JPH09299931A - Aldehyde-based surfactant and treatment of waste water from industrial, commercial and public facility - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the purifying property of waste water when removing impurities associated with a splitting, nonionic surfactant in an aqueous flow by adjusting pH of the aqueous flow to acidic pH so that surfactant may be irreversibly split into a water insoluble fraction and a water soluble fraction and removing a water insoluble phase from the aqueous flow.

SOLUTION: In the case of purifying waste water, pH of an aqueous flow is adjusted to sufficiently acidic pH so that a surfactant may be split into a relatively water insoluble fraction and a relatively water soluble fraction. In this way, impurities are released from the association with the surfactant, and a water insoluble phase including the released impurities is formed, and treatment is made so as to separate it from the aqueous flow. In this case, the splitting nonionic surfactant is that represented by any one of the formulas I, II or a mixture thereof. In the formulas, R is hydrogen, R' is a residual group of organic compounds derived from aldehyde having the formula III (R is hydrogen, R' is a residual group of organic compounds having about 8-20 total carbon atoms), X is hydrogen or the like, and Y and Z are hydrogen, methyl or the like.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION This invention relates to non-ion-splitting surfactants and includes fats, oils and greases (FOGs), total petroleum hydrocarbons (TPHs), and other hydrophobic materials such as those mentioned above. Water-insoluble oily or waxy contaminants
For industrial, commercial, and utility applications to treat aqueous streams that retain impurities, typically effluent streams,
Regarding the use of these surfactants. The present invention provides compositions and methods contemplated for treating the aqueous stream to remove hydrophobic materials such as those mentioned above. These aqueous streams generated during processing operations contain the contaminants retained in the form of relatively stable emulsions by the action of the surfactants. The contaminants can be removed from the aqueous effluent by acidifying the wastewater, resulting in the release of the contaminants. Specific examples of said effluents are used laundry wash water, contaminated oil / water emulsion from metalworking processes, aqueous streams from textile dyeing, wash water streams from metal (vehicle) cleaning operations, deinking. Includes waste or recycle streams from the process.

[0002]

[Prior Art] Direct emission of pollutants or public treatment plant (POT)
W: Public Owned Treatment
Emissions of pollutants into Works generate large volumes of aqueous effluent containing FOG, TPH, and / or other emulsified oils (organic matter) commonly referred to as oily wastewater, for many industries such as industrial laundry. Raise important issues in metal processing, food processing, metal cleaning, etc.

The discharge of the wastewater stream to the POTW or the direct disposal of the cleaning solution into the waterway must be done according to environmental regulation standards. To meet these requirements, wastewater streams can be pre-treated to pollutants (eg FOG, TPH, etc.)
It is common to reduce emissions and comply with emission regulations. In the case of industrial laundry operations, this problem is particularly important because large volumes of laundry wastewater are generated containing various pollutants. These contaminants are removed from the soil during the washing operation,
The impurities are then held in aqueous solution and come into association with the surfactant used to form the relatively stable emulsion.

Metalworking fluids are used to provide cooling and lubrication during many of the cutting, polishing and forming operations used during machining. Metalworking formulations include, for example, emulsification,
It is a complex mixture containing additives to perform various functions such as corrosion inhibition, lubrication, coupling, defoaming, wetting, dispersion and the like. Surfactants are used primarily in metalworking formulations as emulsifiers, wetting agents and corrosion inhibitors.
Reduce the need for emissions and waste treatment (cost savings)
Therefore, the fluid is continuously recirculated for a long time. However, after a period of use, the efficacy of metalworking fluids has decreased significantly due to contaminants introduced into the fluid from the working operation. These contaminants include machine oil (often called trump oil), metal particles, anion salts, cations,
And impurities such as other contaminants collected in the metalworking fluid. These fluids are then drained to a reservoir where a number of treatment techniques are used to remove oil (some of which is recirculated) and grease, and the required local pretreatment regulations (typically The aqueous phase is adapted to oil and grease concentrations up to 100 mg / liter).
One of the processing techniques involves chemical emulsion (oil / water) disruption to add an emulsion disrupting agent such as alum or polyelectrolytes to facilitate phase separation. The method works by neutralizing the charge that promotes the emulsification of oil droplets. Typically in metalworking formulations,
This ability of anionic surfactants, such as soaps, petroleum sulfonates, etc., that have negatively charged ions that retain surface-active properties, to neutralize the charge (thus giving surfactant properties) Used to destroy). Anionic surfactants have undesirable properties as compared to nonionic surfactants, such as foaming and lack of hard water stability. However, nonionic surfactants have no charge and are not adaptable to this type of chemical emulsion breakage.

Hard surface cleaning formulations are used to remove working fluids, oils, mud, debris, etc. from hard, usually smooth surfaces such as metals, ceramics and the like. Alkaline detergents are usually used for aqueous systems and surfactants are used as wetting and dispersing agents.
Cleaning of hard surfaces can be done by dipping or spraying. The surfactant should be stable to alkaline pH and low foaming. Decontamination chemicals are contaminants (eg oils) from cleaned surfaces such as metal parts, ceramic tiles etc. after several cleaning operations.
To retain the contaminants accumulated sufficiently to limit the efficacy of the surfactant to remove and prevent redeposition (due to emulsification). Although additional surfactants can be added to alleviate this problem, the additional surfactants increase the likelihood of unwanted foam formation, and waste treatment (oil / water) when the bath is discarded. Emulsion) is more difficult. Alkylphenol ethoxylates [for example, Union Carbide Co., Danbury, Connecticut, USA,
Triton® X-100] is known to be a good surfactant for metal cleaning operations. However, these materials are non-ionic, which makes waste disposal difficult.

Deinking formulations are used to remove printing ink from old newsprint, magazines, office paper and the like.
In one method, referred to as the "wash" method, printed waste paper is fibrous in the presence of an ink removal formulation in an alkaline environment under elevated temperature and mechanical agitation.
Various washing steps are employed in order to obtain a thick suspension of pulp fibers which contains little ink. Surfactants are used during the deinking process as wetting agents and as emulsifiers to facilitate dispersion of the ink and binder. Alkylphenol ethoxylates and primary and secondary fatty alcohol ethoxylates are commonly used because of their low foaming and good dispersibility. The effluent from the washing process containing these surfactants has an emulsion / dispersion (e.g. ink in water) that must be waste treated. In addition, the recycled water stream from the process needs to be treated.

