MXPA99007921A - Recovery and reuse of anionic surfactants from aqueous solutions - Google Patents

Abstract

Improved surfactant recovery upon ultrafiltration of a surfactant-containing aqueous solution can be obtained using a system comprising anionic surfactants.

Description

RECOVERY AND REUSE OF TENS - ANIONIC COACTIVES FROM AQUEOUS SOLUTIONS DESCRIPTION OF THE INVENTION The present invention relates to the unexpected discovery of surfactants that demonstrate improved surfactants coated from aqueous solutions in ultrafiltration. Due to the environmental and economic concern, it is important to remove and desirably, cover to reuse active ingredients from waste solutions or aqueous by-product. Coating and recycling not only reduces or eliminates the discharge of contaminated water into the environment but also reduces the total cost of industrial processes. This is of particular importance in processed aqueous solutions containing surfactants as it can be a costly component of the solution. The ultrafiltration equipment can be used to overcome certain problems of waste disposal in relation to aqueous solutions, whether sintered metal oxide / sintered metal or polymeric filters are used. However, the economics of these processes in surfactant recovery has been seriously hampered by many of the conventional surfactants that are not easily transferred to the permeate. Therefore, the ability to recycle and reuse surfactants. Coated aqueous solutions is significantly reduced, and the subsequent addition of surfactant is necessary to bring the surfactant into the aqueous solution at the original level. This is a significant problem in the recycling area when the complete economy can not be achieved. Nonionic systems have been discovered in US Pat. No. 5,205,937 which claims significant recovery of water-based cleaning systems in the permeate product in the ultrafiltration of waste solutions, although expressions of satisfaction have been adjacent concerning the filterability and recovery of water-based cleaning formulations being currently used commercially. The present invention is directed to the discovery that surfactant containing aqueous compositions contain a certain group of surfactants improvisedly provided by improved surfactants coated in the permeate product after ultrafiltration. It has unexpectedly been found that the recovered increased surfactant can be obtained by an ultrafiltration process by the use of aqueous solutions containing certain systems of anionic surfactant which, when ultrafiltered, performs a permeate product characterized by increased concentrations of surfactants. The present invention also provides a process for filtering contaminants from a solution containing aqueous anionic surfactant by passing a feed solution containing the contaminants through an ultrafiltration membrane, preferably a metal oxide membrane in a ceramic support. In another aspect, the present invention relates to a process for separating a surfactant from a solution of aqueous surfactant containing contaminants, such as oils, fats, waxes, emulsified lubricants and the like by ultrafiltration, that is, by passing the solution through a multi-crystallized sintered monolithic metal / metal oxide ultrafiltration membrane in a ceramic support to coat the surfactant in the permeate. The sintered membrane has a nominal pore size in the range of approximately 50 to 1000 Angstroms. The present invention provides an efficient and effective composition and processes for separating surfactants from aqueous solutions for recycling and reuse. It has unexpectedly been found that the compositions of this invention contain anionic surfactants, are adapted for substantial recovery in ultrafiltration.

