CA1152852A - Micellar solutions of thin film spreading agents comprising resinous polyalkylene oxide adducts - Google Patents

Abstract

TITLE: MICELLAR SOLUTIONS OF THIN FILM SPREADING
AGENTS COMPRISING RESINOUS POLYALKYLENE OXIDE ADDUCTS

ABSTRACT OF THE INVENTION
The invention provides a homogeneous, micellar solution of a water-insoluble thin film spreading agent, comprising: (a) from between about 5% and about 75% by weight of resinous polyalkylene oxide adducts; (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

~5;2~35Z
.
BACKGROUND OF THE INVENTION
1. 'l'IELD 0~ T~IE INVL~'N'rlON: The invention rclates to a ncw ' and irnproved micellar solutlon of a thin Eilm'spreading agent -' comprising resinous polyalkylene'oxide adclu~ts wlli'ch'is particularly useful for breaking or preventing petroleum emulsions. More specifically, the invention relates to a composi~ion in which water replaces all or a substantial part of the organic solvents formerly required for preparation of liquid solutlons of this interfacially active compound'.

2. DESCRIPTION OF THE PRIOR ART:- One of the principal uses ~ .
of the preselit composition is in the'~reaking~oE petroleum emulsions to permit the separation thereo into two bulk phases. Much'of .
the crude p~troleum oil produced throughout the world is accompan-ied by some water or brine which'originates in or adjacent to the geological formation from which'th;e oil is produced. The amount of aqueous phase àccompanying the oil may vary from a trace to a very large'percentage'of the total fluid produced. Due'to the natural occurrence in most petrolewm of oil-soluble or dispersible : emulsifying agents, much'of the'aqueous phase produced with oil is emulslfied therein~ forming. stable water-in-oil émulsions, The-literature contains numerous references to such emulsions, the problems resulting from their occurrence, and the methods .
employed to break tllem and~separate salable yetroleum. See, for example, "The Technology of Resolvlng Petroleum Emulsions" by L.
T. Monson and R. W. Stenzel> p. 535 et seq ~n _o loid Chemi ry Vol VI, Ed. by Jerome Alexander, Rheinhold Publishing Corp., New York (1946) and "Interfacial Eilms Affecting the Sta4'ility o~' Petroleum'Emulsions" by Chas. M. Blair, Jr. in Chemis y nd Industry (London), p. 538 et seq (1960~. ~
Early demulsifiers used to resolve petroleum'emulsions were water-soluble soaps, Twitchell reagents, and sulfonated glycerides.
These products were'readily compounded with water to form easily 2~35~
purnpable liquids and were cl)nveniently applied by p~npin~ into f1OW l;nes at the well head or by washi.ng down the casing annulus with water to colT~ingle wlth well fluids prior to their flow to the surface. These products, however, were effective only at relatively high concentrations and their use added substantialiy to the cost of production.
Some time ago, it was discovered that certain lig1ltly sul- -fonated o1ls, acetylatecl caster oils and various polyesters, a7l of which were insclluble'in water but soluble in alcohols and aromatic hydrocarbons, were much more effective in breaking emulsions. Accordingly, essent1ally all cornmercial demulsifier devélopment has led to production of agents which are insoluble in both water and petroleum oils and have other properties to be described below which cause them to spread at oil-water inter-faces to form very thin, mobile films which displace any emulsify-ing agent present in the oil to allow coalescence of dispersed water droplets. Generally, such interfacially active'compounds are hereafter referred to as Thin Film Spreading Agents, or "TFSA's".
In the past, these have had to be compounded with and dissolve~
in alcohols or highly a~omatic hydrocarbon solvents in order to produce readily applie'd liquid compositions. A wide variet.y'of-such compositions are required to treat the many'different emul-sions encountered throughout the world.
~lile prese-nt TFSA compositions are highly effective, being, perhaps, up to fifty to a hundred times more'effective'per unit volume than the original water-soluble demulsifiers, they suffer serious practical deficiencies because of their solubility charac-teristics. For example, alcohols and the aromatic hydrocarbons, which are required for preparation of liquid> pumpable compositions, are quite expensive, today approaching in cost that of the active c1cmulsifier in~rc~icnt itself. 1urther, such solvents are fla~-, ~1~;28~Z
l - mable and thus create safety problems and entail more expense in sllipping, storing alld use. rrhe low flash point Elalnmability can be improved by using high boiling aromatic solvents, but these are increasingly rare, expensive and dangerous from the standpoint of carcinogenicity and dermatologlcal effects.
Still further, present demulsifiers cannot generally be used in a subterranean oil or gas well, inject1on well, or the like, since ~hey cannot be washed down with either water (or brine) or a portion of the produced o1l, and, ~eing v;scous liquids w11ich are required in very ~small amounts, théy cannot be reliably an~
continuously delivered several thousand feet down at the fluid level in a typical well without use of elaborate and expensive delivery ~eans.
Other-applications of TFSA compos1tions would be acilitaLed i they were readily solubIe or dispersible in water. For exanple, much heavy, viscous oil is produced in the United States by steam injection procedures.~ Typically, wet steam is injected i~to the oil producing strata for several weeks in order to heat the oil, lower its viscosity and increase reservoir energy. Steam injec--tion is then stopped and oil is f10wed or pumped from the bore hole which was used for steam injection. Much of the t~ater resulting from condensation of the steam is also produced w1th the oil in emulsified form. Since emulsions are more viscous than the external phase at the same temperature, and thus crea~e increased resistance to flow, product1vity of the steamed well~
can be improved by injecting a water-soluble demulsiier into ihe wet steam during thé steam injection period to prevent emulsion formation. See, or example, U.S. Patent 3,396,792, dated Apr~l l, 1966, to F. D. Muggee. At present, the requirement of water solubi]ity scriously lilnits the chvice of de~lulsifiers for use in steam or water injection to the relatively inefficient composi_ions.

As disclosed in my co-pending Canadian applications, Serial Number 353,251, filed June 3, 1980 and entitled "Method Of Recovering Petroleum From A Subterranean Reservoir Incorporating A Polyether Polyol", and Serial Number 353,233, filed June 3, 1980, and entitled "Method Of Recovering Petroleum From A Subterranean Reservoir Incorporating Poly-epoxide Condensates Of Resinous Polyalkylene Oxide Adducts And Polyether Polyols", TFSA's are useful in processes for enhanced recovery of petroleum. Used in such processes in-volving displacement of residual oil by aqueous solutions, polymer solutions and other aqueous systems, these agents act to increase the amount of oil recovered. Such action possibly arises from their ability to further water wetting of reservoir rock, lessen the viscosity of the oil-water interfacial layer and promote coalescence of dispersed drop-lets of either water or oil in the ot:her phase.
By use of the present aqueous micellar solutions, the introduction of TFSA into aqueous displacement or flooding fluids is greatly facilitated. In addition, the present mi-cellar solutions, per se, or in combination with other components, can be used as the flooding agent or as a pre-treating bank or slug ahead of other aqueous fluids.
Other applications for the present TFSA micellar solu-tions include their use as flocculation aids for finely ground hematite and magnetite ores during the desliming step of ore beneficiation, as additives for improving the oil removal and detergent action of cleaning compositions and detergents designed for use on polar 85~ `
materials, for the i.mprovem~nt of solvent extractiOn proccsses SUCh C1S tl-ose used in extracLiorl of anti~-)iotic products from aqueous fermentation broths W.~th organ;c solvents, or l-.he ;.mPIOVe-ment of efficiency and phase'separation in the'purificat;on an~
concentration of metals by solvent extract;.on with organic solu tlons of metal complex-f.orming agents, and as assistants to improve the wetting and dying of natural and synthetic fibers 2nd for other proces.ses normally involving the i.nterface be~ween surfaces of differing polar'ty or wetting characteristics, : ' SUMMA Y OF r~ E N'VENTION
A pr,irnary object of the present invention is to provide . aqueous, liquid compositions of these TF~A's having new and useful characteristics which allow production o~: petroleum emulsion breakers and emulsion preventing compositions ~ree or relatively free of highly flammable and environmentally obj ection-able aromatlc hydrocarbons; compositions having a comparativel~
low cost; compositions which 'are'soluble or dispersible'in water and whichJ' therefore, can often be a.ppl-ied by more'effective methods than can existing products; compositions which can be used in enhanced recovery operations such as steam flooding and aqueous medium flooding where present products oannot be readily applied;'and compositions which can be compounded with wa~er-soluble reagents of other types, such as corrosion inhibitors, wetting agents, scale inhibitors, biocides, acids, etc., to provide multipurpose compounds for use in solving many oll well completion, yroduction~ transportation and re~fining problems.
In accordance with the'present invention, these airns are accornplished by means oE amphipathic agents which 'are'capable of forming micellar solutions and which'by this mechanism or other undefined actions, combined with 'those of a second es'sential ~;285~

component which will be referred to as a hydrotropic agent, are able to form homogeneous aqueous solutions containing a relative-ly 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 abo,ut 6.8 to about 8.5, with a majority in the range of from between 7.0 and about 7.9; and