The textile industry also produces several wastewater effluent streams from those processes. For example, during scouring (washing method) of artificial fibers, a surfactant is added in order to remove chemical additives (for example, lubricating oil) remaining on the fibers. Surfactants are used for detergency and for the dispersion of washed-off particles. Alkylphenol ethoxylates are commonly used because of their low foaming and good dispersibility. Effluents from washing steps containing these surfactants retain emulsions (eg oil-in-water) that are difficult to dispose of. In addition, in the disperse dyeing method, a surfactant is used to disperse the water-insoluble dye and ensure uniform distribution in the dye bath. If these baths have to be discarded, the resulting dispersions are difficult to dispose of.

In the process known as tertiary oil recovery, the oil deposits remaining after the primary and secondary oil recovery are extracted. In chemical flooding of deposits, chemicals are added to water to aid recovery. Among these chemicals are surfactants used to reduce the surface tension between oil and water. That is, the surfactant (and optionally the co-surfactant) forms an emulsion of the crude oil and water, which removes the oil from the deposit. Micellar flooding
In the ing method, the surfactant is pumped with the crude oil into the oil deposit over a period of several days to further extract the crude oil. Generally, anionic surfactants (eg petroleum sulfonate, ether sulphate, ether carboxylate etc.) are used.

The above uses for the following compounds in the present invention are not exclusive and illustrate the problem:
Therefore, it illustrates the need for the present invention for industrial, utility and commercial treatments to generate wastewater streams containing FOG, TPH and other water insoluble contaminants that are emulsified due to the presence of surfactants. To do.

One of the desirable properties of effective surfactants is to efficiently emulsify water-insoluble ingredients. However, the separation of these components and other contaminants, which can now be considered impurities, from the aqueous effluent is complicated by the emulsifying properties of the surfactant. Therefore, the stronger or more efficient the surfactant in removing and suspending hydrophobic compounds in aqueous solution, the more difficult the subsequent separation of hydrophobic impurities from water.

What is needed by businesses and industries that eventually use surfactants in the ambient discharged process stream is to initially emulsify the hydrophobic agents and suspend them in water. It can be used as a conventional surfactant, and then permanently reduce or eliminate its surfactant capacity, first releasing and separating the hydrophobic components associated with the surfactant and in suspension. And is a highly effective surfactant that can be modified to aggregate.

This problem has been addressed in some industrial laundry industries by the use of amine-based surfactants and various improved processes based on their use. These methods generally treat the aqueous stream holding the amine-based surfactant and the emulsified hydrophobic contaminants with an acid to deactivate the surfactants and release the hydrophobic contaminants. And then agglomerate the contaminants and then remove them, usually by skimming or other physical separation methods. A typical method among them is US Pat. No. 5,076,937,
5,167,829, 5,207,922 and 5,374,
No. 358 is disclosed in each specification. However, amine-based surfactants have not proven to be fully satisfactory. Because their detergency is lower than the best commonly used surfactants for laundering, such as nonylphenol ethoxylate (NPE), which is generally considered to be the industry standard. Is. Furthermore, the amine-based surfactants tend to improve and restore their surface activity, for example, when the pH is increased to neutralize the stream prior to discharge to the POTW. Problems (eg foaming) may occur downstream.

[0013]

SUMMARY OF THE INVENTION According to the present invention, alkaline or high pH
It has been found that certain acetal-based surfactants that act as nonionic surfactants in the environment exhibit excellent end-use performance combined with desirable surfactant fissionability. However, these surfactants chemically cleave the hydrophobic portion of the surfactant from the hydrophilic portion in acidic environments due to the presence of the chemical functionality of the acetal. This destroys the surfactant's surface activity, thereby eliminating the association of the surfactant with the hydrophobic component and making it easier to separate the surfactant from the aqueous phase. This practical bond-breaking action that causes a hydrophobic substance portion and a hydrophilic substance portion is called "fissile property". Agent. It should be noted that, contrary to prior art amine-based surfactants, which are generally considered to be "reversible substances," the surfactants of the present invention are surfactants even when the pH is again raised to the alkaline range. Not modified to.

Broadly speaking, the present invention provides a fissile nonionic surfactant of any of the following formulas or mixtures thereof:
And a method for removing impurities associated with the surfactant in an aqueous stream, the method comprising:

(A) adjusting the pH of the aqueous stream to a pH that is sufficiently acidic to irreversibly split the surfactant into a relatively water-insoluble fraction and a relatively water-soluble fraction. By inactivating the surfactant to release impurities from association with the surfactant, the released impurities and the water-insoluble fraction of the surfactant forming a relatively water-insoluble phase,
Then

(B) removing at least a portion of the water-insoluble phase from the aqueous stream,

In this case, the fissile nonionic surfactant has the formula:

Embedded image Or

Embedded image {Where R is hydrogen and R'is of the formula:

Embedded image An organic compound derived from an aldehyde (wherein R is hydrogen and R'is a residue of an organic compound (substituted or unsubstituted) having a total of about 8 to about 20 carbon atoms) (substituted Or unsubstituted) residues; X is hydrogen or a hydrophobic endcap residue; Y is hydrogen, methyl, ethyl or a mixture thereof;
Z is hydrogen, methyl, or ethyl; m is 0 or 1
And n is an integer from 1 to about 40} or a mixture thereof.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the purification of commercial, industrial and utility wastewater streams to bring them into compliance with dischargeable environmental standards. Although the compositions and methods of the present invention have broad industrial applicability and use as described above, for convenience, the present invention is described primarily with regard to its highly effective applicability to industrial laundry processes. It will of course be understood by a person skilled in the art that the advantageous results can also be obtained in a number of other industrial applications by adjusting the formulation if necessary.

The present invention provides a method for removing contaminants such as FOG and TPH, as shown in a preferred embodiment, from the effluent of laundry wastewater on a batch or continuous basis. During the treatment process, contaminants disposed of in the fabric to be cleaned are treated with an alkaline detergent containing a splittable nonionic surfactant of the type described herein to emulsify or otherwise It causes an association between the active agent and the contaminant. The surfactant is disrupted by acidification of the wastewater effluent, destroying the emulsifying properties associated with the surfactant, thus phase separating contaminants from the water. FOG, TPH and other contaminants are then removed from the wastewater by conventional methods (eg skimming, chemical treatment, dissolved air flotation, etc.). And the laundry wastewater can be discharged to the POTW after the final pH adjustment to make the waste effluent comply with environmental regulations.