The surfactants that have been found to provide the benefits of this invention include the following, they can be represented by the formula. I R- [0 (E0) a (P0) b] n-S03 -? +, II. [R- [0 (E0) a (P0) b] n-] m-P (0) (0M) 3- «, III. R4-0-C (0) -CH2-CH-C (0) -0-R5, SO3-Y IV. R- [O (EO) a (PO) b] n-CH2-C (O) -0 ~ Y + V. and mixture thereof; wherein, R is selected from the group consisting of alkyl, aryl, alkaryl, alkylarylalkyl, arylalkyl, alkylamidoalkyl, alkylaminoalkyl and R] .- C (CO [O (EO) a (PO) b] n -R2- (O) p- where Ri is C12-C22 alkyl and R2 is C1-C18 alkylene and substituted hydroxyl derivatives thereof, wherein the alkyl group contains from about 1 to about 12 carbon atoms, the aryl group represents a phenyl portion , diphenyl, diphenylether, or naphthalene and wherein the total carbon atom content of the R group is not greater than about 18 carbon atoms, R is preferably C 4 to C 4 alkyl or alkylamido alkyl, R can be illustrated by butyl, hexyl , 2-ethylhexyl, octyl, nonyl, decyl, and the like. ~ Substituents from natural sources contain mixed carbon chain lengths which can be used or purified to reduce the number of chain lengths in the alkyl groups.The preferred alkylaminoalkyls are butylaidoethyl, octylamidopropyl, and decylamidopropyl. M represents hydrogen, an alkali metal such as sodium or potassium or - [R3 - [(E0) a (PO) b (BO) c] "- O-] qP (O) (0M) 2 Y represents a counter ion, preferably an alkali metal, and more preferably sodium, EO represents ethyleneoxy radicals, PO represents propyleneoxy radicals, BO represents butoxy radicals a, b and c are independently numbers from 0 to 50, a is preferably from about 0 to about 15, b is preferably from about 0 to 10 and c is preferably 0 to 10, wherein the radicals EO, PO and BO can be mixed randomly or in discontinuous blocks. n is 0 or 1, m is 1 and / or 2 giving either a mono or disphosphate ester or mixtures thereof, p is O or l; R3 is alkylene of Ci-Cs; Rj is C4-Cß alkyl or C-β alkylamido; R5 is C4-C8 alkyl or Y; R g is hydrogen or C 4 -C 2 alkyl; and Q is 1 to about 10 Preferably, the surfactants are low or unfoamed when foaming can create filtration difficulties. The anionic compounds of Formula I-V are well-known compounds and can be made by methods recognized in the standard art. This group of surfactants can typically be incorporated into aqueous solutions having a high alkaline acid content, particularly having a relatively high alkaline content, for example, within the range of 0.01 to about 50%, and preferably from about 0.1 to about 40%. potassium or sodium hydroxide or an equivalent such as sodium carbonate, silicate phosphate and amine solutions. The ultrafilterable surfactant solutions of the present invention have a surfactant content in an effective amount by the requirement of the final extreme request, eg, cleaning and, ultimately, the ultrafiltration process. The primary anionic surfactants may comprise up to 100% of the total weight of the surfactant actives. Preferably, the primary anionic surfactants of this invention are used in combination with other zwitterionic, amphoteric, anionic and / or cationic surfactants to achieve optimum surfactant characteristics in the final extreme used formulation. Since a preferred objective of this invention is the formulation of a recyclable surfactant of cleansing composition, alternative surfactants are also preferred separated from the waste stream cleaning solution by ultrafiltration. Typically, solutions containing "aqueous surfactant in the end-use area have total active surfactant concentrations from about 0.001 to about 99, preferably from about 0.01 to about 40.; more preferably from 0.01 to about 15 active percent based on the total weight of the solution. Of this total active surfactant composition, the primary anionic compounds of this invention comprise above 100% and preferably from about 5 to about 100% of the active weight of the total active surfactants in the aqueous solutions. When the primary anionic surfactants are used in combination with amphoteric or zwitterionic surfactants, which are the preferred secondary surfactants, the amphoteric or zwitterionic surfactants may comprise up to about 95% of the surfactant mixture. Preferred amphotericics can be combined with the anionics of this invention which are those such as the true sultaines and betaines and amphoteric as amphoacetates and amino oxides as described in US Patent 4,891,159 and the co-pending US Patent Application USSN 08 / 445,244 filed On 05/19/95 both of which are incorporated herein by reference. The most preferred amphotericics