3. ~pread~at the interface betw~en whlte, refined mineral:
oil and distilled water to ~orm films having a cal- :
culated thickness no greater than about 20 Angstroms at a spreading pressure of about 16 dynes per cm. :
TFSA compositions having these properties are generally . :
: organic polymers or semi-polymers having molecuIar weights ranging from about 2!000 to about 100,000 and having structures ~0 - containing a multiplicity of distributed hydrophilic and hydro-pho~ic moieties~arranged:in linear or planar arrays~whLch make them surface active and lead to their adsorption at oil-water interfaces to form very thin films.
Unlike most commonly encountered surface-active compounds, the presen TFSA appears to be incapable of forming a micelle in either oil or water. The distributed and alternating occurrence of polar and nonpolar or hydrophilic and hydrophobic groups in the molecule apparently prevents the kind of orgranization required for micelle formation and thus impairs dispersion or solution in either water or low plurality organic solvents~
The TFSA's useful in the present invention have the ~52~35~:
previously recited properties:
1. The-_olubility in water a'nd in lso'octane at about 25C is less than ab'out 1% by v_'Lume.
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 graduated cylinder of the type which may be closed with a ground glass stopper.
Thereafter place 99 ml of water in the cylinder, close, place in a 25C water bath until thermal equilibrium O is reached, and remove from the bath and shake vigorously for one minute. Return the sample to the bath for five minutes and then repeat the shaking procedure. Pinally, return the sample to the bath and allow it to stand;quietiy ~or one hour. The cylinder contents should be carefully examined and any cloudiness or opacity of the liquid phase or the appearance of any sediment or undissolved material in the cylinder noted, thus indicating that the sample satisfied the requirement for insolubility in ~0 water~
Isooctane solubill~y is determined similarly by substituting this hydrocarbon for~the water used above.
2.
between about'6'.9 an'd''abo~'t 8'5,- inclusive Methods of determination of solubility parameter are disclosed in Joel H. Hildebrand, "The Solubility of Nonelectrolytes", Third Edition, pgs. 425 et seq.
However, a simplified procedure, sufficiently accurate for quàlification of a useful TFSA composition may be utilized. Components of agiven solubility parameter are generally insoluble in hydrocarbon ~non-hydrogen-'~`
1'~

~i2852 bonding) solvents having a lower solubility parameter than themselves. Therefore, the present composition should be insoluble in a hydrocarbon solvent of a solubility parameter of about 6.8. Since the solubility parameter of mixtures o solvents is an additive func-tion of volume percentage of components in the mixture, test solutions of the desired solubility parameters may be easily prepared by blending, for example, benzene (S~P. 9.15) and isooctane (S.P. 6~85) or LO perfluoro-n-heptane (S.P. 5.7~. ~
A mixture of about 72 par~s of benzene with about ~ .
28 parts of isooctane will provide a solvent having a:
solubility parameter o about 8.5 at room temperature (about 25C). Per~luora-n-heptane has a solubility ~:
parameter of about 5.7 at 25C, so:a mixture o~ 68 parts of this solvent with 32 parts of benzene pro-vides a solvent with a solubility parameter of about : 6.8, or isoocta~e of a solubility parameter 6.85 may :
be used.
~0 When 5 ml of the TFSA~are mixed with 95 ml of an 8.5 solubility parameter solvent at room temperature, a clear~solution should result. ~hen 5 ml of TFSA is mixed with a 6.85 solubility parameter solvent, a cloudy mixture or one showing phase separation should result. Solvent mixtures have a solubility parameter between about 7.0 and about 7.9 may be prepared as described above and utilized in a similar test pro-cedure.
In interpreting the solubility parameter and other tests, it should be recognized that the TFSA consists not of a single material or compound but a cogeneric mixture of products containing a range of products of "~

i285~ .
molecular weights distributed around 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 para-meter tests, very slight appearances of cloudiness or lack of absolute clari~y should not be interpreted as a pass or a failure to pass the criteria. The intent o~ 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 centrifuging, after which the separated non-solvent phase can be removed, any solvent contained in it can be evaporated, and the actual weight or volume o* separated phase can be determined.
3. The TFSA should spread at the interface between distilled water and refined mineral oil to ~orm ilms (0.0020 micrometer? t a fil~ ~res-ur- of about 16 dynes- per cm (0.016 Newton per meter).
Suitable methods of determining film Pressure are disclosed in N. K. Adam, I'Physics and Chemistry of Surfaces", Third Edition, ~
London, 1941, pgs. 20 et seq. and C. ~. Blair, Jr., "Interfacial Films Affecting The Stability of Petroleum Emulsions", ~ (London), 1960, pgsO 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 product or its solution in a volatile solvent has been placed. Since spreading pressure is numerically ,, ~

;28S~
equal to the change in interfacial tension resulting from spreading of a film, it is conveniently deter~ined by making interfacial tension measurements before and after ad~ing a known amount of TFSA to an interface of known area.
Alternatively, one may utilize an interfacial film balance of the Lungmuir type such as that describ-ed by J. H. Brooks and B. A. Pethica, Transactions of t~ (1964), p. 20 et seq, or other ~0 methods which have been qualified for such interfacial spreading pressure determinations.
In determining the interfacial spreading pressure 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 treat:ed with sulfuric acid and other agents to remove nonhydrocarbon and aromatic constituents. Typical of such oils is l'Nujol", dis-tributed by Plough, Inc. This oil ranges in density from about 0.85 to 0.89 and usually has a solubility :~
parameter between about 6.9 and about 7.5. Numerous similar oils of greater or smaller density and viscos-ity are commonly available from chemical supply houses and pharmacies.
Other essentially aliphatic or naphthenic hydro-carbons of low volatility are equally usable and will yield similar value of spreading pressure. Suitable hydrocarbon oils appear in commercial trade as re~ined "white oils", "textile lubricantsl', "paraffin oil", and the like. Frequently, they may contain very small s~ ~
quantities of alpha-tocopherol (Vitamin E) or similar antioxidants which are oil-soluble and do not inter-fere with the spreading measurements.

~0 - lla -sz~
1 .~li'le the existence of Inicelles and of oily or aqueous ~ micellar solutlons have been known for some time (see, e.g., "Surface Activity", Moilliet, Collie and Black, D. Van Nostrand &
Co., New York (1961) ) and are probably involved in many opera~ions involving detergency where either oily (nonpolar) or earthy (highly polar) soil particles are to be removed, their utility in cooperation with hydrotropic agents for the present purposes is an unexpected and unpredictable discovery.
Tn U.S. Patent No. 2,356,205, issued August 22, 1944, to Chas. M. Blair, ~r. & Sears Lehman, Jr., a wide variety of micellar solution.s designed to dissolve'petroleum oils, bitumen, wax, and other.relatively nonpolar compounds are described for : purposes of cleaning oil formation faces and for effecting en-hanced recovery of petroleum by solution thereof. At this early date, however, the use of miceIlar principles was not contem-plated for the pr'eparation of solutions Or the relatively high molecular weight demulsifiers.
~owever, some of the principles disclosed in the above patent, omitting the main objective'therein of dissolving rela-tively large amounts of hydrocarbons, chlorinated hydrocarbons, .
and the li.ke, are applicable to preparatlon of the present com-positions.
The four necessary components of the micellar solutions of TFSA are: ' 1. A mice~le-formin~ a phipathic ~ ent. Such ~ay be anionic, cationic, or nonionic and, if ani.onic or cationi.c, may be either in salt form or as the free acid or free base or mi.xtures thereo.
2. A hydrotropic agent. ~his is a sl~all to medium mole-cular weight semi-polar compound containing oxygen, nitrogen or sulfur and capable of forming hydrogen ~2l3SZ
l bonds. It is believed that such a~cnts cooperate in some manner with the amphipathic agent to form clear or opalescent, stable compositions.
3. Water.

