MXPA96002983A - Composition and method driven by the best ph to separate sewage waste using an another carboxylate and a cation composiciondestabilizante - Google Patents

Abstract

The present invention relates to a method for the treatment of a contaminated aqueous effluent having a substantial amount of emulsified hydrophobic organic dirt, to remove dirt from the effluent, the method comprising: a) forming a contaminated aqueous effluent comprising the emulsified dirt and an effective pH phase separation amount of an amphoteric dicarboxylate surfactant of the formula: wherein A is R, or R is alkyl of 9 to 17 carbon atoms, m and n are independently 0-6, m + n > 1, "and" and "z" are independently 1-6 and X- is an alkali metal or ammonium cation, b) contacting the contaminated effluent with a cationic emulsion destabilizing composition, at a pH of less than 7, to forming a hydrophobic soil phase and an aqueous phase, and c) removing the hydrophobic soil phase from the aqueous phase, to produce a purified aqueous effluent with less than 500 ppm of hydrophobic soil

Description

COMPOSITION AND METHOD IMPULSED BY THE IMPROVED PH FOR SEPARATION OF WASTEWATER USING AN ANOTHER CARBOXYLATE AND A CATIONIC DESTABILIZING COMPOSITION Field of the Invention The invention relates to the separation of an emulsified hydrophobic organic soil from an aqueous effluent stream, using a combination of an amphoteric carboxylate and a cationic coagulant, a flocculating or destabilizing material, and an acidic pH. The amphoteric material and the destabilizer can be added together or separately, and can be added at any point. Preferably, the amphoteric is added in a detergent, and the destabilizing materials are added after the organic soil is emulsified in the aqueous stream. This polluted aqueous effluent commonly occurs in a number xie institutional and industrial facilities. These polluted aqueous waste streams can not be disposed of directly in municipal waste treatment systems. These waste streams can be treated with materials that can cause the hydrophobic organic soil to separate from the aqueous streams in a number of chemical addition protocols. The invention also relates to an improved cleaning composition for a spunbond or spunbonded article containing fiber contaminated with substantial amounts of organic hydrophobic soils, such as greases, oils, and consistent greases, and methods for separating these soils from the effluent from the cleaning process. The cleaning method comprises an active chemical addition and contains a step of changing the pH before discharging the effluent, which causes rapid separation of the hydrophobic organic soils from the effluent or waste water. The cleaning composition may contain both organic and inorganic materials which cooperate to obtain a cleaning and rapid separation of the hydrophobic dirt from the effluent.

Background of the Invention A number of institutional and industrial operations produce an aqueous effluent contaminated with substantial proportions of hydrophobic organic soils. These soils are commonly found in waste streams as emulsified droplets dispersed in the waste stream. These emulsions are commonly stabilized by the presence of one or more surfactants that are part of the effluent material. Commonly, non-ionic surfactants act as stabilizing agents. These waste streams are most commonly a result of the disposal of the hydrophobic waste or a result of a cleaning operation where large quantities of hydrophobic dirt are cleaned from the environmental surfaces, from clothes, from rags, from dishes and pots, etc. , and other objects that contain hydrophobic dirt. The resulting aqueous effluent may contain substantial proportions of hydrophobic organic soils typically derived from fat and oil. Before discarding, the aqueous effluent must be treated to separate these soils before the effluent can be safely discharged into municipal sewer systems. The use of alkaline cleaning compositions containing an inorganic detergent and builders components in combination with organic surfactant compositions and other components, have been common for many years in laundry operations. Typical laundry processes involve contacting the spunbond or non-spunbond fabric with an aqueous cleaning composition containing proportions of laundry chemicals dissolved or suspended in the aqueous medium. The organic and inorganic chemicals that operate to remove dirt from the fabric. The dirt becomes suspended by chemical cleaning agents in the aqueous stream through the action of active chemical cleaners. In commercial laundry operations, the Dirt load and type of dirt can create substantial operational difficulties. A substantial proportion of the laundry's workload will constitute articles contaminated with such hydrophobic organic dirt. These items include mechanic's clothing, workshop rags, workshop towels, contaminated uniforms, thrown clothes, machine covers, mop heads, and other typically manufactured units, either synthetic or natural fibers, spun or otherwise assembled into typically flexible units that can be soaked or saturated with substantial amounts of hydrophobic organic soils. The hydrophobic organic soils typically involved in the cleaning methods and compositions of the present invention comprise consistent fats, oils and fats. Fats are typically organic materials derived from natural sources, such as animals and plants. The fats are typically liquid or solid glycerol fatty acid esters, phospholipids, etc., and are typically produced in food processing, but also have a number of industrial uses. Oils are commonly liquids produced from the refining of petroleum, but may also include materials, such as liquid vegetable oil, silicone oil, etc. Consistent greases are commonly considered to be a solid or semi-solid hydrocarbon, thick and heavy, or suspensions of materials in solid, organic and inorganic particles in a base of fat or oil. Consistent greases are typically substantially semi-solid or solid materials used for lubrication purposes. Commonly, these hydrophobic organic soils are generated in the kitchen, in the bar, or in other food service environments, in workshop environments, such as printing workshops, metal workshops, auto repair shops , fast food businesses, restaurants, etc. In the operations of these facilities, substantial amounts of fat, oils and greases are used, and may come into contact with the walls and floors of the installation, and with the clothing worn by employees. The environment of the facilities is commonly cleaned using mops, workshop towels, bar towels, bar mops, kitchen rags, cleaners, rags and other cleaning instruments. The dirt load can be as much as 20 percent by weight, typically 5 percent by weight to 17 percent by weight on the fabric. Municipal, county, state, and federal regulations often place strict requirements on the concentration of a variety of contaminants in the effluent. After washing the dirty items, the substantial amount of organic dirt in the effluent of the Laundry is often unacceptable to the environment, due to the presence of up to 2,000 ppm of hydrophobic dirt and often more. In the production of the effluent from commercial laundries, it is often required that the consistent fats, oils and greases be substantially less than 250 ppm, and often between 10 and 100 ppm, measured by the analytical method of EPA 180.1. The efficient laundry chemicals in the aqueous medium remove the hydrophobic dirt creating an emulsion of the dirt in the aqueous medium. The emulsion comprises small hydrophobic droplets sometimes called mycelia, which are surrounded and stabilized by the detergent or surfactant materials. The dispersed nature of the dirt in the aqueous medium is a substantial barrier for its removal after washing. Before the removal can be obtained, the mycelium must be destabilized, the emulsion must be decomposed, fats, oils and fats consisting of a single phase must be reassembled, and the hydrophobic material in a single phase must be separated from the aqueous solution . A number of methods have been tried to separate the fats, oils and greases consistent from the laundry effluent. A useful alternative involves changing the pH of the washing medium from neutral or moderately alkaline to acid, to decompose the emulsion of the organic hydrophobic soil.