to be used in this invention are the sultaines represented by the formula OH Rb I 1 Ra -CHCH 2 -Q-sr-Rd-S03"I c wherein Ra is alkyl, aryl, alkylaryl, wherein the group alkyl is C -C? 8, or alkoxymethylene, wherein the alkoxy group is Cj-Cs, R and Rc each independently is alkyl of C? -Cs and hydroxy derivatives thereof, (E0) to (P0) b0H wherein EO represent ethyleneoxy radicals, PO represents a propyleneoxy radical, a and b are each independently 0 to 20 wherein at plus b, they do not exceed about 20, and the ethoxy or propoxy groups can be randomly or blockwise distributed in the polymer chain; Rb and Rc can together be -CH2CH2OCH2CH2- or -CH2CH2SCH2CH2- as well as to form together with the nitrogen atom a ring of morpholine or thiomorpholine Ra is C? -C alkylene or hydroxy, substituted alkylene, preferably C? -C2. Q is a covalent bond or Rc ZII -N- (CH2) m -CHCH2- wherein Rc is hydrogen or -CH2CH (OH) CH2S03M wherein M is hydrogen or an alkali metal such as sodium or potassium, and m is 0 or 1. Z is hydrogen or an electron donor group such as OH, SH, CH30 or CH3S. Typically, the R4 group contains approximately 4 to about 12, commonly from about 4 to about 8 carbon atoms. Preferably, R4 is alkoxymethyl containing from about 4 to about 8 carbon atoms in the alkoxy group such as butoxymethyl, hexyloxymethyl, 2-ethylhexyloxymethyl and the like, Rb and Rc are each preferably methyl, hydroxyethyl, 2-hydroxypropyl or a morpholino ring . Where Q is not a covalent bond, Z is preferably hydrogen and m is preferably 1. Q is preferably a covalent bond. The most preferred amphoteric surfactants are the hydroxypropyl alkyl ether sultaine, specifically those selected from the group consisting of OH CH3 OH I I I C4H9? -CH2CH: CH2-N'-CH2CHCH2S? 3" CHS C2H5 OH CH, OH C4H CH- CH20-CH2CHCH2-N "-CH2CHCH2SO; CH, and mixtures thereof. Solutions containing surfactants of this invention in addition to the surfactants described above, may contain other materials such as silicates, phosphates, pyrophosphate and polyphosphates, for example, in a form of sodium salts. Other additives that may be presented include lower alcohols of 1-6 carbons, glycols, glycol ethers, chelating agents, thickeners, such as amide, cellulose derivatives, defoaming agents, builders, sequestering agents, buffers, and polyacrylates. In some cases, additional amphoteric, zwitterionic, cationic or non-anionic surfactants that include inhibitors and hydrothopes may be present. The solutions of the present invention are filtered, preferably using a polymeric, ceramic or sintered metal / metal oxide filter in a ceramic backing. For example, an ultrafiltration membrane system may include a feed tank and a separation membrane unit that is composed of a metal oxide membrane, eg, zirconium oxide or titanium, optionally with an ytterbium oxide stabilizer, or a ceramic carrier for example, alpha-alumina, with or without titanium dioxide having 1 or more channels in a monolithic support. The flow can be maintained at acceptable levels to allow soils to be concentrated in the retentate with minimal contamination through the extended operating times while the surfactant content solution passes through the filter to be recovered by permeating to recycle and reuse. While an effective pore size is readily determinable by one skilled in the art, nominal pore sizes from about 50 to less than about 1000 Angstroms and preferably less than about 500 Angstroms can be used.

The filtration percentage can be varied depending on the filter pore size, pressure, temperature and the like. As used herein, the term "" contaminants "may include, either singly or in mixtures of oils used in metal sealing, forming, waiting, grinding, grinding, machining, and polishing under medium molecular weight hydrocarbons, Paraffin waxes, waxes, petrolatums, hydrocarbons of high chlorine viscosity, chlorinated and sulphurized hydrocarbon mineral oils, and vegetable oils Also included in this term are materials that are partially soluble in the aqueous solution or that form water stable microemulsions such as mixtures of polyethylene, propylene glycol and oleic surfactants, machined cooling water soluble cutting fluids, mono-, di- and unsaturated triglycerides, animal fats, fatty acids and esters included in the term "contaminants" are insoluble solids such as particles of Extremely fine structural material, solid, inorganic, inert or elementary particles , and undissolved metal oxide particles by the aqueous solution containing a particular surfactant. The present invention will be further illustrated in the examples that follow.