4. TFSA, having the properties recited above.
In addition to these cornponents; the micellar solutions may contain, but are not required to contain, salts, hydrocarbons, or small amounts of other inorganic or organic material. ~uch constituents may be impurities, solvents, or by-products of syntheses used in forming the liydrotropic agent, or may be addi-tions found useful 1n forming the compos1tion of this invention.
As an example of the latter, small amounts of inorganic salts such as NaCl,.Na2SO4, KN03, CaCl2, and the like, are sometimes helpfùl in promoting homogeneity with a minimum of amphipathic ~15 and hydrotropic agents. They may also yield compositions of lower freezing point, a property useful when`the composition is employed in cold climates. Similarly, ethylene glycol, methanol, ethanol, acetic acid, or similar organic compounds may be incor-.
porated into the compositions to improve physical properties such ~2-0 as freezing po1nt, viscosity, and~density, or to 1mprove stability.
; ~ As stated above, the micelle-forming amphipathic agents which may be used in preparing the aqueous solutions herein contemplated may be either cation-active, anion-active, or of the nonelectrolytic type. Amphipathic agents generally have present at least one radical containing about lO or more carbon atoms and not more than about 64 earbon atoms per molecul-e. This is true of the arnphipathic agents employed in the present invention as a component of the vehicle or solvent or dispersant employed in the present compositions. The hydrophobic portions of these agents may be aliyhatic, alicyclic, alkylalicyclic, aromatic, arylalkyl, or alkylaromatic. The preferred type of agents are those in ~ ~2l3SZ
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, dloctyl sodium sulfosuccinate/ sodium naphthenate, and the like. Other suitable sulfonates are disclosed and taught in U.S. Patent No. 2,278,171, issued;February 17, 1942, to De Grotte and Keiser.
Sui~able cation-active compounds include cetyl pyridinium ~chloride, stearamldoethyl pyridinium chloride, trimethyl-heta-decyl ammonium chloride, dimethyI pentadecyl sulfonium bromide, octadecylamine acetate, and 2-heptadecyl-3-diethylene diamino-midazoline diacetate;
Sultable nonelectrolytic amphipathic agents include the oleic acid ester of nonaathylene glycol, the steric acid ester of polyglycerol, oxyethylated alkylphenols~ and long chain alcohol ethers o~ polyethylene glycols.
It is of course, well known that amphipathic compounds are readily and commercially available, or can be readily prepared to exhibit the characteristics of more than one of the above mentioned types. Such compounds are disclosed in U.S. Patent No. 2,262,743, dated November 11, 1941, to De Groote, Reiser and Blair. For convenience, in such instances where a surface-active material may show the characteristics of more than one of the above described types, it is understood that it may be classified under either or both types.

~i2852 The mutual solvent or hydrotropic agents of the solution utilized in the present invention are characterizable as com~
pounds ~ .

- 14a -'~

~;2~5Z -.
1 oE a hydropllobic hydrocarbon resic]ue of colllparatively low mo]ecularweight combined with a hydrophilie group of low mo]eeular weight and are free from surface-active properties. ~he hydrophobie residue may contain from 2 to 12 carbon atoms-and may be alkyl,

5 ' alicyclie, aromatie, or alkyl substituted alieyelie or aromatie, or may be the hydroearbon portion of a hel:erocyclie or hydro-earbon substituted he~erocyelie group. The hydrocarbon residue may have brancbed or normal chain structure, but no braneh may have a length of more than 7 earbon atoms from the point of ~10 attachment to the hydrophilic residue, counting a benzene or ' cyclohexyl group as being equivalent in length to an aliphatie ' chain of three carbon atoms. Where the hydrocarbon residue con-SlStS of not more than 4 earbon atoms,'struct-ures of the normal pri~ary alkyl type are preferred. Where'the residue is'made up ~ of more than four carbon atoms, then structures of secondary and tertiary types are also good where the second and third branehes may be methyl or ethyl groups.
This hydrophobie hydrocarbon residue'is eombined either direetly or indirectly with a hy~rophilie group of one of the following groups~
~a) A hydroxyl group whieh may'be aleoholie, phenolie,' ' or earboxylie;
- (b) An aldehyde group;
(e) A earboxy amide group;
(d) An amine salt group;
(e) An amin~ group; and (f) An alkali phenolate group.
By i'indirectedly combined with one of these groups" is meant -that the hydroearbon residue is combined as by etherifieation, esterifieation, or amidifieation, or the like, with another organie residue which contains not more than four carbon atoms ancl also one or n,~. e of the hydrnpllilic c3roups na ed above, provi~ed `~ that after said combination, at lec st c~r)e of the bydrophile ~roups rcmains free. Specific examples illustratinJ lhis class of compounds are: Ethyl alcohol, n-amyl alcohol, alphaterpineol, p-cresol, cyclohexanol, n-butyralde-hyde, ben~aldehyde, n-butyric acid, ylycol mono-butyrate, propyl lactate, mono n-butyl amine hydrochloride, n-propionamid, eLhylene glycol rnono n-butyl amine hyclrochloride, n-propionamid, ethylene ~ylycol mono n-butyl ether, pyrldine, methylated pyridine, piperidine, or methylatecl piperidines.
The solubilizer (mutual solvent or ilyclrotropic compound above described) is essentially a semi-polar liquid in tile 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 properly desiqnated as semi-polar.
The solubilizer or semi-polar liquid indicated may be illustrated by the formula X -- Z, in which X is a radical having 2 to 12 carbon atoms, and which may be alkyl, aliGyclic, aFomatic, alkylalicyclic, alkylaryl, arylalkyl, or alicyclicalkyl in nature, and may, furthermore, include hetero-cyclic compounds and substituted heterocyclic compounds. There is the - added limitation that the longest carbon atom chain must be less than ei~3ht carbon atoms, and that, in such characteri~ation, cyclic carbon atoms must be counted as one-half. Z represents:

~U /~ --CN/; --COO; or -- OMe ~

where U and V are hydrocJen or a hydrocarbon substituent and Me is an alkalie metal;

e~ N~
/o- /-79 if X is a cyclic teritary amine nucleus;

8S~`

"
if X is a cyclic secondary amine'nucleus.
The semi-polar liquid also may be indicated by the following fo~nula: - X--Y ~ ~~~(Z)n Here X and Z have their previous significance, R ls -~CH2 -, ~ C2H4- , - C3Hs - , - C3H6 or and n is either one or two a-s the choice of R demands. Y is one of the following:
~10 -~ - N - ; - N - C -; C 0-; - 0 - ~ 0 ; -S -.

In general, these hydrotropic agents are l~qulds having di-.
electric constant values between about 6 and about ~6, and have at least one polar group containing one or more atorns of oxygen, 15~ and/or nitrogen. It is signlficant, perhaps, that all of the solubilizers are of types knpwn to be able to form hydrogen bonds. ' --The choice of solubilizer or common solvent and its pro-porti~n in the mixture depends somewhat upon the amphipathic agent used, the amount and kind of TFSA used, and the proportion of water'used, and is best determined by preparing experimental mixtures on a small scale.
In some cases, it i's desirable to include in the solution small amounts of acid, alkali, or inorganic salts, as it has'been found that th~e yresence of these electrolytes ofteri gives solutions having greater stability and a wider range of miscibility with water and organic material. Excess acid, when used, will usually be in solutions containing a cation-active or nonelectrolytic wetting agent, but not exclusively so. Excess alkali, when used, will usually be in a solution contàining anion-active wetting agents, but, again, not exclusively.