More specifically, the present invention relates to a method for removing impurities in an aqueous effluent associated with certain pH-accepting, fissionable nonionic surfactants. It is known that anionics, cationics and amphoteric surfactants containing charged ions can be neutralized (ie loss of surface activity) by adjusting the pH of the mixture. However, this does not apply to conventional nonionic surfactants other than certain amine-based surfactants, as they have no charged moieties. It has been found in accordance with the present invention that certain cyclic acetals having pendant hydroxyl groups can function as the hydrophobic moiety of pH-splitting surfactants. This material, whether alkoxylated or otherwise modified, has a wide range of HLBs and unexpectedly superior performance characteristics to those exhibited by other surfactants of related chemical structure. It is possible to provide a surfactant having

Surfactants useful in the present invention are known in the art, particularly US Pat. Nos. 3,948,953 and 3,909,4.
No. 60 Specification and Polish Provisional Patent No. 115,
527 and 139,977. However, the present invention improves upon the teachings of the art by providing optimal molecular structures and extending their application to a wide variety of end uses where the above surfactants were previously unknown. As described in more detail below, the surfactants of the present invention exhibit unexpectedly superior cleaning performance comparable to NPE in the area of laundering, particularly industrial laundering, and are environmentally friendly such as phosphate builders. Significantly reduce problem substances. In other end uses, the surfactants of the present invention exhibit unexpected advantages for good oil / water emulsification, metal cleaning, low foaming, and waste treatability of metalworking formulations.

The pH-accepting, splittable, nonionic surfactants useful in the present invention include acetal-based surfactants derived from the condensation of an aldehyde with a polyol followed by alkoxylation. Specifically, the surfactant of the present invention has the formula:

Embedded image Or

[Chemical formula 26] {In the above formula, R is hydrogen and R'is the formula:

Embedded image Wherein R is hydrogen and R ′ is an organic compound (substituted or unsubstituted) having a total of 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, and most preferably 12 to 15 carbon atoms. A residue of an organic compound (substituted or unsubstituted) derived from an aldehyde represented by the formula: X is hydrogen or a residue of a hydrophobic end cap, for example, CH ₂ Ph, t -Butyl; Y is hydrogen, methyl, ethyl or mixtures thereof; Z is hydrogen, methyl or ethyl; m is 0 or 1;
n is at least 1, preferably 1 to about 40, more preferably 2 to about 12, most preferably 3 to about 9} or a mixture thereof.

As used herein, the phrase "residue of an organic compound" includes all acceptable residues of an organic compound. (The term "acceptable" means all residues, moieties, etc. that do not significantly interfere with the performance of the surfactant for its intended purpose.) In a broader sense, the acceptable residue is an organic compound. Acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic residues of. Examples of the residue of the organic compound include, for example, alkyl, aryl, cycloalkyl, heterocycloalkyl, alkyl (oxyalkylene), aryl (oxyalkylene), cycloalkyl (oxyalkylene), heterocycloalkyl (oxyalkylene), hydroxy. (Alkyleneoxy) and the like. The acceptable residues can be substituted or unsubstituted for the appropriate organic compound and can be the same or different. This invention is not intended to limit the permissible residues of organic compounds in any manner.

The term “substituted” as used herein includes all permissible substituents of organic compounds. In a broader aspect, the permissible substituents are acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic groups of organic compounds,
Includes aromatic and non-aromatic substituents. Examples of the substituent include, for example, alkyl, alkyloxy, aryl,
It includes aryloxy, hydroxy, hydroxyalkyl, halogen and the like. The carbon number in them can range from 1 to about 20 or more, preferably from 1 to about 12. The permissible substituents may be one or more and the same or different for appropriate organic compounds. The present invention is in no way limited by the permissible substituents of organic compounds. The structural formulas (I) and (II) above represent polyoxyalkylene derivatives of acetals and are composed of a mixture of ethoxylates, propoxylates or butoxylates produced by either random or block processes. It is understood by those skilled in the art that it is possible. Although there are no specific known limits on the molecular weight of the aldehyde, the resulting surfactants become more paraffin-like in nature as the carbon number of the aldehyde exceeds about 12-15. While this can lead to better phase separation, such aldehydes are not readily available (in industrial quantities) due to the difficulty of preparing and purifying them.

The splittable nonionic surfactants of the above formula can be prepared by conventional methods known in the art.
(For example, U.S. Pat. No. 3,948,953 and its CIP No. 3,9, which mention the pH splitting properties of the above compounds.
09,460 and Polish provisional patent No. 115,
527 and 139,977). For example, a surfactant of the above formula uses a polyol starting material having at least three hydroxyl groups, two of which form the cyclic 1,3-dioxane or 1,3-dioxolane functionality, It can be produced by treating a polyol with a suitable aldehyde. Examples of such polyols are, inter alia, for example glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (trimethylolpropane), 1,1,1-tris (hydroxymethyl) -ethane ( Trimethylolethane), sorbitol and mannitol. Glycerin and trimethylolpropane are preferred. Examples of suitable aldehydes include 2-ethylhexanal, octanal, decanal, 2-propylheptanal and isomers (from aldol condensation of valeraldehyde), undecanal, and dodecanal. Among these, 2-ethylhexanal, 2-propylheptanal, decanal, and dodecanal are preferable. Most preferred is a sequence of isomers produced by the "Oxo" reaction of C ₁₁ -C ₁₄ olefins. This isomer can be obtained from EniChem Augusta, Inc., Milan, Italy.

The first step in the synthesis of the splittable surfactants of this invention is about 0 based on total charge, under suitable reaction conditions, usually atmospheric pressure and a temperature of about 40 to about 175 ° C. The polyol is removed in the presence of an acid catalyst such as sulfuric acid or toluenesulfonic acid in an amount of 0.01 to about 10, preferably about 0.01 to about 0.5% by weight, while removing the water resulting from the condensation reaction. Forming the acetal moiety by treatment with an aldehyde. Phosphoric acid has also been found to be preferred. This is because phosphoric acid has a slightly slower reaction rate, but it produces somewhat more light and more desirable color in the product. The aldehyde is mixed with about 1.1 to 1.3 molar excess of polyol. Heptane is added as a solvent to facilitate azeotropic removal of water from the system. A 5-membered ring (1,3-dioxolane) is preferentially formed.

The resulting acetal having at least one free hydroxyl group is suitable for alkoxylation reactions usually carried out under basic conditions. The reaction involves reacting an acetal with a suitable alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. Conventional reaction conditions such as temperatures of about 80 to 150 ° C. and moderately elevated pressure can be employed. Suitable basic catalysts include tertiary amines, sodium hydroxide, potassium hydroxide and the corresponding metals, hydrides and alkoxides. The resulting acetal-based alkoxylation reaction product is represented by formulas (I) and (II) above. Typically, about 1 to about 100 moles, preferably 1 to about 40 moles of alkylene oxide can be used per mole of acetal.