EXAMPLE 1 Filterable surfactants are evaluated against a commercially available composition by comparing the concentration of surfactants in the solution at pH 12 before and after passing through the KERASEP ultrafiltration membrane filter (sold by Tech Sep). Two gallons of surfactant solution in an activity as set out in the tables is prepared and sent to the filtration unit work tank. The work tank solution is heated and maintained at 52 +/- 2 ° C during operation.

The working tank solution is circulated through the membrane. The internal pressure is adjusted to 20psi. The retentate and the permeate are bonded to the work tank in such a way that the concentration of the work tank is constant. The sample solutions are collected from the permeate product, and the work tank in the established time intervals. The percentage of the permeable surfactants is expressed as the ratio of the active concentration per cent by weight of the working tank. Surfactant concentrations are determined by the measured surface tension techniques. TAB A 1 PERCENTAGE OF THE SURFACTANT I THAT GOES THROUGH THE MEMBRANE [Initial concentration (Ci) = 0.25% active, pH = 12, pore size 0. lμm] The SURGICAL I is a sodium hydroxide acetate (MIRANATEP sold by Rhéne Poulenc) TABLE 2 PERCENTAGE OF THE SURGICAL II WHICH GOES THROUGH THE MEMBRANE [Initial concentration (Ci) = 0.25% active, pH = 12, pore size O.lμm] The SURFACTANT II is phenol ethoxylate (6 mol), phosphonate ester (RHODAFACR BP-769 sold by Rhéne Poulenc) TABLE 3 PERCENTAGE OF THE SURGERY I THAT GOES THROUGH THE MEMBRANE [Initial concentration (Ci) = 0.25% active, pH = 12, pore size 0. lμm] The SURGICAL III is sodium 2-ethoxylate phosphate (RHODAFACR PEH sold by Rhéne Poulenc) TABLE 4 PERCENTAGE OF BRULIN 63G THAT GOES THROUGH THE MEMBRANE [Initial concentration (Ci) = 3% Brulin 63G *, pH = when active, pore size 0. lμm] * Brulin 63G is a Brulin brand for a mixture of sodium xylene sulfonate, potassium phosphate, sodium silicate and two nonionic surfactants (weight in mole of approximately 2750 and approximately 910 respectively) which has an alcoholic portion of approximately 100%. and about 50 moles of EO / PO (approximately 32 mol EO / 18 mol PO randomly distributed). TABLE 5 PERCENTAGE OF THE AQUATEK RP2000 THAT GOES THROUGH THE MEMBRANE [Initial concentration (Ci) = 0.25% active *, pH = 12.0. pore size lμm] * Aquatek RP2000 is the trademark for a pharmaceutical formulation sold by Rhone-Poulenc where the surfactant present in the formulation is a Tertiary Thioethoxylate (7) (non-ionic) surfactant As can be seen from the data in Tables 1, 2 and 3, a long proportion, generally between about 60% and as high as about 100% of the surfactant composition of the invention, passes through the ultrafiltration membrane and is captured in the permeate product. The data in Table 1, 2 and 3 demonstrate that the permeate product of an aqueous solution contains a surfactant of this invention that can be effectively recycled for reuse. This elevated coating of the surfactant also reduces the pressure in the environment that should otherwise occur without a high surfactant recovery. In contrast, the data in Table 4 show that only a small amount of surfactant from a solution containing commercially available aqueous surfactant passes through the ultrafiltration membrane and reaches part of the permeate. The worked solution was prepared as before a sufficient amount of the commercial solution was used to provide an initial (calculated) concentration of about 3% with a pH "as is". The data in Table 4 show that with the non-ionic aqueous solution of Brulin 63G, the surfactant must remain in the retentate and in which 10.5% passes through the ultrafiltrator with the permeate product. Table 5 further illustrates the difficulty encountered when one attempts to pass a certain nonionic surfactant through the ultrafiltration membranes. The working solutions are prepared as before and the concentration of the nonionic surfactant measured in the permeate. As the data indicates, most surfactants remain in the retentate and less than 12.0% pass through the ultrafilter with the permeate. While the invention has been explained in relation to its preferred embodiments, it is understood that various modifications thereof will be apparent to those skilled in the art in reading the identification. Therefore, it is understood that the invention described herein is intended to cover such modifications that fall within the scope of the appended claims.