~ 2 ~5~' l The resinous polyalkylelle oxide adducts or TFSA utilized in this invention is generally an organic polymer or semi-polymer with an average molecular weight above about 800'and bel'ow about 30,000 and has a structure whi'ch will allow orientation on polar surfaces with much or most of the elements of the molecule 'in a thin plane.' To be effectively adsorbed at oll-water or oil-rock . interfaces and sub$equently to be'desorbed at water-rock interfaces, the TFSA mus~ generally contain constituents which give'it a highly distributed hydrophile and hydrophobe character, and ~without such 'concentrations of either hydrophilic or hy'drophobic groups as to produce water solubiIity or oil solubility, in the ordinary macroscopic 'sense. The TFSA also appears-to diffe'r from former'ly used surfactants in that the' effec~s on oil-wat'er inter-facial tensibns as a function of concentration are limited.
While spreading efficiently at such'interfaces to form thin films with spreading pressures up to about 35 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 littl'e or no tendéncy to stabilize'either oil-in-- water or'water-in-oil emulsions when present in normal use amounts.Usually the TFSA constituents applicable'to the practice of the invention are organic molecules' containing carbon, hydrogen and oxygen, although in some instances they may also contain sulfur, nitrogen, silicon, chlorine, phosphorous or other elements.
Small amo~mts of inorganic material such as alkalies, acids or salts may appear in the compositions as neutralizing agents, catalyst residues or otherwise~ The critical requireménts for the TESA compositions are not so much'compositional as structural and physical. They must be made'up of hydrophilic (polar) moieties, 'usua].ly ones capable of forming hydrogen bonds, s'uch''as hydroxyl, 3S~

1 carbonyl, ester, ether, sulfonium, ami.no, ammonium, phospho or similar hydrogen bonding groups, connected by or'to hy'drophobic groups, such.as alkylene,' alkyl, .c'ycloaklyl, aryl, aryl~ene!' aralkyl, polyalkyLene, polyalkylyne,' c'ombinations of such'groups and such grou.ps containing relatively non-polar substituents, such as hydrocarbon, chlorine, fluorine and the like.' Sometimes the hydrophobic moieties'.are larger and contain more atoms than ; the polar groups in the molecule, having a minimum of two carbon atoms in each'group and up to as many as 36 carbon atoms, although ~ the.actual ratio of s.izes' depends greatly on the'structure'of the hydrophilic moiety. Most commonly, the hydrophobic 'groups will - contain 14 to 22 carbon atoms and will have'linear or sheet-like .. . . .
conformations'allowing for reIatively flat orientation on surfaces.' Polar moieties other than hydrogen bonding ones are not excluded from these compositicns and, indeed, may be'deliberately included in some structures to improve'adsorption and interfacial ' ' spreading tendencies. For example,: quater'nary ammonium groups, ~ while incapable'of for~ling hydrogen bon~dsj can improve'spreading:
:~ and interfacial adsorption -in some applications by way of their 20 . highly ionized form which`lmparts cationic charac-ter to the mole-.
cules in which they occur and, via coulombic repulsion effects, .
' can improve spreading in a film. ~ ' :
Generally, the TFSA constituents will contain at least two each of the required hydrophilic (polar~ and hydrophobic moieties per molecule and commonly will contain many more'of each, The' effective products, however, must'have the three properties' described above.' While, as pointed out.above,' the effective TFS~' may be derived from a wide'variety o che'mical rcactants and may contain numerous different groups or'moi'eti'es, I have'found that particu-.
larly effective'products are'those'wh'ich are`described as a ~;;Z 852 polyalkylene oxide adduct of a fusible, water-insoluble organic aromatic hydrocarbon solvent-soluble synthetic resin, wherein said resin has from between abouk 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 alde-hyde, said condensate resin being thereafter further condensed with an alkylene oxide containing less than above five carbon atoms in an amount equal to at least one mole of alkylene oxide per phenolic moiety of said resin. These adducts must conform to the physical property parameters set forth above.
These compositions are broadly described in U.S. Patent 2,499,365, entitled "Chemical Manufacture", dated March 7, 1950, to DeGroote, et al. These compositions also include materials wherein less than one or two alkylene oxide units may be react-ed with each reactive structural group of the starting resin.
The most common resin is an alkyl ox cycloaliphatic sub-s~i~uted 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 paraformalde-hyde or trioxane, under mildly alkaline or acidic conditions toform 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. This resin is then con-densed, usually with an alkaline catalyst, with an alkyleneoxide or a mixture of alkylene oxides containing 4 or fewer carbon atoms and exemplified by ethylene oxide, propylene oxide, buty-lene oxide, glyceryl chlorohydrin, epichlorohydrin andglycidol.
To be suitable for use in the present process, addition and condensation of oxide must not be carried to the point of pro-ducing water-soluble products. Where ethylene oxide alone is condensed with the resin, the amount added prefsrably will be between one and five moles per phenolic moiety in the resin.

~ii21352 -The actual amount will vary with the size of the alkyl or cyclo-alkylene group attached to the phenol ring as well as, apparent-ly, with the composition and properties of the oil, aqueous phase and xock formation encountered in the method.
Where propylene or butylene oxides or mixtures of one or both of these wi~h ethylene oxide are aondensed with the phenol-ic resin intermediate, generally a greater amount of such oxides may be reacted without leading to extremely polar, water-insol-uble products. In contrast, the amount of epichlorohydrin 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 mixt-~re o~ 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~
The final product should contain at le!ast about one mole of alkylene oxides per phenolic moiety of the resin.
The compositions suitable for practicing the present inven-tion are prepared by reacting formaldehyde or a substance whichbreaks down to formaldehyde under the reaction conditions, a.g., paraformaldehyde and trioxane, and a difunctional, with respect to reaction with formaldehyde,-alkyl phenol, often a crude mix-ture of alkyl phenols for economic reasons, by heating the re-actants between about 100 and about 125C in the presence of a small amount of an acid catalyst such as sulfamic acid or muri-atic acid.or, alternatively, in the presence of an alkaline catalyst such as sodium hydxoxide or sodium methylate and, preferably, under substantially anhydrous conditions, excepting the water produced during the reaction. The aqueous distil~ate which z~s~
1 begins to form is collected and removed from the reaction mixture.
After several ho'tlrs of heating at temperatures slightly above the' boiling point of water, the mass becomes viscous and is permitted to cool to about 100 - 105C. At this point, an aromatic hydro-carbon fraction such as xylené may be'added, and heating is resumed. Further aqueous distillate'bep,ins to Eorm, and heatirlg is continued for an additional number of hours ~mtil at least about one mole`of aqueous distillate ~er mole of the ormaldchyde has been distilled off. Xylene'or other hydrocarbon'which may be distilled with the water is returned to the rea'ction mass. The temperature at the`end of the react~ion reaches' about'l80 - 250C.
The product is permitted to cool to yleld thc' phenol-ormaldehyde condensation product in the aromatic solvent.
The molecular weight of these intermediate'condensation products cannot be ascertained with'certainty, but it is estimated that the resins employed herein should contain from'between about 4 to about 15, preferably from about 4 to about 6, phenolic nuclei per resin molecule. Tilé'solubility o~ the condensation'product in hydrocarbon solvent would indicate'that the'resin is a linear or sheet-like polymer ? thus distinguishing it from the'more co~mon phenol-formaldehyde resins of the insoluble cross-linked type.
Having prepared the intermediate phenol-formaldehyde'produ`cts, the next step is the oxyalkylation of the con-densation products with aIkylene oxide. This is achieved by mixing the'intermediate phenol`-formaldehyde condensation product as is or'contained in the aromatic solven-t with'a small amount of a suitable'catalyst, usually potassium hydroxide or sodium methylate~,` in an autoclave.
The condensation product is heated above 100C, and ethylene`
-30 oxide, propylene`oxide,` butylene`oxide or mixtures of two' or all three of these'oxides, elther as a mixture`or`by sequential 2 ~52"
1 addition of Eirst either one or another of the oxides is charged lnto the'autoclave'until the' pressure is ;n t'he'vic;nity of 75 ~
100 psi.
The reaction mixture is gradually heated~until an exothermic reaction begins. The external heating is then removed, and aIkylene oxide or'oxide rnixt~lre is adcled at such a rate that the temperature is maintained between about 130 - 160C in a pres-sure 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'sub~stantially complete'react'ion'of 'the alkylene oxide.' The'res'ulting product is the'alkylene oxide adduct of an alkyl phenol-formaldehyde condensation product, in ' - which the welght ratio of the oxide'to the condensation product (on a solvent-free basls) is betweeri about l-to-10 and about 10-to-l, preferably between about 1-to-5 and about 3-to-1, and c'ontalnlng at least about one mole~'of alkylene'oxide'per phenolic ; ~moiety of the;resin.
As to the limits'c,f the'variou's constituents of the micellar solutions containing TFSA, the'following will serve'as a guide,~
~20 the~percentages being by weight: ' ' Percent-.
- .
~ ~ ~ TFSA Constituents about 5 to about 75 .
' Hydrotropic Agent ~ about 2 to about 30 Amphi'pathic Agent about 2 to about 30 Water 'about' 15 to about 9 Although the exact function of the electrolytes previously referred to is not completely understood, the effect, in part, may be due'to the'ability to bind water, i.e.', to become'hydrated.
- This suggests'that certain other' materials which are highly hydrophile'in character and clearly difEerentiated from'the' classes of'non'-polar solvents and s'emi-polar solubilizers may be i2~52~` -1 the functional equivalent ol' an electrolyte. Substances of this class which ordirlarily do not dissociate'include'glycerol, ethylene'glycol, digly~erol, s'ugar, glucose, sorbitol', mannitol, and the l;ke.' Also, as stated above, these solutions may con'taln other organic cons~i~uents such'as hyclrocarbons. 'rhcsc requently are used as thinning agents, aæetropic dlstillation aids or reflux ~temperature controllers in the manufacture of the TFSA constituent ~ and may be left -therein when the present miceIlar solutions are prepared-. T the e~tent that such''compounds are'present they aypear to compete~somewhat wi'th the TFSA constituent far micelle space, thus limiting, to som'e'extent, the maximum amount of TFSA
' constituent which can be'brought'into homogeneous solution' , Selection of an eEfective TFSA composition for a gîven'pet-roleum emulsion and determination of the amount required is~
usually made by so-called "bottle'tests", conducted, in a typical sit~ation, as follows ' A sample'of fresh emulsion'is obtained and-lOO'ml portions are poured into each of sever~l 180 ml screw top prescription or similar graduated bottles'. Dilute solutlons (1% or 2%) of var-ious TFSA constituents are preyared in isopropyl alcohol. By means of a graduated pipette, a small volume of a TFSA solution is' added to a bottle.' A similar volume'of each composition lS added to other bottles containing emulsion. The bot't'es are'then closed and transerred to a water bath hel'd at the sarne temperature as that ernployed'in the field treating plant. After reaching this temperature, the bottles are'shaken briskly for several'minutes.
After the'shaking period, the bottles are'place'd upright in the water bath'and allowed to 'stand quietly. Periodically, the volume of the separated water layer is recorded along with'o'bser-vations on'the'sharyncss of the oil-water interface, appearance of the oil and clarity of the water phase. ' --2~-s~
.