Once the emulsion is decomposed, a separate phase of hydrophobic soil forms, which can be easily removed. Boettner et al., U.S. Patent No. 3,117,999, disclose a tertiary carbonimine substituted with both ethylene oxide and propylene oxide blocks to form nonionic surfactant materials. Dupre et al., U.S. Patent No. 3,118,000, disclose alkyl amine compositions substituted with both ethylene oxide and propylene oxide blocks to produce a nonionic surfactant material. Maloney et al., U.S. Patent No. 4,605,773, disclose a low foaming pH sensitive amine polyether amine surfactant that can be used in the production of recycled secondary fiber paper. The surfactants described are sensitive to pH, and have substantial surfactant properties. Cohen, United States Patent Number 5,110,503, discloses compositions and methods for cleaning contaminated tola containing hydrophobic organic soil, with methods of separating the hydrophobic soil from the laundry effluent. Cohen uses a composition of matter comprising a first component, comprising a reaction product of an α, β-unsaturated acid, and a chain amine short, such as a β-aminodipropionic acid, having a structure assigned as RN (CH 2 CH 2 C 0 2 H) 2, with a variety of ether surfactants, such as a block copolymer of ethoxylate-propoxylate, sulfates or sulfonates and alkoxylated phosphates. Finally, McFarlan et al., U.S. Patent No. 5,207,922, primarily relate to a method for the treatment of laundry effluent or wastewater for the purpose of separating fats, oils and greases. In Column 3, lines 19-60, McFarlan et al. Describe chemical compositions of typical laundries. The comparative ability to separate the hydrophobic organic soils, such as fats, oils and greases consistent with the laundry effluent, is typically characterized by the concentration of the chemicals used in the laundry, and the pH at which the separation of the laundry occurs. phases, the speed of phase separation, and the final concentration in the aqueous effluent of hydrophobic dirt, such as fats, oils and residual consistent fats. The degree of separation is sensitive to pH. Reducing the pH as low as 2 can cause a clean decomposition; however, this low pH requires substantial amounts of acid, and also exposes the operating equipment and personnel to an unacceptably low pH. In addition, even at such a low pH, some compositions fail to reach an acceptable level of fats, - oils and fats consistent with the effluent. We have discovered in our work with chemical pH-sensitive laundry systems that many of these prior art systems have an unacceptably low pH requirement for clean separation, or fail to reduce the concentration of consistent fats, oils and fats. in the aqueous effluent to a level sufficient to meet environmental regulations. There continues to be a substantial need for a method to reduce the residual concentration of hydrophobic soils in the aqueous waste streams by using a pH change in the chemical addition protocol. In addition, there is a need to improve chemical laundry systems that can be used in cleaning processes involving articles that have a substantial load of hydrophobic organic soil in the laundry effluent. Systems are needed that produce an effluent that can be treated after washing to separate the fats, oils and greases consistent, such that the final concentration in the aqueous effluent is less than 250 ppm and preferably substantially less than 100 ppm. .