Claims (3)

1. CLAIMS 1. a method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the step of: (i) preparing an aqueous solution comprising a surfactant composition comprising a surfactant anionic (ii) ultrafiltrate the solution containing aqueous surfactant at a pressure not higher than 45 psi to generate a permeate; and (iii) coating the surfactant of the permeate. The method according to claim 1, characterized in that the aqueous solution comprises from about 0.001 about 99 percent by active weight of the surfactant composition. 3. The method according to claim 1, characterized in that the aqueous solution comprises from about 0.01 to about 40 percent by active weight of the surfactant composition. . A method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the steps of: (i) preparing an aqueous solution comprising a surfactant composition comprising surfactants selected from the group consisting of from: II. [R- [0 (E0) a (P0) b] n-] m-P (0) (0M) 3_m III. R4-0-C (0) -CH2-CH-C (0) -O-R5, S03"Y + IV. R- [0 (E0) a (P0) b] n-CH2-C (0) -O'Y" 1 V. and mixtures thereof, wherein R is selected from the group consisting of alkyl, aryl, alkaryl, alkylarylalkyl, arylalkyl, alkylamidoalkyl, alkylaminoalkyl, R? -C (O) - [O (EO) a (PO) b] n -R2- (O) p- and substituted hydroxy derivatives thereof wherein the alkyl groups contain from about 12 carbon atoms, the aryl group is a phenyl, diphenyl, diphenylether, or naphthalene moiety, provided that the total number of carbon atoms in any group R is not greater than '18. Ri is C12-C22 alkyl, R2 is Ci-Cis alkylene Ri is Cj-Cs alkyl or Cj-Ca alkylamide R5 is C4-C8 alkyl or Y Re is hydrogen or C4-C12 alkyl M is hydrogen, alkali metal or - [R3- (EO) a (PO) b (BO) c] n-0] qP (0) (0M) 2, R3 is C1-C5 alkylene, Y is a counterion EO represents an ethyleneoxy radical , PO represents a propyleneoxy radical, and BO represents a butoxy radical a, b, and c are each independently from 0 to 50, wherein EO, PO, and BO can be mixed randomly or in discontinuous blocks. N is 0 or 1, M is 1 and / or 2. P is 1 and / or 2. q is 1 to about 10: ii) Ultrafiltrate the solution containing aqueous surfactant at a pressure not higher than 45 psi to generate a product permeated; iii) coating the surfactant of the permeate. EO represents an ethyleneoxy radical, PO represents a propyleneoxy radical, and BO represents a butoxy radical, a, b and c are each independently 0 to 50, wherein the EO, PO and BO can be mixed randomly in discontinuous blocks. n is 0 or 1 p is 0 or 1 and ii) ultrafiltrate the solution containing aqueous surfactant to generate a permeate and iii) coat the surfactant of the permeate. A method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the steps of: i) preparing an aqueous solution comprising a surfactant composition comprising a surfactant of the formula : [R- [0 (EO) a (PO) b] n-S03"Y +" wherein R is selected from the group consisting of alkyl, aryl, alkaryl, alkylamidoalkyl, alkylaminoalkyl, Rx-C (O) - [O ( EO) a (PO) b] n -R2- (0) p_ and the hydroxy substituent derivatives thereof Where the alkyl groups contain from 1 to about 12 carbon atoms, the aryl group is a phenyl, diphenyl, diphenylether moiety or naphthalene, with the proviso that the total number of carbon atoms in any group R is not greater than 18. Ri is C 2 -C 22 alkyl, R 2 is C 1 -C 8 alkylene, and is a counter ion EO represents an ethyleneoxy radical, PO represents a propyleneoxy radical, and BO represents a radical dical butoxy, a, b and c are each independently 0 to 50, wherein the EO, PO and BO can be mixed randomly in discontinuous blocks, n is 0 or 1, p is 0 or 1 and ii) ultrafiltrate the solution containing surfactant aqueous at a pressure not greater than 45 psi to generate a permeate product; and iii) coating the surfactant of the permeate. 