After the standing period, which may range from 30 minutes to several hours, depending upon the tempera~ure~ the viscosity of the emulsion and the amount of TFSA compositions used, small samples o~ the oil are removed by pipette or syringe and centri-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 o~ the generally most effective TFSA
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 tes~s should be repeated at lower concentrations until good discrimination is possible.
In practicing the process for resolving petrolsum emulsions of the water-in-oil type with the present micellar solution, such solution ls 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 o~
demulsification procedure to recover clean oil. In t~is pro-cedure, the emulsion is admixed with the micellar TFSA solution, for example, by agitating the tank of emulsion and slowly drip-ping the micellar TFSA solution into the emulsion. In some cases, mixing is achieved - ~5 -5;285;2 . ~
l by heating the emulsi.on whi'l.e driyping in the rnicellar T~SA solu-tion, depending upon the convection'currents in the'emulsion to produce sa~isfactory admixture.' In a third modifica'tion of this type of treatment, a clrculating pulnp withdraws emulsion from, e.g., ~he bottom of the tanlc and reintroduces ~it into the top of :~ 'the tank, the micellar TFSA solution being added, for example, at : the suction side of said c`irculating pump. ' ' ' ~ : . In a second type of treating procedure, the micellar TFSA
;~: solution is introduced in'to the'well fluids at the' wellhead, or10~ at some'point between the wellhead~and the final oil sto.rage' tank, by means of an adjustable.proportiPning mechanism or propor-tiDning pump. Ordlnarily, the~flow of fluids through the subsequent lines and fittings sufflces.to produce the desired degree~of mlxing~ of micel~làr TFSA solution and emulsion, although, in some instances, add1tional~mix1ng devlces may be:introduced into the flow.system. In this general procedure, the system may include' ;.: varlous mechanic~al devlces: for withdrawing free'water, separat1ng ~: : entrained water, or a.ccomplishing quiescent settling of the chemically~treated emulsion. ~Heating devices may likewise~'be~ :~
20~ ' 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~1ntroduce: the micel,lar soIution elther ~:: : periodically or continuously in' d:iluted form into the well and to allow it to:come to the'surface with the'well fluids, and then to : .
flow the chemical-containiDg emulsion through any d~esirable;
surface equipment, such as emp.loyed in the other treating pro.-cedures. This particular type of application is es'pecial'ly useful when the micellar solution is used in connection with acidification of calcareous oil-bearing strata, especially i~
dissolved in the acid employed for ac1dification.

; . ' . ;'' .' sz 1 In all cases, it will !:)e apparent fL^om the forcgoing descrip-tion, the broad process consists simply in lntrodllcing a relatively small proportion of micel'lar TFSA solution into a rel'atively 'large proportion of emulsion, admixing the chemical and emulsion eltller through natural flow, or through special ~pparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles ~rom the mass. ' Besid'es thelr utillty for breaking petroleum emulsions, the present micel'lar TFSA solutions, as mentioned eàrlier, may be used to prevent emulsion formatlon'in steam flooding, in secondary waterflooding, ln acidlzing of oil-producing formatlolls, and th~
llke. '''''''~'' ~'~' Petroleum oils, even after demulslficatlon, may contain substantial amounts of inorganic salts, either in solid form or as small remalning brine droplets.' For this reason, most petroleum oils are desalted prior to refining. The desalting step is ~
effected by adding and mixing with the oil a-ew volume'percentages o~ fresh water to' contact the brine'and salt. In the'absenc~. of demulsi~ier, such added water would also become emulsified with-out effecting its washing actlon. The present mlcellar solutions may be added to the fresh water to prevent its emulsification and to aid in phase separatlon and removal of. salt by the'desaltlng ' process. Alternat;vely, if deslred, they may be aclded to the oil phase as are present aromatic solvent compositions.
Most petroleum oil, al~ong with its accompanylng brines and gases, is corrosive to steel and other metallic structures with whlch lt comes ln contact. Well tubing, caslng, flow lines, separators and lease tanks are often serlously attacked by well fluids, especlally where acidic gasés such as H2S or CO2 are produced wlth the liquids, but also 'in systellls Erce of such gascs.

z~s~

It has been known for some time, and as exemplified in U.S. PatPnt 2,466,517, issued April 5, 1949, to Chas. M. Blair and Wm. F. Gross, that such corrosive attack of crude oil fluids can be mitigated or prevented by addition to the fluids of small amounts of organic inhibitors. Effective inhibitors composi-tions for this-use are usually semi polar, surface active com~
pounds containing a nonpolar hydrocarbon moiety attached to one or more polar groups containing nitrogen, oxygen or sulfur or combinations of such elements. Generally these inhibitors or their salts are soluble in oil and/or water (brine) and fre-quently appear to be able to form micelles in one or both of these phases. Typical inhibitors include amines such as octyl amine, dodecyl amine, dioctodecyl amine, butyl naphthyl amine, dicyclohexyl amine, benzyl dimethyldodecyl ammonium chloride, hexadecylaminopropyl amine, decyloxypropyl amine, mixed amines prepared by hydrogenation of nitrile derivatives of tall oil fatty acids, soya acid esters of monoethanol amine, 2-undecyl, l-amino ethyl imidazoline and a wide variety of cationic nitro-gen compounds of semi-polar character. Also eifective i~ some applicatLons are nonyl succinic acid, diocty}naphthalene sul~
fonic acid, trimeric and dimeric fatty acids, propargyl alcohol, mercaptobenzothiozole, 2, 4, 6-trimethyl-1, 3, 5-tithiane, hexadecyldimethyl benzimidazolium bromide, 2-thiobutyl-N-tetro-decylpyridinium chloride, tetrahydronaphthylthiomorpholine, and the like.
In contrast to the TFSA, corrosion inhibitors appear to function by forming on the metal surface strongly adherent, thick, closely packed films which pxevent or lessen contact of corrosive fluids and gases with the metal and interfere with ionic and electron transfer reactions involved in the corrosion process.