The fissile nonionic surfactants of the present invention have a wide distribution of alkoxylated species, which is expected from a base catalyzed alkoxylation process. For example, M. J. Snick, Nonionic S
Reference should be made to urfactants, Volume 1, published by Marcel Dekker, Inc., New York, NY (1967), pages 28-41. The splittable nonionic surfactants of the present invention are commercially available in the art (eg, US Pat. Nos. 4,754,075, 4,820,673).
And narrowed, but balanced, alkoxylated species by the use of limited molecular weight catalysts (eg, those based on calcium) disclosed in U.S. Pat. No. 4,886,917). It can be manufactured to have a distribution. These catalysts produce surfactants that are substantially higher, ie, relatively free of large amounts of alkoxylated moieties having at least 3 more alkoxyl groups than the average peak alkoxylate species. Conveniently, when the most widely occurring alkoxylated moiety has 4 or more alkoxy units, i.e., in areas where conventional catalysts provide a relatively wide range of alkoxylated species.
These narrow distributions can be obtained. It is common for those skilled in the art to adapt the alkoxylates to enhance end use performance. The advantage of the limited molecular weight product is that, under the given method, compared to the more mundane distribution obtained under alkoxylation using a typical (eg potassium hydroxide) base catalyst. Can be determined by the evaluation in. The number of moles of alkyleneoside added to the acetal starting material is related to various factors related to the end use, such as the desired hydrophilic / lipophilic balance (HLB) for emulsification, cloud point and the like. There is no single preferred alkoxylate for all applications. Within certain applications, a mixture of low molar (eg 3-mol) alkoxylates and high molar (eg 9-mol) alkoxylates as compared to a single product (eg 6-mol alkoxylate) is preferred. There is. It should be noted that, in some applications, compared to a substance added with ethylene oxide only, ethylene oxide /
It may be shown that the propylene oxide / butylene oxide mixture is excellent in either random or block addition.

Surfactants are typically combined with one or more "builders", as is well known in the detergent formulation industry, particularly in laundry applications. Such materials are, for example, water hardness ions.
It is added to the composition for a variety of reasons including: sequestration, facilitating the removal and suspension of dirt, preventing redeposition, maintaining pH in the basic range, and the like. Commonly used inorganic builders include
Phosphates (eg sodium tripolyphosphate) typically used in concentrations of about 5 to about 30% by weight, silicates and metasilicates typically used in concentrations of about 5 to about 40% by weight. , Sodium carbonate and sodium bicarbonate, typically used in concentrations of about 0 to about 40% by weight, caustic, typically used in concentrations of about 0 to about 10% by weight, and zeolites and so on. Commonly used organic builders include carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), ethylenediaminetetraacetic acid (E
DTA), citric acid, etc. Such materials are necessary and are usually used with conventional nonionic surfactants such as nonylphenol ethoxylates, primary and secondary alcohol ethoxylates and the like. For environmental reasons, there has been significant pressure on detergent manufacture to find alternatives to phosphates in detergent compositions. To date, this has only succeeded in limited cases (eg nitriloacetic acid as a substitute for phosphate in household powders). Because phosphates not only soften water, but also other properties that facilitate cleaning and removal of impurities from contaminated fabrics (eg, thawing and suspending insoluble materials, emulsifying oils, etc.). Because it has. It is desirable to identify components in detergent compositions that minimize or eliminate the need for phosphates. It is a surprising feature of the compositions of the present invention that the use of phosphate builders can be largely or completely avoided with little or no effect on cleaning performance. The phosphate content may preferably be limited to no more than about 10% by weight of the total dry detergent formulation and more preferably to 0 to about 5% by weight. 1 in prescription
Silicate or metasilicate normal when it is desirable to include one or more builders
Concentration is preferred.

Since the main purpose of the present invention is to coalesce or agglomerate the FOG into a form which can be easily removed, substances in effective concentrations which prevent coalescence, such as phosphoric acid, can be used. It is desirable to avoid the use of redeposition aids such as salts, polyacrylates and CMC. Generally, dispersant aids should be used sparingly or, preferably, avoided to maximize the phase separation that occurs after the surfactants of this invention split.

As described above, the metalworking fluid is mainly composed of
Used for cutting, polishing or forming metal to give good quality finish to the machined parts while minimizing wear of machine tools. These fluids cool and lubricate the metal / machine interface while assisting in the removal of metal fines and chips from the metal pieces to be molded. Metalworking fluids have evolved from single oil to complex systems based on oil-in-water emulsification. For those skilled in the art, metalworking fluids of the water-based technology type are generally classified as soluble oils, semi-synthetic fluids, or synthetic fluids. Each type of fluid offers different benefits for metalworking. For example, soluble oils, which are fluids with a high oil content, give better lubricity compared to synthetic fluids. Conversely, synthetic fluids, which are generally water soluble and contain no mineral oil, provide better cooling, hard water stability, and resistance to microbial degradation as compared to soluble oils.
A third type of metalworking fluid, a semi-synthetic, was developed to have the advantages of both soluble and synthetic oils. These semi-synthetics are water-based fluids and contain some of the oil-based components that emulsify in water to form a microemulsion system. Thus, semi-synthetic and synthetic metalworking fluids are more difficult to treat wastewater than soluble oils.

As is well known to those skilled in the art, surfactants are combined with one or more chemical additives to formulate metalworking fluids that can serve multiple functions. These functions include such things as corrosion inhibition, lubrication, defoaming, pH buffering, dispersion and wetting. These chemical additives include fatty acids, fatty alkanolamides, esters, sulfonates, soaps, chlorinated paraffins, sulfurized fats and sulfurized oils, glycol esters, ethanolamines,
It includes chemically functional substances such as polyalkylene glycols, sulfated oils, and fatty oils. Such additives are necessary and usually used with conventional anionic and nonionic surfactants. Metalworking formulations using anionic surfactants are relatively easy to waste treat as these materials can be treated by acidification or reaction with cationic coagulants. However, metalworking fluid formulations containing conventional nonionic surfactants are much more difficult to waste treat because they cannot be subjected to this type of chemical treatment. For example, J. C. Childrens
Written by Metalworking Fluids, J. Am.
P. Byers, published by Marcel Dekker, Inc., New York City, NY (1994) (1994)
, Pp. 185 and 367-393. As a result, the formulation is prepared for wastewater treatment when a nonionic surfactant (eg, nonylphenol ethoxylate) is used as an emulsifying agent for metalworking fluids. In fact, many metalworking fluid formulations using conventional nonionic surfactants are first, and most preferentially, prepared to be waste disposable after use. This emphasis on waste treatment results in a metalworking fluid that may not exhibit the best possible end-use performance, such as corrosion inhibition, lubrication, dispersion or wetting. Conventional nonionic surfactants are still used in metalworking formulations, despite their waste disposal difficulties. This is because nonionic surfactants offer significant advantages over anionic surfactants (eg hard water stability, “tighter” emulsions, diverse HLB, low foaming, etc.). .