Brief Discussion of the Invention We have discovered that organic dirt Hydrophobic emulsified in an aqueous effluent stream can be separated using the combined action of a cationic destabilizing material and an amphoteric surfactant as stipulated below. In a preferred mode, a laundry effluent or other effluent from a cleaning process containing an amphoteric carboxylate by the laundry detergent, can be treated with a cationic coagulant or a destabilizing material, at a low pH, to make the dirt separate from the aqueous stream. These materials, in combination with pH change, cause rapid demulsification, and rapid separation of hydrophobic dirt from the aqueous stream. Within a short period of time, the emulsion decomposes, and a phase separation occurs when the hydrophobic soils are separated from the aqueous medium, leaving a residual low concentration of dirt. The cationic materials and the amphoteric carboxylate surfactant can be added in a number of different ways at different stages of wastewater generation, and transferred to the discharge outlets, including a single addition, a portion addition, and a continuous addition. . We have also discovered an alkaline cleaning composition useful in the processes of the invention, which comprises an effective amount of detergent from a source of alkalinity, an effective amount of a surfactant of amphoteric carboxylate of the formula: R-X-N-R2 R3 wherein: X is a linear or branched alkylene, hydroxyalkylene, or alkoxyalkylene group, having 1 to 4 carbon atoms; R is R4, wherein R4 is a linear or branched, saturated or unsaturated alkyl group having from 6 to 22 carbon atoms, or R4; R1 is hydrogen, A or (A) nX-C02 ~ Z +, wherein A is a linear or branched alkyl, hydroxyalkyl, or alkoxyalkyl, having 1 to 4 carbon atoms, n is an integer from 0 to 6, and Z is an alkali metal cation, a hydrogen ion or an ammonium cation; R2 is (A) n-X-C02-Z +; and R3 is absent or is A; or, preferably, wherein R4 is alkyl as defined above, having from 9 to 17 carbon atoms, X is a linear alkyl group having from 1 to 3 carbon atoms, n is from 0 to 3, and Z is an alkali metal or ammonium cation, for example, the (ono- and di-) acetates or alkylamino propionates, and the (mono- and di-) acetates or propionates of amido, and the betaine and the dihydroglycinates of the previous formula; and a composition nonionic surfactant comprising, either, an alcohol ethoxylate of 8 to 18 carbon atoms having from 3 to 15 moles of ethylene oxide, or an alkyl phenol ethoxylate of 8 to 9 carbon atoms having from 4 to 15 moles of ethylene oxide per mole of surfactant. The detergent can be used with a flocculant or destabilizer to initiate a separation of the organic hydrophobic soils from the laundry effluents by adjusting the pH. The effective pH scale is between 2 and 7, and preferably between 3 and 6.5. In addition, once the effective pH is reached and separation occurs, the concentration of the hydrophobic organic soils in the effluent can be as low as 100 ppm or lower. In our experimental work with the systems of the present invention, we have discovered that the materials reach a separation in a maximum concentration of hydrophobic organic soils in the effluent, which is substantially and surprisingly better than the operation of the laundry chemicals of the art. previous when comparable quantities of chemicals are used.

Detailed Description of the Invention Emulsified hydrophobic soils can be effectively separated from aqueous streams using a combination of a cationic coagulant or a material destabilizing agent and an amphoteric carboxylate surfactant. In a preferred laundry process, the amphoteric carboxylate is added in the laundry detergent. The pH adjustment of the effluent, followed by an addition of the cationic destabilizer, causes a rapid de-emulsification of the aqueous stream, a rapid phase separation of the hydrophobic organic soil from the aqueous material, which can then be easily separated. The amphoteric surfactant may be added at any stage in the production of the contaminated stream (for example, in a chemical laundry system, introduced into a downstream pipe or conduit, or added later with the cationic destabilizer.) The cationic destabilizer is typically added after adjustment of the pH The resulting treated aqueous stream containing minimal residual amounts of hydrophobic soil can then be discarded to a municipal waste treatment system The separation method of the invention uses a cationic destabilizer with an amphoteric carboxylate in a protocol pH change to remove dirt Laundry compositions of the invention include an effective concentration for detergent purposes, a source of alkalinity, a nonionic surfactant, and an amphoteric carboxylate containing surfactant to clean objects and surfaces contam inadas Cationic or destabilizing flocculant In the compositions and methods of the invention, a cationic flocculant or destabilizer is added after adjustment of the pH to acidic conditions. The flocculant causes small emulsified particles to form in large removable droplets, or a separate phase of hydrophobic material. Cationic materials are a well-known class of monomeric or polymeric chemicals that are used in the separation of liquid and solid dirt phases from aqueous streams. These cationic materials are described in Polyelectrolytes for water and waste water treatment, Schowyer, W.L.K. (CRC Press, Boca Raton, FL 1981). In general, the cationic materials are inorganic or organic, and are monomeric, oligomeric or polymeric. Inorganic cationic materials include polyaluminum chloride, aluminum sulfate or other alum materials, such as ammonium alum or ammonium alum, potassium alums; calcium chloride, ferric chloride, ferric sulfate, ferrous sulfate, sodium aluminate, sodium silicate that has an excess of sodium oxide on silicon dioxide, etc. Polyaluminum chloride is a polyaluminum oxide compound with a proportion of the oxide atoms replaced by chlorine atoms. Organic cationic materials or cationic polyelectrolytes are typically prepared using a common polymerization of free radical addition, condensation reactions, a hepophoxide addition reaction, and a variety of other reactions in the base structures of existing polymers, including Hofmann degradation, Mannich reaction, and nucleophilic shifts. High molecular weight polymerized cationic materials are manufactured by the polymerization of a cationic monomer. Cationic monomers include acrylic monomers, such as acrylates containing tertiary nitrogen, acrylic amides containing tertiary nitrogen, acrylates containing quaternary nitrogen and acrylic amides containing quaternary nitrogen; heterocyclic aromatic cyclic vinyl monomers, such as vinyl imidazolines, vinyl pyridines, vinylbenzyl quaternary ammonium salts, and allylic amines. Examples of the cationic acrylic monomer of the general formula are quaternary ammonium salts (using quaternizing agents, such as methyl chloride, dimethyl sulfate, and benzyl chloride) of dialkylaminoalkyl (meth) acrylates [such as (meth) acrylate dimethylaminoethyl, diethylaminoethyl (meth) acrylate, 3-dimethylamino-2-hydroxypropyl (meth) acrylate], and dialkylaminoalkyl (meth) acrylic amides [such as dimethylaminoethyl (meth) acrylic amide and 3-dimethylamino-2 acrylic amide -hydroxypropyl].

