleum, petroleum fractions, or petroleum extracts.

93. The method of Claim 41 wherein the amphipathic agent comprises sodium stearamidoethyl sulfonate;

94. The method of Claim 41 wherein the amphipathic agent comprises dodecylbenzene sulfonate.

95. The method of Claim 41 wherein the amphipathic agent comprises dioctyl sodium sulfo-succinate.

96. The method of Claim 41 wherein the amphipathic agent comprises sodium naphthenate.

97. The method of Claim 41 wherein the amphipathic agent comprises cetyl pyridinium chloride.

98. The method of Claim 41 wherein the amphipathic agent comprises stearamidoethyl pyridium chloride.

99. The method of Claim 41 wherein the amphipathic agent comprises trimethyl-heptadecyl ammonium chloride.

100. The method of Claim 41 wherein the amphipathic agent comprises dimethyl-pentadecyl sulfonium bromide.

101. The method of Claim 41 wherein the amphipathic agent comprises octadecylamine acetate.

102. The method of Claim 41 wherein the amphipathic agent comprises 2-heptadecyl-3-diethylene diamino-imidazoline diacetate.

103. The method of Claim 41 wherein the amphipathic agent comprises the oleic acid ester of nonaethylene glycol.

104. The method of Claim 41 wherein the amphipathic agent comprises the steric acid ester of polyglycerol.

105. The method of Claim 41 wherein the amphipathic agent comprises an oxyethylated alkylphenol.

106. The method of Claim 41 wherein the amphipathic agent comprises an alcohol ether of a polyethylene glycol.

107. The method of Claim 41 wherein the amphipathic agent is anionic.

108. The method of Claim 41 wherein the amphipathic agent is cationic.

109. The method of Claim 41 wherein the amphipathic agent is nonionic.