The splittable nonionic surfactants described herein provide good emulsification and wetting of soluble oils, semi-synthetics, and synthetics with the additional advantage of easier wastewater treatment. I will provide a. In addition, the use of fissionable nonionic surfactants has led to the development of improved metalworking formulations that give better end-use performance as compared to metalworking fluids prepared to be waste disposable. can do.

Metal cleaning fluids are used in a variety of metal forming and metal coating processes to clean working fluids, oils, mud, debris, etc. from metal surfaces. There was a trend towards the development of aqueous based cleaning systems as a number of widely used organic solvents such as methyl chloroform, trichloroethylene, methylene chloride, etc. are at various stages of being banned in the workplace. Therefore, aqueous alkaline detergents are increasing in their use and formulations are being developed to maximize their utility. Conventional nonionic surfactants such as Triton® X-100 are commonly used as wetting agents, dispersants and emulsifiers.

A problem typically encountered with metal cleaning solutions is the accumulation of oil in the cleaning bath. As the oil increases in the clean bath, it becomes more difficult for the surfactant to emulsify the oil. To solve this problem, larger amounts of surfactant can be added to the bath. However, the problems of effluent foaming and wastewater treatment are even more pronounced due to the presence of large amounts of surfactant. It is desirable to have a surfactant that provides cleanliness, low foaming, and waste disposability.
Prior art US Pat. No. 5,114,607 discloses an ethylene oxide / propylene oxide block copolymer interface as a surfactant in an alkaline formulation that provides good metal cleaning, low foaming, and waste disposability. Disclosed is the use of activators and defoaming inverse ethylene oxide / propylene oxide block copolymer surfactants. In order to maintain the suspension, the hydrotrope (hydr
must be added. After cleaning, the hydrotrope is neutralized with acid. This is in consideration of phase separation. This technique can be seen as similar to the reversible surfactants described above. The nonionic fissionable surfactants of the present invention provide low foaming, cleaning and waste treatability previously unavailable with conventional nonionic surfactants. Propylene oxide or other hydrophobic moieties (eg, t-butyl, benzyl, methyl,
Etc.) can be added to minimize additional defoamer. Wastewater treatment can be performed as detailed above. Again, suspension agents (eg, phosphates) should be minimized in the cleaning formulation for phase separation.

Similar results can be obtained in other applications, where FOG, TPH and other water-insoluble contaminants are emulsified in the wastewater effluent due to the presence of surfactants. By using the non-ion-splitting surfactant of the present invention, the pH of the wastewater effluent can be lowered (≦ about pH 6) to initiate the hydrolysis of the acetal, whereby the hydrophobic part and the hydrophilic part are separated. This results in release and thus loss of surface activity. The end result is a phase separation of oil and water. The non-ion-splitting surfactants of the present invention are compatible with other wastewater treatment processes, including primary stage treatments (eg gravity separation) and secondary stage treatments. The present invention is directed to second-stage processing involving membranes (eg, ultrafiltration systems that often become fouled by impurities resulting in significant downtime), centrifugation, and dissolved air flotation (DAF) devices. Significant value can be added to it. The end result is greater throughput and minimal use of expensive waste treatment chemicals.

According to the method of the present invention, the acetal-derived fissile nonionic surfactant is hydrophilic because the acetal functionality is chemically destroyed (breakage of two carbon-oxygen bonds) at the pH of the solution. Adjusting to an acidic pH sufficient to produce a fraction and a hydrophobic fraction will cleave in aqueous solution to release impurities from association with detergents. In most methods, this bond breaking is performed in an aqueous environment, so this splitting step can also be referred to as acetal hydrolysis. The pH can be adjusted by conventional procedures using conventional acids. Suitable acids include, for example, sulfuric acid, hydrochloric acid, acetic acid, hydrofluoric acid, nitric acid and the like.
The pH of the adjusted solution is preferably about pH 3 to about p.
Up to H6. The amount of acid added is sufficient to cause cleavage of the surfactant and is related to the volume and composition of the solution. The fissionable nonionic surfactant is a well-known solid heterogeneous acid [eg Nafion ™, silica gel, Amberlyst 15,
Mixed metal oxides, etc.]. The use of solid heterogeneous acids is particularly useful in fixed bed processing.

Catalytic hydrolysis of acetals has been extensively studied in the art. For example, T. H. By Fife,
Accounts of Chemical Rese
arch, Vol. 5 (1972), pp. 264-272, and E. H. Cordes and H.C. G. FIG. Bull
Written, Chemical Reviews, Vol. 74 (1
974), pp. 581-603. From these studies it is clear that the rates and reaction conditions necessary to cause the breaking of the acetal carbon-oxygen bond are complex. Without wishing to be bound by theory, the splittable nonionic surfactants of the present invention are capable of splitting at atmospheric pressure or over a wide range of pressures from subatmospheric to superatmospheric, preferably atmospheric. I can.

The deactivation temperature ranges from about ambient temperature to about 1
It can be as low as 00 ° C. In general, surfactant splitting times are shorter at temperatures above ambient, but in processes that do not choose temperatures above ambient (eg, for economic reasons), fissile nonionic surfactants The agent will still hydrolyze. Generally, a temperature of about 40-80 ° C is preferred.

The chemical constituents in the effluent effluent, in combination with the splittable nonionic surfactant, can give rise to the effect subsequently called the "matrix effect".
These matrix effects may inhibit rapid hydrolysis of the acetal moieties and / or prevent phase separation of the treated effluent. The hydrolytic reactivity of the fissionable nonionic surfactant is considered to be inferior to that of the fissionable nonionic surfactant in water in a complex matrix composed of a large number of chemical components. Conversely, certain chemical constituents in the matrix (eg, silicates) may actually facilitate hydrolysis of the fissile nonionic surfactant and / or phase separation of the treated effluent.

Treatment of the effluent effluent to disrupt the fissile nonionic surfactant and ultimately to cause phase separation is as follows:
It is carried out for a minimum time sufficient to cause hydrolysis or splitting of the surfactant, followed by partial phase separation of the organic and aqueous components. Both of the above components have been emulsified so far. The exact reaction time employed will depend in part on factors such as temperature, matrix effect, degree of agitation, and the like. The reaction time is usually in the range of about half an hour to about 10 hours or more, preferably about 1 hour or less to about 5 hours.