Cationic vinyl imidazolines include N-vinyl imidazoline and tertiary and quaternary salts thereof; the pyridines include 2-vinyl pyridine, 3-vinyl pyridine, N-vinyl pyridine, and tertiary and quaternary salts thereof; the vinylbenzyl quaternary ammonium salts include trialkyl ammonium salts of 1 to 4 vinylbenzyl carbon atoms, such as those described in British Patent Specification No. 862,719; and the allylic amines include (meth) allylic amines (denoting allylic amine and ethylic amine collectively, which expression will similarly be used subsequently herein as specified in the specification), and mono- and di-alkyl substitution products of 1 to 4 atoms carbon thereof, di (meth) allylic amines and alkyl substitution products thereof, and quaternized products of these (meth) allyl amines substituted by alkyl. Other ethylenically unsaturated monomers optionally copolymerized with the aforementioned cationic monomer are nonionic monomers, such as (meth) acrylic amides, (meth) acrylic N-mono- and N, N-di-alkyl amides of 1 to 14 atoms carbon, (meth) acrylonitriles, alkyl (meth) acrylates of 1 to 4 carbon atoms, styrene, vinyl esters (such as vinyl acetate), vinyl ethers (such as vinyl methyl ether), and vinyl halides (such as vinyl chloride), and monomers anionic, such as unsaturated carboxylic acids [such as (meth) acrylic acids and maleic acid], unsaturated sulfonic acids [such as aliphatic sulfonic acids, including vinyl sulphonic acid and (meth) allyl sulfonic acids, aromatic vinyl sulfonic acids, including vinyl toluenesulfonic acid and styrenesulfonic acid, sulfo (meth) acrylates, including alkyl sulfo (meth) acrylates of 2 to carbon atoms, and 2-hydroxy-3- (meth) acryloxypropanesulfonic acids, and sulfo (meth) acrylic amides , including 2- to 4-carbon-sulphonic acid amide (meth) acrylic acid, and 2-hydroxypropanesulfonic acid 3- (meth) acrylic acid, and salts thereof, such as alkali metal salts (Na, K , etc.), ammonium salts and amine salts, including mono-, di-, and tri-ethanolic amines and alkyl amines (of 1 to 4 carbon atoms). The cationic monomer ratio is generally at least 5 percent, desirably at least 10 percent, and in a particularly desirable way at least 30 percent, based on the weight of all monomers involved. The proportion of the (meth) acrylic amide is generally on a scale of 0 to 95 percent, preferably on a scale of 0 to 70 percent. The proportion of the anionic and hydrophobic monomer is generally not greater than 20 percent, preferably not greater than 10 percent. The polymer and the cationic monomer copolymer optionally with some other monomer are among those described in U.S. Patent Nos. 4,152,307 and 3,259,570. Other examples of the cationic high molecular weight destabilizers are the cationically modified polyacrylic amides, chitosan, polyethylene imines and epihalohydrin-amine condensates, and cationized starches. Specific examples of the cationically modified polyacrylic amides are Mannich modification products (such as are described in U.S. Patent Specification No. 2,328,901), and Hofmann modification products of polyacrylic amides. Examples of the polyethylene imine are polyethylene imines of polymerization degrees of 400 or more, preferably 2,000 or more, the N-methyl substitution products thereof, and the tertiary and quaternary salts thereof (such as are described) in US Patent Specification No. 3,259,570 Specific examples of epihalohydrin-amine condensates are polycondensates of epichlorohydrin with an alkylene diamine of two to six carbon atoms.The specific examples of cationized starches are cationic starches , described in the Encyclopedia of Chemical Technology (2nd edition), Volume 18, pages 688-689.The specific examples of the chitosan are the products obtained by heating derived chitins from shellfish, such as squid, shrimp, etc. The inorganic or organic cationic material is typically added to the wastewater stream after the stream is collected in a containment or treatment tank. An effective amount of the cationic polymer is added, typically up to about 1,500 parts per million, based on the total cumulative effluent, to the effluent, to participate in the coagulation, destabilization, or removal of the emulsified hydrophobic soils. Preferably, the cationic material is added in a concentration of about 100 ppm to 1,000 ppm, preferably about 200 ppm to 800 ppm, based on the total collected effluent.