~"

~ 85 Z
1 Corrosion inhibitors are quite common'ly introduced down the casing annulus of oil wells where'they commingle'with the well fluids before their travel' up'the'wel'l tubing and thus can effec-tively preven~ corrosion of wel:l equipment. Whe're corrosive -5 attack occurs at the surface, the' inhibitor may be introduced at or near .the well head> allowing it to adsorb on the flow lines and surface equipment to insure protection.
Addi.tion of inhibitor at either downhole or surface-locations may be combined conveniently with'demulsifier addition since the 1.0 latter is also frequently introduced in one of these locations.
. Inhibitors such as those mentioned above> may generally be : incorporated into the TFSA m1ce1lar solutions, replacing:a port~on o or~in-addltion to the-TFSA constituent.' Also, since -~
many of these'inhi'bitors`are themse.lves rnicelle-'forming amphi-pathic agents> they may be included in the micellar solution as such~ rep].acing other amphipathic agents which might be otherwise ut~l:ized. Combining the~micellar solutlon with corrosion 1ohibitor permits more.economic 'chemical treatment by'reducing inventory to .
; one compound> requiring only one chemical injection system rather than two and lessening the'labor and~supervision required. -Still another important effect of uslng the micellar solution of TFSA and corrosion inhibitor.results from the prevention of emulsification by the'inhibitor. Frequently> it has been found that inhibitor in the amount required for effective protection 25 causes the formation of very refractive'emulsions of water and.
hydrocarbon> especially in systems containing light> normally' onemulsifying hydrocarbons such as distillate> casing head gasoline> kerosene, diesel fuel and various refinery fractions.
Inhibitors are conunonly used in refinery systems where emulsifi-cation is highly objectionable and where the compositions could be'designed to 'include an effective emulsion preventative micellar solution of TISA.
~2-~5285~
l Inhibitor use may range. from a few to several hundred parts per million based on the'oil to be'treated, depending upon the' severity oE corrosion. For a giv'en oil fiel'd or group oE wells, tests will normally be'run to determine'the'requirement for micel'lar solution of TYSA and for inhibitor and a composition incorporating these components in approximately the des'ired ratio , will be prepared. In some'instances, the requirement for miceIlar ' solution o'f TFS~ in the best concenLratio1l may result in IISC o corrosion inhibitor, employed as micel'le-'former, in some excess ~10 over that required for~inhibition. This will not afect the ut1lity of the' micel'lar solution and will provide'a comEortable excess of inhibi.tion which can be'helpful during the periods when higher corrosivity may be'encountered. '-- - -Examples of micellar solutions employing TFSA with'inhibitor 15 ~ in water dispersible, micellar solutions are g1ven below.
SeIection of the proper corrosi'on inhibitor for'a given system or oil is usually made by conducting laboratory tests under conditions simulating those'encounter~d in the well or flowline. Such tests are'exemplified'by that described in Item ~20 No. lKl55, "Proposed Standardized Laboratory Procedure ~or ~
Screening CorrosLoD Inh1bitors for Oil and Gas Wells", published by the National Association of~Co'rrosion Engineers, Houston, Texas.
. ' ' . ' .
~ rl~5 ~F TH'N F1L~ .r~lA-ING AGENTS

EXAMPLE'I
Reference is made to U.S.' Patent No. 2,499,365, to M. De Groote, issued March'7, 1950, which 'described generally the manu-facture'of demulsifiers by the oxyaIkylation of fusible,' organic .. . ..
~ solvent-soluble, alkylphenol resins. The procedure of'Example ,.

~5i2l5152 -1 74a of ~his patent was followed to prepare a fusible, xylene soluble p-dodecylphenol res'in in xylene solution. The'acid cata lyst was neutralized, water was'removed by azetropic 'distillat1on of some zylene and 0.5% by weight of sodiulh ll~ethyl.~te catalyst W.lS
added. Using the procedtlre of ~xarnple lb of the cited patent, 25% by weight of ethylene oxide, based on the'final batch weight, was added and reacted,with the'resin.
The product met the'three'reqtlirements rel'ating to solubility, solubility parameter and ability to spread'at interfaces. It,was also foundtto be an effeçtive additive for improving oil recovery by waterflooding., .

EXAMPLE'~
"- Into a 2,000'gal. stainless steel reactor equipped with jacket 15~' and coils for steam heating and cooling, a dec'anter-condensor and appropriate inlet and-outlet fittings was placed 2,400 lbs.`of -co~nercial grade p-nonyl pheno~l, 1,200 1bs. of high boiling aromatic ' hydroca~bon solvent and 420 lbs. of flake'paraformaldehyde. After - stirring ~'or about 30 minutesj 9 lbs. of dipropylnaphthalene'sul-' fonic acid was added to the vessel contents and the reactor was closed.
The contents were warmed to about 40C at which point an exothermic reaction started. The temperature:was allowed to rise-at 120C, using cooling when neces'sary to maintain this maxirnum.
The pressure rose to 60 psi and the vessel was vented wben needed to maintain the pressure at or below this point. After h,eating and stirring under these conditions for about one'hour, the temper-ature was lowered to 95C and the vessel was opened to the reflux decanter system. The temperature wa,s then increased and water was collected in the'decanter whlch was adjt1sted to,reflux aromatic solvent back 'to the''reactor and discard the water. 'The temperature was gradually raised to about 230C and hel'd until no more water -3I- , ~S;~85Z
1 was evolved, at which point i:he finished resin was cooled to 130~
and an additional 1,200 lbs. o~ aromatic solvent was added.
AEter completion of the resin synthesis the'decanter-condensor system was closed and 40 lbs. o~ a 50% solution of potassium hydroxide was added'slowly to the'reactor contents while stirring.
A nitrogen stream WdS then introduced through a bottom discharging tube and allowed to flow through'-the contents for one'hour while the temperature was brought to'110C. The nitrogen was then shut of~ and introduction of a propylene oxide was started. The temper-ature was allowed to rise'to 150C and was,maintai,ned between 140 and 160C untll 2,000 lbs. of the oxide'had been added and ' reacted The'propylene oxlde line was then cl.osed and ethylene - oxide,was slowly introduced and allowed to react until a total of 800 lbs. had been added.
, Th~s product was then cooled and'pumped to storage. Aromatic solvent was,vacuum distilled from a sample of this batch.' It was found to have a solubility parameter of 8.0'and was insoluble to ' the extent of 1% in water and lsooctane. It was found to spread '' reapidly at a white oil distilled water interface with"a spreading pressure of 20 dynes per cm at a claculated thickness of 13 Angstroms and a spreading~pressure of 29 dynes per cm at a calcu-, lated thickness of 20 Angstroms.

EXAMPLE III
The procedure of Example II was followed except that 45 lbs.
of a 5% solution o sodium hydroxlde in water was.used in place of the dipropylnaphthalene sul~onic 'acid of Example'II. An alkà-line catalyzed resin thus resulted after removal of the water.
At this point 25 lbs. of sodium methylate were added in place of the potassium hydroxide of Example III, acting as additional catalys't for the'subse~uent addition o the propylene and ethylene oxides.

The product was more viscous than that of Example II. A
purified, solvent-free sample met the three criteria for TFSA
recited above.

EXAMPLES CF MICELLAR SOLUTIONS OF TFSA's EXRMPLE A
Wt.
Oleic Acid 7 Triethanolamine 7 Borax 3 10 ; Water 29 : 20~NaCl ~in water) 5 Product of Example I 3 Isopropanol 14 EXAMPLE B
Wt. ~ ;
Product of Example I 30 Dodecyldimethylbenzyl ammonium chloride 8 Cyclohexanone 10 : Water ~ 52 In addition to being a demulsifier for water-in-oil petroleum emulsions, this product has strong biocidal activity as a result of the blo-toxicity of the amphipathic and hydro- ;
tropic agents employed (dodecyldimethylbenzyl ammonium chloride and cyclohexanone, respectively).
Where the water separated from emulsions is to be disposed of by injection into a subsurface formation or where it is to be reinjected for flooding or pressure maintenance into the oil producing formation itself, it is especially important to pre-vent - r~

~ ~ ~Z ~ 5Z ' l biological growths. Such glowths create serious plugging problems on and within the subsurface formatlon and lead, as we'Ll, to sulide production and corrosion problems in inject'ion and pro-duction wells. ~' This formula, as a result of its inclusion of the surface-active quaternary ammonium'salt, also assists in the cl'arification of the separated water, discharging the inherent negative surface charge on oil droplets and sollds which may be'dispersed therein - during the demulsification and sedimentation steps, and thus further improving wa'ter quality prior to its reinjection or disposal.