6. A method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the steps of: i) preparing an aqueous solution comprising a surfactant composition comprising surfactant of the formula: [R- [0 (EO) a (P0) b] n-3m-P (O) (OM) 2 wherein R is selected from the group consisting of alkyl, aryl, alkaryl, alkylarylalkyl, arylalkyl, alkylamidoalkyl, alkylaminoalkyl R ? -C (O) - [O (EO) a (PO) b] n -R2_ (0) p- and the substituted hydroxy derivatives thereof, wherein the alkyl groups contain 1 to about 12 carbon atoms, Aryl group is a phenyl, diphenyl, diphenylether or naphthalene moiety, with the proviso that the total number of carbon atoms in any group R is not greater than 18. Ri is C12-C22 alkyl, R2 is alkylene of Ci-Ciß; and M is hydrogen, alkali metal or - [R3- [EO] a (PO) b (BO) c] n-0] qP (0) (OM) 2 r R3 is C1-C5 alkylene EO represents an ethyleneoxy radical , PO represents a propyleneoxy radical, and BO represents a butoxy radical, a, b and c are each independently 0 to 50, wherein the EO, PO and BO can be mixed randomly in discontinuous blocks. n is 0 or 1; m is 1 and / or 2, p is 0 or 1 and q is i to about 10; ii) ultrafiltering the solution containing aqueous surfactant at a pressure not higher than 45 psi to generate a permeate, iii) coating the surfactant of the permeate. A method for coating at least 5% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse comprising the steps of: i) preparing an aqueous solution comprising a surfactant composition comprising surfactant of the formula: R4 -0-C (O) -CH2-CH-C (O) -O-R5, SOy-Y "wherein R5 is C4-C8 alkyl or C4-C3-alkylamide R5 is C4-C8 or Y alkyl, and Y is a counter-ion, ii) ultrafiltrate the solution containing aqueous surfactant at no greater pressure 45 psi to generate a permeate product iii) coat the surfactant of the permeate product. 8. A method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the steps of: i) preparing an aqueous solution comprising a surfactant composition comprising surfactant of the formula: R- [O (EO) a (PO) b] "-CH2-C (O) -0" Y + wherein R is selected from the group consisting of alkyl, aryl, alkaryl, alkylarylalkyl, arylalkyl, alkylamidoalkyl, alkylaminoalkyl, Rj-C (O) - [O (EO) a (PO) b] n -R2- (O) p_ and the hydroxy substituent derivatives thereof wherein the alkyl groups contain from 1 to about 12 carbon atoms, the aryl group is one phenyl, diphenyl, diphenylether or naphthalene portion, with the proviso that the total number of carbon atoms in any group R is not greater than 18. Ri is C12-C22 alkyl / R2 is Ci-Ciß alkylene and Y is a counterion EO represents an ethyleneoxy radical, PO represents a r propylene oxide, and BO represents a butoxy radical, a, b and c are each independently 0 to 50, wherein the EO, PO and BO can be mixed randomly in discontinuous blocks. n is 0 or 1; ii) ultrafiltering the solution containing aqueous surfactant at a pressure not higher than 45 psi to generate a permeate product and iii) coating the surfactant of the permeate product. A method for coating at least 95% of a substantially pure anionic surfactant of