Amphoteric Carboxylate Amphoteric carboxylate is a compound having the following formula: R - X - N - R \ R3 wherein: X is an alkylene, hydroxyalkylene, or linear or branched alkoxyalkylene, having 1 to 4 carbon atoms; R is R4, wherein R4 is a linear or branched, saturated or unsaturated alkyl group, having from 6 to 22 carbon atoms, or R4; R1 is hydrogen, A or (A) nX-C02 ~ Z +, wherein A is a linear or branched alkyl, hydroxyalkyl, or alkoxyalkyl, having 1 to 4 carbon atoms, n is an integer from 0 to 6, and Z is an alkali metal cation, a hydrogen ion or an ammonium cation; R2 is (A) nX-C02"Z +; and R3 is absent or is A. Particularly valuable materials for use in the present invention are amphoteric dicarboxylate and monocarboxylate materials, such as, for example, disodium cocoamphodiacetate, cocoamphodipropionate disodium, disodium cocoaminodipropionate, sodium cocoanifomonoacetate, cocoamidopropyl betaine, alkyl betaine, for example, cetyl betaine, dihydroxyethyl tallow glycinate, sodium lauriminodipropionate, or mixtures thereof These materials are available from Mona Industries, Inc. ., Patterson, New Jersey, and Rhone-Poulenc, Inc. The amphoteric carboxylate surfactant material described above can be added separately to the water current at any point during its creation or treatment. The amphoteric carboxylate may be added in a single portion, divided into several portions and added separately, or continuously introduced into the aqueous stream. Typically, the amphoteric material is added before the addition of a cationic or flocculent destabilizer, and before any change in pH or initiation of separation. A preferred way to use the amphoteric carboxylate material in the separation of hydrophobic soils from an aqueous stream, involves using a detergent composition formulated with the amphoteric carboxylate material. These aqueous detergents can be used in a variety of cleaning protocols, including laundry, floor cleaning, equipment cleaning, etc. The detergent composition contains a fully formulated builder system utilizing the amphoteric carboxylate as a component of the detergent. The detergent composition may contain a variety of other ingredients, including functional materials, both organic and inorganic, builders, etc. The nonionic surfactant materials that can be used in laundry compositions of the invention, comprise, either, an alcohol ethoxylate of 8 to 18 carbon atoms corresponding to the following formula: Alkyl C8_18-0- (EO) m-H wherein the alcohol ethoxylate has from 3 to 15 moles of ethylene oxide, or an alkyl phenol ethoxylate of 8 to 9 carbon atoms corresponding to the following formula: wherein the alkyl group may be straight or branched chain, or may be substituted by a common substituent, and the ethoxylate compound may comprise from 3 to 15 moles of ethylene oxide, preferably from 3 to 12 moles of ethylene oxide , and most preferably from 4 to 9.5 moles of ethylene oxide. When the separation technology of the invention is employed in a laundry composition, it can be combined with an alkaline source. As used herein, the term "alkaline source" refers to alkaline compounds that are known to be useful as builders in detergent compositions to improve the function of soil removal. Typical sources of alkalinity include sodium and potassium hydroxide, and sodium and potassium silicates. Sodium carbonate is also a typical source of alkalinity in detergent compositions. These sources of alkalinity are commonly f "available in either an aqueous or powder form, which can both be used in general in the formulation of typical detergent compositions.A second detergent component useful in a detergent composition is a surfactant. organic compounds that include both a hydrophilic fraction and a hydrophobic fraction on the same molecule and, therefore, can help in the operation of a detergent composition by improving the wetting of the substrate, the suspension of the removed contaminants, and other different functions. Wide selection of anionic and nonionic surfactants that provide different combinations of characteristics commercially available from a number of sources For a detailed discussion of surfactants, see Kirk-Othmer, Encvclopedia of Chemical Technology, Second Edition, Volume 19, pages 507-592 A third component of detergent useful in a detergent, is a chelating / sequestering agent. In general, chelating agents are the molecules capable of coordinating the metal ions commonly found in natural water, and thus prevent the metal ions from interfering with the operation of the other detersive components of the composition. Useful chelating agents include aminocarboxylic acids, condensed phosphates and polyacrylates. Suitable aminocarboxylic acids include specifically, but not exclusively, N-hydroxy-ethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), and diethylenetriamine-pentaacetic acid (DTPA). Suitable fused phosphates specifically, but not exclusively, include phosphates such as sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate. Suitable polyacrylates specifically, but not exclusively, include polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid-methacrylic acid, hydrolyzed polymethacrylic amide, copolymers of hydrolyzed polyamide-methacrylic amide, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, and hydrolyzed acrylonitrile-methacrylonitrile copolymers. For a detailed discussion of the chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, page 16, Volume 6, pages 1-24. Many colored materials contain a conjugated chain (a chain of alternating single and double bonds) with a terminal atom or group of atoms, which can resonate between two different covalent states. The color of These materials can be destroyed by breaking one of the double bonds in the conjugated chain and / or by chemically breaking the atom or terminal atoms to prevent resonance. Accordingly, any chemical compound capable of chemically decomposing a conjugated double bond, and / or capable of modifying an atom or group of resonant atoms to interfere with resonance, can be effective as a bleach. Broadly, the five categories of bleaching materials include: (i) chlorine, (ii) hypochlorites and chloramines, (iii) hydrogen peroxide and other peroxy compounds, (iv) chlorite and chlorine dioxide, and (v) reducing agents. In general, the preferred bleaching agent for use in laundry, dishwashing, and hard surface cleaners, are bleaching agents capable of releasing a kind of active halogen, under the conditions normally found in cleaning processes. Based on the superior bleaching performance and phase or availability, the preferred halogen-releasing compounds typically include the alkali metal dichloroisocyanurates, chlorinated sodium triphosphate, the alkali metal hypochlorites, monochloramine and dichloramine. Bleaching agents are generally deactivated when placed in an alkaline environment, such as is found within detergent compositions containing an alkaline source. In accordance with the foregoing, additional measures may be required to maintain the activity of a bleaching agent within a detergent composition. See, for example, Patents of the United States of North America Nos. 4,657,784 and 4,681,914. For a detailed discussion of bleaching agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Volume 3, pages 550-566. A fifth useful detergent component in a detergent composition is a defoamer. Typical defoamers are those compounds that have a suitable hydrophilic / hydrophobic balance to reduce foam stability. The hydrophobicity is typically provided by an oleophilic moiety, such as an alkyl or aromatic aralkyl group, or an oxypropylene group, or a chain. Hydrophilicity is typically provided by an oxyethylene group or a chain, or an ester group. The most frequently used defoamers include the phosphate esters, and the nonionic organic surface active polymers (surfactants) having both a hydrophobic group or block, and a hydrophilic ester or block group, such as a nonylphenol ethoxylate. A discussion of defoaming nonionic surfactants can be found in the Patents of the United States of America Numbers 3,048,548 (Martin et al.), 3,334,147 (Brunelle et al., And 3,444,242 (R et al.) A sixth detergent component useful in a detergent composition is an effective enzyme to catalyze the decomposition of different contaminating compounds commonly found in substrates that The enzymes commonly used include proteinases that are able to catalyze the hydrolysis of proteinaceous materials, amylases that are able to catalyze the hydrolysis of polysaccharides, and lipases that are capable of catalyzing the hydrolysis of fats. In addition to these previously described components, other conventional detergent components can be incorporated into the detergent composition, provided they do not interfere significantly with the cleaning or with the pH initiated phase separation.These components can include such compounds as bactericides, brighteners, anti-redeposition agents, inorganic salts, dyes and fragrances. The formulated detergent composition of the invention may correspond to the following proportions stipulated in Table I.