The splittable nonionic surfactant splits into a relatively water-insoluble fraction (hydrophobic) and a relatively water-soluble (hydrophilic) fraction. The water-insoluble fraction comprises the starting aldehyde and the water-soluble fraction comprises the alkoxylated polyol. None of the fractions produced from hydrolysis are surface active, which frees FOG and TPH from association with surfactants, eg emulsions. FOG,
The hydrophobic fraction of TPH and surfactant forms a relatively water insoluble phase in the aqueous stream. At least a portion of this phase in the spent aqueous stream is recovered by conventional methods such as filtration, skimming and the like. Preferably, a substantial portion of the water-insoluble phase, for example 100 of the spent aqueous stream.
Recovered to have less than ppm FOG. The recovered water-insoluble phase can be disposed of, for example, at the waste treatment site or by burning in a furnace, or can be subjected to an oil recycling process. The remaining aqueous stream is POT after final pH adjustment to a relatively non-acidic pH that makes the waste effluent comply with environmental regulations.
It can be discharged to W or, in some cases, recycled for further use. Recirculation is particularly attractive when the aqueous stream is further treated by a membrane system to remove all water-soluble organics, including water-soluble alkoxylated polyols present after the fissionable nonionic surfactant is hydrolyzed. Target. It is another advantage that the splittable nonionic surfactants of the present invention can be used in conjunction with a membrane system to provide an aqueous effluent that is substantially free of organics. Pretreatment of the aqueous effluent containing the compounds of the invention according to the method described above results in an aqueous phase containing considerably less of the FOG and TPH responsible for membrane fouling. This results in longer membrane life and shorter downtime during wastewater treatment.

Tergitol NP-
4, nonylphenol ethoxylates known under the trade names of Tergitol NP-6 and Tergitol NP-9 surfactants are 4-mol, 6-mol and 9-mol, respectively.
-Mole ethoxylate. Triton
on) The octylphenol ethoxylate known under the trade name of X-100 surfactant is 10-mol ethoxylate. The amine ethoxylate known under the Triton RW-75 surfactant trade name is 7.5 mole ethoxylate. The secondary alcohol ethoxylate known under the surfactant trade name of Tergitol 15-S-9 is 9-mol ethoxylate. Neodol 25-9
The primary alcohol ethoxylates known under the trade name of Surfactants are 9-mol ethoxylates.

It will also be appreciated by those skilled in the art that the compositions and methods of the present invention are not limited to the particular uses discussed above. For example, in certain cases it may be possible to treat the internal process stream with a surfactant of the invention, to separate the susceptible material by the method of the invention and then to recycle the remaining stream to the process. Done quickly. In another variant,
The stream retaining the material emulsified by a surfactant not of the invention is treated with the surfactant of the invention to replace all or part of the other surfactants as described above and then the invention. The separation method was carried out and other surfactants could be returned to the process by recycling. Similarly, it will be appreciated that it is not necessary that the method of the present invention result in complete inactivation of the surfactant. For example, sufficient passivation can be employed to reduce contaminants to acceptable levels and return the treated stream to the process until the contaminant levels rise to the point where additional treatment is required.
It is clear that the above technique can be applied either on a continuous basis or on a batch basis.

In another useful embodiment, the surfactant of the present invention co-emulsifies (in an aqueous stream) an emulsion of the hydrophobic material present with an unemulsified hydrophobic material also in the stream. -Emulsification), and then the resulting co-emulsifying material can be used in a method of disrupting by lowering the pH of the stream according to the methods described above.

[0046]

The present invention will be described with reference to the following examples. However, the present invention is not limited to any embodiment.

Via condensation of aldehyde and polyol
General procedure for the production of acetals (Examples A to L) [Explanation for "Table 1" below) Aldehyde in a multi-neck round bottom flask equipped with a condenser, a Dean-Stark trap and a heating mantle. Polyol, heptane, and p-toluenesulfonic acid monohydrate were added. The flask was purged with nitrogen three times and depressurized. The mixture was then heated to reflux with removal of the heptane / water azeotrope until such time as no additional water was available in the Gene Stark trap overheads. The reaction mixture was cooled and placed in a separatory funnel to remove unreacted polyol (in the case of glycerin) separated from the reaction mixture as the lower layer. The product was purified on a rotary evaporator under reduced pressure. In some cases,
Additional heptane was added to the reaction mixture prior to purification of the product, which was then extracted 3 times with a 10 weight percent sodium carbonate / water solution (using a separating funnel) to remove additional polyol, The catalyst was neutralized. The aqueous solution (bottom layer) was discarded and the organic solution was purified as described above. In some cases additional purification was required to give acceptable purity of the acetal (≧ 97% purity). Acetal, length 30 meters, inner diameter 0.
Analysis was by capillary gas chromatography (FID) using a 25 mm, 0.1 micron thick DB5HT column.

Producing a surfactant derived from acetal
General procedure for alkoxylation of acetals to form
Examples A-L The general procedure for making base catalyzed starting materials is as follows. The acetal was charged into a reactor or a round bottom flask equipped with a water cooler. A catalyst (typically 0.05-5.0 wt% sodium hydroxide or potassium hydroxide) is added to the acetal and the mixture is heated under reduced pressure (10-50 mm / Hg) at 140 ° C. for 1 hour. During this period, the water overhead distillate was removed. After this time the kettle product was suitable for alkoxylation as described below.

The procedures described herein were used to prepare the splittable nonionic surfactants of the present invention. The reactor for these manufacturing procedures was a 2 gallon agitator autoclave with an automatic ethylene oxide (or other alkylene oxide) feed system in which the ethylene oxide feed was controlled by a motor valve to maintain a pressure of about 60 psig. It was a thing. Acetal starting material (Examples AL) in a 2 gallon agitator autoclave,
Ethylene oxide and catalyst (either carried out as described above or generated in-situ by heating the contents and removing water from the system) were added.
Ethoxylation is performed under a nitrogen atmosphere (20 psig) at 140
It was carried out at a temperature of ° C. Propoxylation is 110-1
It was carried out at a temperature of 15 ° C. The ethoxylation is continued until the desired moles of ethoxylates (or mixed alkoxylates) are obtained, after which the oxide feed is stopped and the contents "cook out" (maintaining constant reactor pressure. I was allowed to do it. An aliquot was drained through a discharge valve, cooled, then partially neutralized with an acid (eg, acetic acid, phosphoric acid, etc.) to ensure an alkaline pH. Ethoxylation was continued on the residue in the autoclave by continuing to add ethylene oxide until the next mole of ethoxylate was obtained. A series of products (usually 3-, 6-, 9- and 12-mol
This procedure was continued until the ethoxylate) was obtained.