EXQMPLE C
Wt. %
Product of Example I 16 Cyc]ohexylamino-dodecylbenzene sulfonate 2 Sodium p-nonylphenoxy-pen'taethoxy sulfate 8 High boiling aromatic hydrocarbon ~ ' 6 Dipentene' 10 Ethylene glycol monobutyl ether 10' Water '' ' 48 - This compositlon is particularly useful for down-the-hole application where'the oil is high]y paraffinic and of high pour polnt. It contains demulsifier along with an' effective wetting agent and solvents for prevention and/or'removal of waxy'or asphaltic deposits whlch may form in the tubing and flow line of the well~ ' Reference was made'previously to the incorporation of water-insoluble treating agents such as biocides, scale inhibitors, etc., into the'present compositions-to form multifunctional compounds for'use'in oil field and refinery treating operations, ~1~i21352 1 It should be made clear, ho.~ever, that other inherently water ins'oluble rea'gents or compounds. as well. may be incorporate'd into the present compositions by way of micellar solution also to provide very useful' multiEunctional composit;ons.
EX~MPLE D
Wt. /O
Product of Example II 32.2 ~nonium Tetradecyl,Benz'enesulfonate' 8.8 10 n-Butanol - ' 10.'0`
S,odium chlorlde' . 0.1, Water , , 48.9 . ~ This composition is an èffective'demulsifier alone or in combinations with other aqueolls compositions of TFSA. It is an especially effective'a'dditive for aqueous flooding fluids injected into oil producing formations -to effect enhanced recovery of oil.
This composition, when tested by the'laboratory procedure described earlier,.gave res'ul`ts shbwn in the table'beIow'. `
Among procedures which:have'been found useful in selecting effective micellar TFSA solutions for this use, one'involves a determination of oil displacement efficiency from prepared o.il-containing rock c,ores in equipment described.below. A tube of glass or transparent polymethacrylate'ester,'having an inside diameter of about 3.'5 cm -(1~ in.) and a length''of about 45 cm C18 in.), is fitted with inlet connections and appropriate valves a~
each end. Tlie tube is mounted vertically on a rack in an air bath e,quipped with a fan, heater and thermostat which'allows selection and maintenance' of temperatures in the range of between about 25 - 130C.
To select an effective micel'lar TlSA solution for use'in a given oil for~atiorl', samples' of the oil, of the proclucing rock . -35-~;2~5Z
1 formation and of the water l:o be used in the Eloocling operation were obtained. The formation rock is extracted with'toluene to remove oil, is dried and is then ground in a ball mill to the point whe're a large percentage passes a 40 mes'h'sieve. Th'e' fractioll between 60 and ]00 mesh :in size is retained. The tuhe described above is removed from the'air bath, opened and, after insertion of a glass wool retainer at the'lower end, is pack'ed with the ground formation rock. The tube is tapped gently'from time-to-time during filling to ensure'close packing and is visually inspected to assure'absence'of voids.-~
- The tu'be'is then returned to the''air bath,' connected to the inlet tubing, the temperature ls adjusted to the''oil formation .
temperature and water representative of thàt produced from the formation is admitted slowly through the'bottom line from a calibrated reservoir in an amount ~ust sufficient to fill the packed rock plu~ in the tube. This volume is determined from the calibrations and is referred to as the "pore volume", being that volume'of water just sufficient to ill the pores or interstices of the packed plug rock.
The upper line to the'reservoir is then connected to a calibrated reservoir containing the oil representing that from - the formation to be-flooded. By proper manipulation of valves, the line LS filled with oil-which is then slowly pumped into the core from the reservoir after the'lower valve is opened to allow displacement of the'formation water.
As breakthrough of oil at the bottom is noted, pumping is stopped and the volume of oil introduced into the sand is deter-mined from the reservoir readings. This lS referred to as the volume of oil in place. The tube of sand containing oil is then left in the'air bath at the'temperature'of the formation for a period of three'days to allow 'establishment of equilibrium between ~2852 1 the ground formation roclc alld the oil with respect to adsorption of oil constituents on the`rock and lowering of interfacial tension. The time allowe'd for equilibrium may be'varied widely.
At higher temperatures, the'time'required to reach equilibrium is 5' probably reduced. Usually, for comparatlve tests, three'days are allowed to age the oil-rock plug. Results with'this procédure closely simulate work wi'th'actual cores of oil-bearing rock.
The'oil and water samples used for test purposes are'prefer-ably taken under an inert gas such as high purity nitrogen, and are maintained out of contact with air during all minipulations in order to prevent oxid-ation of the oil and concomitant intro-duction of spurious polar, surface-active constituents in the .. . . .
oil. At this point, th-e rock-oil system simulates the'original oil fonnation before primary production oil has commenced and well before any secondary water'flood operation. ~ -- The upper inlet line'to the tube'is now connected to the sample of water used in the flooding of the oil'formation and, by means of a syringe pump or similar very small volume'positive displacement pump, the water is pumped into the'sand body from the'top to displace flulds out of the bottom tublng connec~ion into a calibrated~receiver. The pumping rate is adjusted to one simulating the rate of flood water advance'in àn actual operation, which is usually in a range of 1 to 50 cm per day. Pumpin~ is maintained at this rate until two pore volumes of water have been pumped throug~h the sand. ~
Th'e volumes of fluids collected in the'receiver are measured and the relative amount of oil and water displaced from the'rock sample are determ:ined and recorded. Of special interest is the volume of oi'l displaced as a fraction oE tlle original pore'volume.
This information may be viewe'd as an indication'of'the approximate percentage'of oil originally in place' which is produced by natural 1 water drive following drilling of a well into the rock formation fol'lowed by the primary pha'se of field product;on carried to the approximate'economic limit.
Iollowing this step, one to tllree additional pore'volumes of water containing'the TFSA micellar solution to be tes'ted are pumped slowly through the plug and the volumes of addi-tional oil and water displaced are determined.- Typically, where such'an initial "slug" of micellar TFSA solution is introduce'd, it may be con~ained in a volume of'fluid ranging from 1% to 100% of the pore volume, but most frequently it will be in a slug volume of 10% to 50% of pore volume.' ' After this final dlsplacement step, thè produced oil and water are again measured. 'By comparing the'amount of oil produced ---' - by this additional injection of water containing, or'preceded by a solution, of micellar TFSA solution with'the amount produced when the same volume of water containing no TFSA solution is ~ injected, one can evaluate'the effectiveness of the particular ; micellar TFSA solution used for enhancing the recovery of additional oil over and above that obtalned by ordinary waterflooding.
Generally, six or more sand columns of the kind described above are mo~mted in the heated air bath. Test of a given micellar TFSA solution is'then run in triplicate, using identical condltions and concentrations, simultaneously with three blanlc tests run similarly'but without addition of micel'lar TFSA solution to the water.
The compositi'on of Example D was tested by this proce'dure with the following conditions:
Oil -- Ranger %one, Wilmington, Calif., field ~PI Gravity approximately 13.5 Water -- Mixed water used in flood operations Airbath Temperature -- 150F (Same'as formation'temperature~

~;28S2 1 Oil was displaced by pl-l.nping two pore volumes of water into the sand. After measuring the volumes of oll and wa~er produced through the bottom line, a further-:0.2 pore volumes of water containing 3,500 ppm o the composition of Example'~ wa's.injected followed by 2.8 volumes of water containing 200'ppm of the com-position bf Example D. Measurement of the volumes''of oil and water produced were read after each 0.2 pore volumes of water was injected.
Results of this test at-the'points'of 2,3 and 5 pore volumes ~,10 of inject'ed water are 'given in the table'below 'wher'ein~averages ' of three'duplicate'determinations are'presented .
Oil Recovery as % of . ' ''.''' O'i'l 'in' P~la'ce ' ' . ' ' , Composition of Ratio of Increment - ~ Example'D of Oi~ Production ~ Added to Water After Initial:2 Pore Volumes' (P.V.) No Chemical after Initial . P.V. Chemical ' of Water In'jecte'd ''' A~d'di't'ion' '2 P.V.''o'f Water No Chemical : , 2 ' 36,.5 36.5 ' -. -~' 3 ' ' ' ~ ~47-5' 3.1 ~' '' 5 43.1 ' 60.0 '3................................. 6 Use of the composition of Example D in the amounts g.iven above resulted in the production of 210VfO more oil from injection of one incremental pore volume, of.water than was produced by water injection alone and gave 260% more oil after three incre-mental pore volumes of treated water injection.