TABLE I The most Preferred powder Preferred Preferred Source of alkalinity 5-95 60-95 60-90 Amphoteric carboxylate 1-20 2-15 2-10 Non-ionic 1-25 2-20 4-15 Sequestrant 0-40 0-20 2-12 The more Preferred Liquid Preferred Preferred Liquid Source of alkalinity 5-20 0-10 0- 5 Amphoteric carboxylate 2-40 10-35 25-30 Nonionic 40-98 50-90 60-75 Sequestrant 0-20 4-15 4-10 The laundry compositions of the invention may comprise a number of product formats. The materials can be manufactured as liquid concentrates, particulate solids, granules or solid materials emptied contained, either in a solid plastic container or wrapped in a water soluble or insoluble film. We have discovered that the hydrophobic soil separation technology of the present invention operates through a cooperative action between the carboxylate surfactant amphoteric and the flocculant (or cationic destabilizer) at a low pH to separate the hydrophobic dirt from the aqueous stream. The preferred mode of addition of the materials in a laundry effluent separation process involves a first use of a fully formulated laundry detergent material containing the amphoteric carboxylate material. The laundry cloth is cleaned of the hydrophobic dirt using the fully formulated laundry detergent. The aqueous effluent containing the hydrophobic dirt passes from the laundry machine to a waste system. The current can be processed continuously, or it can be processed in a semicontinuous manner, or in a batch mode. Since the aqueous laundry effluent contains the amphoteric carboxylate surfactant resulting from the laundry protocol, the stream is first acidified to a pH of less than 7 using a sufficient amount of an acidic material to result in the desired pH. Typically, strong organic and inorganic acids can be added. These acids include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, trichloroacetic acid and others. Once the pH of the aqueous stream is adjusted to a preferred acid pH, the stream is contacted with a source of the flocculant or the cationic destabilizing material. In the process, the aqueous stream is contacted with the flocculant for a sufficient period of time to result in a phase separation of the hydrophobic soil that is sufficiently complete to result in a residual concentration of the hydrophobic soil, which is acceptable for the municipal sanitation operation procedures. In a continuous process, the chemicals are introduced into the stream to result in an effective concentration of the acidifier and the flocculant. The pipe and tanks of the continuous system are sized and configured to ensure proper mixing, and sufficient separation time to result in the desired concentration in the effluent. In a batch process, the effluent stream is directed to a containment tank, where it is treated with an acidulant, followed by a flocculating material, either in the same tank or in separate treatment tanks. The tanks are suitably agitated, and after phase separation, either the aqueous material at the bottom of the tank is removed, or the hydrophobic soil is skimmed from the top of the tank. The treated aqueous stream can be directed to the municipal sewer system. An amount of the amphoteric carboxylate surfactant composition is added to the stream, such that the concentration of the amphoteric material reaches an effective separation concentration by pH change which typically, it is less than about 1,000 ppm, based on the total effluent amount. Preferably, the surfactant material is used in a concentration of about 10 to 1,000 ppm, more preferably about 10 to about 250 ppm. In a similar way, the composition having sufficient acidity to change the pH of the effluent from about neutral or moderately alkaline to a pH of less than 7, preferably less than 6, more preferably in the range of about 3 to about 5.5, is added to the effluent material typically introducing the acidic material into a line leading to the containment or treatment tank, or to the treatment tank directly. The pH of the material in the containment tank or in the line can be monitored to ensure that the acidic material is added in sufficient proportions to maintain an effective pH change. An amount of the flocculant or the cationic destabilizing material is added to the aqueous stream, either in a continuous or batchwise processing mode, such that the flocculant concentration causes a rapid and substantially complete removal of the hydrophobic soil from the stream watery Typically, an effective amount of the flocculant comprises from about 10 to 1,250 ppm of the material, based on the aqueous stream. Preferably, the Flocculant material is added to the aqueous stream in a concentration of about 10 to 1,000 ppm, more preferably about 10 to 500 ppm, for reasons of economy and rapid processing of the aqueous stream. In the laundry chemical practice of the invention, the soiled articles are washed in a commercial washing machine, where the soiled article is contacted with an aqueous cleaning composition containing the ingredients described in the use levels of about 0.23. to 4.5 kilograms (0.5 to 10 pounds) of the composition for every 45 kilograms (100 pounds) of cloth, rag, towel or other dirty unit. Typical laundry cycles are used in the washing of dirty items. After finishing washing, the effluent contaminated with the hydrophobic organic dirt can be accumulated and treated. In the practice of the invention, the effluent is treated after leaving the machine, or it accumulates in any convenient storage container having appropriate handling equipment for the addition of the chemical to change the pH. These pH changing chemicals may comprise a common acidic material capable of changing the pH of the effluent from the pH typically between 8 and 12 to a pH of less than 6. Suitable addition controls, agitators, and pH monitoring equipment are desirable.

In addition, the effluent container could be equipped with a site to remove a sample for testing. The effluent can be tested for residual hydrophobic dirt during phase separation. The effluent container should also be equipped with elements to remove the treated effluent into a sewer discharge. In addition, the container must be equipped with an apparatus that can safely remove the unmulsified dirt to an appropriate waste. In our work with the laundry detergent composition of the invention, we have discovered that the compositions of the invention exhibit superior performance when comparing their pH controlled separation properties with other surfactant systems in terms of residual hydrophobic soil concentration and the pH of the phase break between the hydrophobic portion and the aqueous portion. The compositions of the invention, and the operation of the composition for cleaning and phase separation, are exemplified in the following examples and tables. We believe that the operation of the separation chemicals in the laundry systems set forth below, shows that the chemicals will function in a similar manner in any generic aqueous waste stream that contains hydrophobic soil. The following contains a better mode. The previous discussion, examples and data they provide a basis for understanding the description. However, the invention can incorporate a variety of compositions. In accordance with the foregoing, the invention is found in the claims appended hereinafter.