Limited molecular weight acetals (Example
Procedure for the preparation of surfactants derived from A) In a 1 liter reaction flask equipped with reflux condenser, thermocouple, mechanical stirrer and gas purge inlet, derived from condensation of 2-ethylhexanal with glycerin (Example A). 551 g of acetal and calcium hydroxide 5.
02 g was added. The resulting mixture was heated at 80 ° C. under reduced pressure (180 mm) for 2 hours while removing water from the overhead effluent. The reaction mixture was then cooled to 7 ° C in an ice bath and 4.5g concentrated sulfuric acid was added to the flask. The mixture was stirred for 30 minutes and the reaction mixture was heated to 165 ° C during which time 16 g overhead effluent was removed. The kettle product was then charged to a 2 gallon autoclave, ethoxylated as described above and having a restricted molecular weight product distribution as compared to the product prepared using sodium hydroxide as a catalyst.
A molar ethoxylate was obtained.

Test Procedures and Evaluation Procedures To determine the laundry cleaning efficacy of the non-ion-splitting surfactants of the present invention, Tag O Tome-To assist the evaluation.
The standardization procedure was performed using Terg-O-Tometer and laundry standard surfactant. Pre-selection of detergent detergency was carried out by the Targ-O-Tometer test, and it was possible to indicate the direction of future development.

Laundry clean performance of the non-ion-splitting surfactants described herein was measured using a Model 7243S Targ au Tometer manufactured by Research and Testing, Hoboken, NJ, USA. 100 distilled water in each of 6 buckets
0 mL, 2.5 g of a surfactant and a sodium hydroxide solution were charged to adjust the pH to 10.7 to 11.0. Four standard soiled cloths containing the same amount of soiled motor oil soil were added to the bucket. Four clean pieces were also added for the purpose of making them bulky and qualitatively evaluated for redeposition. The test swatches include Testfabrics, Inc., Middlesex City, NJ, USA, and New York State,
Sparrow Bush City, Scientific Serv
It was obtained from ices S / D. The cloth was washed in a single 10 minute wash step, after which the cloth was removed from the bucket and rinsed with distilled water. The cloth was returned to the bucket with 1000 mL of distilled water and a single 2 minute rinse step was performed. Both wash and rinse temperatures are 14
It was 5 ° F. and the Tag Otometer operating speed was 100 rpm. The wash water and rinsing water were preheated to an appropriate temperature before charging into the bucket. The fabric was dried in a standard home drier and evaluated for cleaning performance.
ABYK-Gardner TCS spectrophotometer was used to obtain the reflectance of the soiled cloth before and after washing.
The following equation: Detergency% = [(A−B) ÷ (C−B)] × 100 (where, A = the reflectance of the stain test cloth after washing B = the reflectance of the stain test cloth before washing C = The percent detergency was calculated using the reflectance of the test cloth before staining). The results are shown in Table A. The test cloth is
Since the stains, conditions and weave of the cloth are different, it was changed for each lot.

Examples 1-9 in Table A were evaluated on the same lot of fabric. Examples 1-5 in Table A were evaluated on the same lot of cloth. Examples 6-11 were evaluated on the same lot of cloth. Examples 12 and 13 were performed on different lots. Under these circumstances, it is best to compare the results by the manner in which it was performed against a standard (eg, Tergitol NP-9) under the same conditions. As the results show, some of the non-ion-splitting surfactants of the present invention showed improved detergency compared to the standard. The 3-mol ethoxylate of acetal A had particularly good performance. The best detergency when using TMP as the polyol is
There was a shift towards higher molar ethoxylates as compared to a similar acetal prepared using glycerin as the polyol (Examples 4 and 7 versus Examples 1 and 6). Furthermore, using propylene oxide to increase the hydrophobicity of the acetal (Example 2) and using a catalyst of limited molecular weight to provide ethoxylates with a narrow distribution (Example 3). ) Results in an improved detergency of 100 moles of 6 mol ethoxylate compared to the original compound (Example 1).
Branched aldehydes give better detergency compared to unbranched aldehydes of similar molecular weight (Examples 1 and 9; Examples 8 and 10). Cleaving nonionic surfactants derived from higher molecular weight aldehydes give improved performance compared to cleaving nonionic surfactants derived from lower molecular weight aldehydes (Examples 12 and 13). ).

To determine the effect (matrix effect) of a wide variety of inorganic and organic builders on the treatability of wastewater effluents of nonionic splittable surfactants, 15 to 25 weight percent of splittable nonionic surfactants and Builder 75
A composition was prepared containing ˜85 weight percent. 10 g of the detergent formed was added to a Targ-O-Tometer bucket (pH ranged from 9.5 to 11.5 depending on builder choice and amount) and evaluated using the procedure described above. Collect the effluent effluent by combining wash and rinse water from the standard Targ-O-Tometer test procedure for each bucket, each through a 35 mesh screen (to remove larger lint). Filter into a gallon bottle. Each mixture was washed and rinsed in a constant temperature bath until the time for treatment (145
Kept in °). Stir each mixed waste thoroughly,
About 800-900 mL was poured into each of two 1 liter beakers. The beaker is 1.from the bottom for the purpose of taking a sample of the water as a clean sidestream from floating oil and debris or settling sludge.
It was remodeled by a 4 mm barrel type water stopcock made of Teflon placed at a position of 5 to 2 inches. These beakers are located in Kingsport, Tennessee, USA, L
It was custom manufactured by ab Glass. The wastewater in one beaker was left unchanged (untreated sample). Wastewater in other beakers (processed sample)
PH was lowered to 3 or 5 using aqueous sulfuric acid. Both beakers were maintained at wash and rinse temperatures (145 ° F) in a constant temperature bath for 30 to 90 minutes. The beaker was removed from the bath and allowed to sit for 20-30 minutes. First gently purging, about 10 to 15
After discarding the mL to remove contaminants from the side arm of the water stopcock, pass a water sample (about 5
mL) was collected. A sample of this water was then analyzed for chemical oxygen demand (COD). This COD is St
andards Method For TheExa
magnetization of Water and Was
tewater, 18th edition (1992), procedure 522.
0D, was measured under the limited and regulated conditions.
As the results show (Table B), organic matter (eg,
The phase separation between water (FOG, TPH, etc.) and water is not good (as evidenced by the high COD value) and therefore the full benefit of the invention for the phase separation of organics and water is not admitted. However, when phosphate was not present in the formulation (Examples 2 and 3), good phase separation was observed after the splittable nonionic surfactant split by lowering the pH to 3. If a conventional nonionic surfactant (eg, Tergitol NP-9) is used, it will not cleave under these conditions. Therefore, no phase separation was observed.