' EXAMPLE E
Wt. /~
Product of Example II . 32 . 95% Ethanol 10' Dodecylbenzene sulfonic 'acid 11 Polyacrylamide (Dow 'NP10) Water 46 -3g-~ ~ ~2 85;~"
1 This aci.dic, homogeneous, aqueous, very viscous composition is especially useful as an emulsion preventer in hydrochl'oric acid solutions used in treatmen,t of calcoreous oil-bearing'strata. ' It is readily dispersible'in 15% hydrocllloric~acid.and mixtures ' , :5 . thereof with hydrofluoric acid, prevents emulsification of the .
~; acid and also prevents eniulsifica'tion of the spent acid solution :~ which is ultimately regurgltated with'th.e produced petroleum. It . is also a particularly effective additive'for aqueous flooding : fluids injected for effecting secondary or tertiary recovery of petroleum; or, it may be'used alone or diluted wlth'one'or two .
volumes' of water to provide improved flow distrlbution in the flooded zone aDd to énhance'oil;recovery. ' : : :~
AI~though the'invention:has been des~cribed in terms of specified embodiments which are set forth in~ detall, it should be ~ ~understood that thls is by illustration~only and that the inven-tlon ls not nec'essarily llmited.thereto, slnce alte~nativ~e~
embodiments~and operating techniques~will become apparent~to ' : tho~se skilled in the art in view of the'disclosure. ~ccordingly, modifications:are contemplated which can be made without departing ;20 ~ ; from the.spirit o~ the described~invention.. ~ - :

,: - : .

Z5 ~ ~ ' ' :' ' , ' . . .

-4~-

Claims (41)

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

1. A micellar thin film spreading agent composition, com-prising: (1) from between about 5% and about 75% by weight of a resinous 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 cylcoaliphatic 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, said adduct 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 Ang-stroms, at a spreading pressure of about 16 dynes per cm;
(2) from between about 2% and about 30% by weight of a hydro-tropic agent having one of the formulas:
(A) X - Z
wherein X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic or sub-stituted heterocyclic radical having 2 to 13 carbon atoms;
and wherein Z is one of: -OH ; ; -CHO ; ;
-COOH; and -OCH3;
wherein U and V are hydrogen or hydrocarbon substituents, (B) -X-Y-R-(Z)n' wherein:
z is one of -OH; ; -CHO; ; -COOH; and -OCH3;
X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic or substituted heter-ocyclic radical having 2 to 12 carbon atoms;
U and V are hydrogen or hydrocarbon substituents;
R is a member selected from the class consisting of, -CH2-, -C2H4-, C3H5=, -C3H6, and -C2H4-O-C2H4-;
n is either a one or two integer, the integer dependent upon the selection of R; 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 composition of Claim 1 wherein said alkylene oxide contains less than about C5.

3. The composition of Claim 1 wherein said ethylene oxide is present in said adduct in an amount between about 1 and about 5 moles per phenolic moiety in said resin.

4. The composition of Claim 1 wherein said resin is an alkyl phenol-formaldehyde condensate.

5. The composition of Claim 1 wherein said condensate is further condensed with said alkylene oxide within a sub-stantially solvent-free environment.

6. The composition of Claim 1 wherein the alkylene oxide is at least one of a member selected from the class consisting of ethylene oxide, propylene oxide, and butylene oxide.

7. The composition of Claim 1 wherein said weight ratio of oxide to condensation product is between about 1-to-5 and about 3-to-1.

8. A micellar thin film spreading agent composition, com-prising: (1) from between about 5% and about 75% by weight of a resinous 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, said condensate resin being thereafter further condensed with an alkylene oxide contain-ing less than about five carbon atoms in an amount equal to at least one mole of alkylene oxide per phenolic moiety of said resin, said adduct at about 25°C: (A) having a solu-bility 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 Ang-stroms, at a spreading pressure of about 16 dynes per cm; (2) from between about 2% and about 30% by weight of a hydro-tropic 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.

9. The composition of Claim 1 or 8 wherein the hydrotropic agent is an alcohol.

10. The composition of Claim 1 or 8 wherein the hydrotropic agent is an hydroxy ester of a polyol.

11. The composition of Claim 1 or 8 wherein the hydrotropic agent is an aldehyde.

12. The composition of Claim 1 or 8 wherein the hydrotropic agent is a semi-polar oxygen-containing compound capable of forming hydrogen bonds.

13. The composition of Claim 1 or 8 wherein the hydrotropic agent is an amine.

14. The composition of Claim 1 or 8 wherein the hydrotropic agent is a carboxy amide.

15. The composition of Claim 1 or 8 wherein the hydrotropic agent is a phenolate.

16. The composition of Claim 1 or 8 wherein the amphipathic agent is a hydrophobic hydrocarbon residue-containing compo-sition wherein the hydrocarbon residue is aliphatic, alkylali-cyclic, aromatic, arylalkyl or alkylaromatic.

17. The composition of Claim 1 or 8 wherein the amphipathic agent contains an uninterrupted chain of from between about 10 and about 22 carbons.

18. The composition of Claim 1 or 8 wherein the amphipathic agent is an anion-active soap.

19. The composition of Claim 1 or 8 wherein the amphipathic agent comprises sodium cetyl sulfate.

20. The composition of Claim 1 or 8 wherein the amphipathic agent comprises ammonium lauryl sulfonate.

21. The composition of Claim 1 or 8 wherein the amphipathic agent comprises ammonium di-isopropyl naphthalene sulfonate.

22. The composition of Claim 1 or 8 wherein the amphipathic agent comprises sodium oleyl glyceryl sulfate.

23. The composition of Claim 1 or 8 wherein the amphipathic agent comprises mahogany or green sulfonates of petroleum, petroleum fractions, or petroleum extracts.

24. The composition of Claim 1 or 8 wherein the amphipathic agent comprises sodium stearamidoethyl sulfonate.

25. The composition of Claim 1 or 8 wherein the amphipathic agent comprises dodecylbenzene sulfonate.

26. The composition of Claim 1 or 8 wherein the amphipathic agent comprises dioctyl sodium sulfo-succinate.

27. The composition of Claim 1 or 8 wherein the amphipathic agent comprises sodium naphthenate.

28. The composition of Claim 1 or 8 wherein the amphipathic agent comprises cetyl pyridinium chloride.

29. The composition of Claim 1 or 8 wherein the amphipathic agent comprises stearamidoethyl pyridium chloride.

30. The composition of Claim 1 or 8 wherein the amphipathic agent comprises trimethyl-heptadecyl ammonium chloride.

31. The composition of Claim 1 or 8 wherein the amphipathic agent comprises dimethyl-pentadecyl sulfonium bromide.

32. The composition of Claim 1 or 8 wherein the amphipathic agent comprises octadecylamine acetate.

33. The composition of Claim 1 or 8 wherein the amphipathic agent comprises 2-heptadecyl-3-diethylene diamino-imidazoline diacetate.

34. The composition of Claim 1 or 8 wherein the amphipathic agent comprises the oleic acid ester of nonaethylene glycol.

35. The composition of Claim 1 or 8 wherein the amphipathic agent comprises the stearic acid ester of polyglycerol.

36. The composition of Claim 1 or 8 wherein the amphipathic agent comprises an oxyethylated alkylphenol.

37. The composition of Claim 1 or 8 wherein the amphipathic agent comprises an alcohol ether of a polyethylene glycol.

38. The composition of Claim 1 or 8 wherein the amphipathic agent is anionic.

39. The composition of Claim 1 or 8 wherein the amphipathic agent is cationic.

40. The composition of Claim 1 or 8 wherein the amphipathic agent is nonionic.

41. The composition of Claim 8 wherein the solubility para-meter at about 25°C of the adduct is from between about 7.1 and about 7.9.