Example 1 Or CH2CH2-OH CH3 (CH2) 4-C II-HH-CH2CH2-N-ICH2CH2C02N? CYH COCONUT- COCONUT- The compositions stipulated in Table II were evaluated for their cleaning ability and for their operation to separate the hydrophobic dirt from the aqueous effluent. The cleaning performance evaluations were based on a Powder laundry detergent based on the chemistry of a surfactant containing amphoteric carboxylate. The formulas to be evaluated including the comparative preparation and Examples 1 to 5, were evaluated using a common laundry procedure stipulated in Table III.

TABLE II FP-EP-25 6 811 LF-EP-61 7 CyNa-50 TOMAH E-T-5 8 CEM OPD-LF 9 CDX ULTRA 10 Sipernate TABLE III Typical Washing Formula Using Alkaline Powder Composition The experimental results summarized in Table IV show the effectiveness of the detergents of the invention and the effectiveness of the separation technology. In Table IV, under the wash quality, a wicking time test is used to demonstrate that the compositions of the invention can be very effective soil removal detergent compositions. In the data called water quality, the capacity of the separation technology is demonstrated to result in a low residual hydrophobic soil. In the wick time data, a fast time shows excellent cleaning properties. In the water quality data, a low number indicates a low residual hydrophobic soil content.

TABLE IV EPA 413.4 -EPA 180.1 RESULTS: Polymer required (in ppm) to de-emulsify the effluent, in such a way that the turbidity of the effluent, measured by the procedure of Turbidity Method of Analysis, Methods for Chemical Analysis of Water and Wastes. EPA-600 / 4-79-020, March 1983, is less than 10 NTUs at 60 seconds after pH adjustment. CatioA is a polymer of Quaternary Ammonium (CAS 42751-79-3), CatioB is a Polyquaternary Amine (CAS 42751-79-1), and CatioC is Aluminum Hydrochloride (CAS 1327-47-9) .

TABLE V Polymer (ppm) 11 11 Minimum concentration of catiopolymer necessary to de-emulsify and separate hydrophobic dirt. 12 Uses the chemical of amphoteric dicarboxylate. 13 Chemistry of the McFarlan patent.

The wicking time test is a qualitative test used to predict cleaning properties on the cleaned cloth with the test formula. In the wicking time trial, a red workshop towel (approximately 30 centimeters (12 inches) by 30"centimeters (12 inches)) is immersed in a tray containing 2.5 to 5 centimeters (1 to 2 inches) The towel hangs over a bar or rope, and is submerged in the water, held in place using a bar or other heavy system, the time needed for the water to reach the level of one inch is measured (2.5 centimeters) or at the level of two inches (5 centimeters) The ability of water to moisten the fabric is characteristic of a high quality cleaning detergent used to clean the fabric.A fabric soiled with oil or residual grease will rise more slowly than A clean cloth According to the above, the rapidity with which the aqueous material moistens and ascends the workshop towel through the fabric mesh, characterizes qualitatively the detergent's possible detergent properties. water quality ion Table IV are obtained using the method of EPA 413.4 to obtain the content of fat, oils and fat consistent (FOG) after five minutes of separation time after the addition of catioor flocculating material. The data tagged with NTU are obtained using the procedure of EPA 180.1 after five minutes of separation. The inspection of the data stipulated in Tables IV and V shows the operation of all the compositions of the invention substantially improved over the comparative compositions of the standard commercial prior art material. In particular, the material identified as Composition (CPl) containing a preferred amphoteric carboxylate has a clearly superior performance.

Example 2 The compositions stipulated in Table VI were evaluated using a common laundry procedure stipulated in Table VI, to determine the amount of amphoteric carboxylate in parts per million, required to decompose the emulsion, compared to the control, where the standard is the amount of non-iosurfactant required.

TABLE VI WASHING PARAMETERS

Claims (23)

1. A method for the treatment of a contaminated aqueous effluent having a substantial amount of emulsified hydrophobic organic dirt, to remove dirt from the effluent, the method comprising: (a) forming a contaminated aqueous effluent comprising the dirt and ulsified and an amount of phase separation of effective pH of an amphoteric carboxylate surfactant of the formula: R - X - N - / * R¡¿ \ R3 wherein: X is a linear or branched alkylene, hydroxyalkylene, or alkoxyalkylene group, having 1 to 4 carbon atoms; R is R4, wherein R4 is a linear or branched, saturated or unsaturated alkyl group having from 6 to 22 carbon atoms, or R4; R1 is hydrogen, A or (A) n -X-C02 ~ Z +, wherein A is a linear or branched alkyl, hydroxyalkyl, or alkoxyalkyl, having 1 to 4 carbon atoms, n is a whole from 0 to 6, and Z is an alkali metal cation, a hydrogen ion or an ammonium cation; R2 is (A) nX-C02"Z +; and R3 is absent or is A; (b) contacting the contaminated effluent with a cationic emulsion destabilizing composition, at a pH less than 7, to form a hydrophobic soil phase and an aqueous phase, and (c) removing the hydrophobic soil phase from the aqueous phase to produce a purified aqueous effluent with less than 500 ppm of hydrophobicity

2. The method of claim 1, wherein the purified aqueous effluent contains less than 100 ppm of hydrophobic soil

3. The method of claim 1, which additionally contacts the contaminated aqueous effluent with a sequestrant

4. The method of claim 3, wherein the sequester comprises sodium tripolyphosphate, pyrophosphate of sodium or mixtures thereof

5. The method of claim 3, wherein the sequestrant comprises ethylenediaminetetraacetic acid or its sodium salt, nitrilotriacetic acid or its sodium salt, po acrylic acid or its sodium salt, or mixtures thereof.