an aqueous surfactant-containing solution for reuse characterized in that it comprises the steps of: i) preparing an aqueous solution comprising surfactant of the formula: where Re is hydrogen of C4-Cj.2, and M is hydrogen, alkali metal, or - [R3 - [(E0) a (P0) b (B0) c] n-0] qP (0) (OM) 2 wherein R3 is C1-C5 alkylene EO represents an ethyleneoxy radical, PO represents a propyleneoxy radical, and BO represents a butoxy radical, a, b and c are each independently 0 to 50, wherein the EO, PO and BO can be mixed randomly in discontinuous blocks. n is 0 or 1; and q is 1 to about 10, ii) ultrafiltration of the aqueous surfactant-containing solution at a pressure not greater than 45 psi to generate a permeate; "and iii) coating the surfactant of the permeate product 10. The method according to claim 1, characterized in that the aqueous solution further comprises up to 95 percent by active weight of an anionic surfactant, the weight percent is based on the weight of the total active surfactant composition 11. The method according to claim 1 I, characterized in that the aqueous solution comprises above 95 weight percent active of an amphoteric surfactant; the weight percent is based on the weight of the composition of the total surfactant. 12. The method in accordance with the claim II, characterized in that the amphoteric surfactant is selected from the group consisting of sultaine, betaine, and mixtures thereof. 13. The method according to the claim 1, characterized in that the aqueous solution comprises above 95 by active weight, based on the total active surfactant weight of an amphoteric surfactant of the formula OH Rb i I Ra-CHCH2-QN "-Rd-S03" I Rc wherein Ra It's alkyl, aryl, alkylaryl, wherein the alkyl group is C4-C? ß, or alkoxymethylene, wherein the alkoxy group is C4-C8, by Rc each independently is i) C? -C6 alkyl or hydroxy derivatives thereof , ii) - (EO) a (PO) bOH where EO represents an ethyleneoxy radical and PO represents a propyleneoxy radical, a and b are each independently 0 to 20, with the proviso that a plus b can not exceed 20 and the radicals EO and PO can be mixed randomly or in discontinuous blocks, or together with the nitrogen, they can form a morpholine ring or thiomorpholine, Rd is alkylene of C? -C4 or substituted hydroxy derivatives thereof, Q is a covalent band or R, -N- (CH2) m-CHCH2-, where Re is hydrogen or -CH2CH (OH) CH2S03M wherein M is hydrogen or alkali metal, m is 0 or 1 and Z is hydrogen or an electron donor group. The method according to claim 2, characterized in that R is C 4 to C 1 alkylamidoalkyl; and Y is sodium. The method according to claim 1, characterized in that the anionic surfactant selected from the group consisting of a sodium butoxyethoxy acetate, a phenylethoxylate phosphate ester, and a sodium 2-ethylhexyl phosphate. The method according to claim 13, characterized in that the amphoteric surfactant selected from the group consisting of: OH CH3 OH I I I C4H9? -CH2CH'CH2-N "-CH2CHCH2S03-; CH3 C 2 H 5 OH CH 3 OH I l l l C 4 HsrCH-CH 2 CH 2 CHCH 2 -. -CH2CHC? 2S? 3-; and mixtures thereof 17. The method according to claim 1, characterized in that ultrafiltration is achieved by using a membrane having nominal pore sizes of less than about 1,000 Angstroms. The method according to claim 17, characterized in that the membrane is selected from the group consisting of polymer membranes, ceramic membranes and metal oxide membrane in a ceramic carrier.