6. The method of claim 1, wherein, in the amphoteric carboxylate surfactant, R is R 4 or R 4 -CO-NH, wherein R 4 is an alkyl of 5 to 17 carbon atoms, X is a linear alkylene group having 1 to 3 carbon atoms, n is 0 to 3, and Z is an alkali metal or ammonium cation.

The method of claim 1, wherein the contaminated effluent, at a pH less than 6.5, is contacted simultaneously with the cationic emulsion destabilizing composition and with additional amounts of the amphoteric carboxylate surfactant.

The method of claim 1, wherein the contaminated effluent is contacted with the phase of the cationic emulsion destabilizing composition, followed by additional amphoteric carboxylate, at a pH between 3 and 6.

The method of the claim 1, wherein a sufficient amount of the cationic emulsion destabilizing composition is added to the contaminated effluent to produce a concentration of the cationic composition comprising from 25 to 1,500 ppm.

The method of claim 1, wherein a sufficient amount of the amphoteric carboxylate surfactant is added to the contaminated effluent, prior to the addition of the cationic material, to produce a surfactant concentration of the amphoteric carboxylate comprising from 10 to 500 ppm of the carboxylate surfactant in the contaminated effluent.

11. A concentrated alkaline cleansing composition, which comprises: (a) an effective detergent amount comprising from 5 to 95 weight percent of an alkalinity source; (b) an effective detergent amount of an amphoteric carboxylate surfactant of the formula: I R1 R - X - N - R ^ \ R2 wherein: X is a linear or branched alkylene, hydroxyalkylene, or alkoxyalkylene group, having 1 to 4 carbon atoms; R is R4, wherein R4 is a linear or branched, saturated or unsaturated alkyl group having from 6 to 22 carbon atoms, or R4; R1 is hydrogen, A or (A) n-X-C02 ~ Z +, where A is an alkyl, hydroxyalkyl, or linear or branched alkoxyalkyl, having 1 to 4 carbon atoms, n is an integer from 0 to 6, and Z is an alkali metal cation, a hydrogen ion or an ammonium cation; R2 is (A) n-X-C02 ~ Z +; and R3 is absent or is A; (c) an effective detergent amount comprising from 1 to 25 weight percent of a nonionic surfactant composition comprising an alcohol ethoxylate of 8 to 18 carbon atoms of the formula: Alkyl C8_18-0- (EO) m-H or an alkyl phenol ethoxylate surfactant of 8 to 9 carbon atoms of the formula: Alkyl (EO) n-H each having from 3 to 15 moles of ethylene oxide per mole of surfactant.

The composition of claim 11, wherein the alkalinity source comprises an alkali metal carbonate.

The composition of claim 11, wherein the source of alkalinity comprises an alkali metal hydroxide.

The composition of claim 11, wherein the source of alkalinity comprises a water-soluble alkali metal silicate.

15. The composition of claim 13, wherein the alkali metal hydroxide comprises a hydroxide of sodium.

16. The composition of claim 11, which additionally comprises a sequestrant.

The composition of claim 16, wherein the sequestrant comprises sodium tripolyphosphate, sodium pyrophosphate or mixtures thereof.

The composition of claim 16, wherein the organic sequestrant comprises ethylenediaminetetraacetic acid or its sodium salt, nitrilotriacetic acid or its sodium salt, polyacrylic acid, or a copolymer of acrylic acid or its sodium salt, or mixtures thereof. same.

The composition of claim 11, wherein, in the amphoteric surfactant, R is R4 or R -C0-NH, where R4 is alkyl of 9 to 17 carbon atoms, X is a linear alkylene group having 1 to 3 carbon atoms, n is 0 to 3, and Z is an alkali metal or ammonium cation.

The composition of claim 11, wherein the alkalinity source comprises a mixture of 5 to 60 weight percent sodium carbonate, and 10 to 70 weight percent sodium metasilicate.

The composition of claim 11, wherein the source of alkalinity comprises a mixture of 5 to 60 weight percent sodium carbonate, 20 to 35 weight percent sodium hydroxide, and 10 to 70 weight percent. 100 percent by weight of sodium metasilicate, each based on the weight of the total composition.

22. A method for cleaning cloth, which contains a substantial amount of oily or greasy dirt, with a composition that can be used to remove dirt from a contaminated aqueous effluent resulting from cleaning, the method comprising: (i) putting in contacting the soiled fabric with an aqueous cleaning composition comprising a greater proportion of water; and an effective detergent amount of a concentrated composition according to any of claims 11 to 21, which results in substantial quantities containing alkaline effluent of organic hydrophobic soil; (ii) adjusting the pH of the effluent to less than 7 to produce an acid effluent, and contacting the effluent acid with a cationic emulsion destabilizer to produce an organic phase comprising consistent fats, oils and fats, and an aqueous phase; and (iii) separating the organic phase from the aqueous phase.

23. A method for the treatment of a contaminated aqueous laundry effluent having a substantial amount of emulsified hydrophobic organic soil, for separating the dirt from the effluent, the method comprising: (a) cleaning in laundry using a fully formulated laundry detergent comprising an effective cleansing and pH phase separation amount of an amphoteric carboxylate surfactant according to claim 11; (b) contacting the contaminated aqueous laundry effluent with a cationic emulsion destabilizing composition at a pH of less than 7 to form a hydrophobic soil phase and an aqueous phase; and (c) separating the hydrophobic soil phase from the aqueous phase to produce an aqueous effluent purified with less than 500 ppm of hydrophobic soil.