The effect of phosphate concentration on the cleaning performance of non-ion-splitting surfactants compared to conventional non-ionic surfactants is shown in Table C. As the results show,
Good detergency was obtained when present in the splittable nonionic surfactant formulation (Example 1) and in the conventional nonionic surfactant formulation (Example 4). Unexpectedly,
In the case where a splittable nonionic surfactant was used (Examples 2 and 3), in the formulation without phosphate, in the formulation for the conventional nonionic surfactant (Examples 5 and 6). Good detergency was maintained as compared to poor detergency in the absence of phosphate.

Emulsification studies, standard foaming tests, and waste treatability data were collected to determine the effect of non-ion-splitting surfactants on metalworking fluid formulations.

The emulsification test was performed by simulating a soluble oil formulation. Naphthenic oil [Ergon high gold (Er
25 g of water was added to a mixture of 16 g of gon Hygold) V-200] and 4 g of a surfactant. 1 hour and 24
Observations were made after standing at room temperature for a period of time. The results are shown in Table D. As the results show, the splittable nonionic surfactants of the present invention provide emulsifying properties similar to Tergitol NP-4, Tergitol NP-6 and Tergitol NP-9. The 6 mole ethylene oxide adducts of acetal K and acetal L were particularly good emulsifiers for this test.

The relative foaming properties of non-ion-splitting surfactants were measured under the limited and controlled conditions described in ASTM Procedure D1173. The results are reported in Table E. As the results show, the non-ion-splitting surfactants of the invention showed significantly less foam after 5 minutes compared to the standard Tergitol NP-9 (Example 12). Acetals derived from lower molecular weight aldehydes are the lowest blowing agents, and aldehydes with carbon branching within a given molecular weight give less foam (Examples 1 and 3). Within a given family, lower molar ethoxylates produced less foam (Examples 7-10).

The waste treatment of nonionic fissionable surfactants in metalworking formulations was compared to conventional nonionic surfactants by treating a mixture containing a metalworking fluid component using the following method. did:

The mixture to be tested is diluted to 0.5% by weight,
Stored at room temperature for at least 24 hours. After this time, the pH of the 0.5 wt% solution was lowered to a pH of 3-5 with a 2.5 wt% aqueous solution of sulfuric acid. Then, add this acidic solution to 2
Heat to 50-60 ° C. for 10 hours. The solution was cooled to room temperature and then adjusted to pH 6-9 with a 2.5 wt% aqueous sodium hydroxide solution. Up to six 600 mL beakers were filled with 250 mL of test solution. 5 to the mixture
Illuminated ba on a Phipps & Bird 6-blade stirrer for 6 minutes.
se) at 95-100 rpm. Cationic polymer (Pittsburgh, Pennsylvania, USA,
50-100 pp of Calgon WT2545)
A maximum of 1200 ppm was added in increments of m while mixing at 95-100 rpm for at least 5 minutes. After this time, 300 ppm aluminum sulphate solution was added to the mixture and mixing continued for at least 5 minutes.
After the required mixing time, the mixing speed was increased to 150 rpm. Anionic polymer (DOLE-Z manufactured by Calgon Co., Ltd.
-2706) 5 ppm was added, then the solution was mixed at 150 rpm for 2 minutes, then 60 r for an additional 2 minutes.
pm. The stirrer was stopped and the mixture was allowed to sit for 5 minutes after which the transparency of the mixture was measured. If no flocculation or transparency is observed, discard the sample and add additional cationic polymer (1200 pp
The process was repeated using (up to m). Aluminum sulphate optimization can be done, but it is not necessary. The treated sample was gravity filtered through a 25 micron filter paper and then the aqueous layer was used to measure chemical oxygen demand (COD) and turbidity.

The chemical oxygen demand (COD) was measured by Stan
dard Methods ForThe Exami
national of Water and Waste
water, 18th edition (1992), procedure 5220.
It was measured under the limited and regulated conditions described in D. Since many of the additives used in metalworking fluids are water-soluble, the surfactants of the present invention are fissionable and still achieve high COD levels despite distinct phase separation. Turbidity can be measured by Standard Methods For T
he Exhibition of Water a
nd Wastewater, 18th Edition (1992)
Yr), under the limited and regulated conditions described in Procedure 2130B, by nephelometry.

Processing studies were conducted using conventional nonionic surfactants and the nonionic fissionable surfactants of the present invention. In these studies, water, triethanolamine, orthoboric acid, sodium omazine (sodium omad) were used to simulate typical metalworking fluids.
ine) and ethylenediaminetetraacetic acid disodium salt were used. Surfactant 5 (wt%) and Ergon Refining Hygold V- were added to this mixture.
The metalworking fluid was formulated by adding 200 (wt%) Oil 200 (Vicksburg, Mississippi, USA). The results of waste treatment of this mixture are shown in Table F. As shown in Table F, unlike the results obtained for wastewater effluent from industrial laundry, the metalworking fluid formulations containing the non-ion-splitting surfactants of the present invention are described above. There was no significant reduction in COD levels by using the described procedure (Examples 1-6). Similarly, conventional non-ionic (eg, Tergitol NP-9)
The same formulation containing the surfactant was not processable under similar conditions (Examples 7-12). These results suggest that more stringent conditions are required for phase separation of metalworking fluids due to the complex matrix effect not present in industrial laundry wastewater effluents. There is. These matrix effects can be overcome by using other ingredients in the formulation that do not interfere with phase separation and / or promote phase separation (eg, silicates).

In order to determine the effect of non-ion-splitting surfactants on the cleaning of metals, the following immersion metal cleaning procedure was performed and compared to standard industrial surfactants.

A stainless steel 304-2B alloy coupon (stock number SS-13) was purchased from Q Panel, Inc., Cleveland, Ohio, USA. A 1/16 inch hole was drilled in the coupon centered at one end so that the coupon could be hung vertically. Prior to use, coupons were pre-cleaned in two different ways. Procedure A used a methanol / potassium hydroxide solution. The panels were soaked in the solution overnight, rinsed with tap water, acetone and then dried at room temperature. Step B is to scrub the dishwashing fluid / water solution with a scrub brush.
ush). After cleaning, the coupons were rinsed with tap water, dipped in methanol, rinsed with acetone and then hung to dry at room temperature. The pre-cleaned coupons are on an analytical balance to the 4th decimal place (0.0000).
g) Weighed. The coupons were soiled by dipping 80-85% (about 2.5 inches) of the coupon in test oil and then hanging vertically for 1 hour. After this time, excess oil droplets on the bottom of the coupon were wiped off with a 1 inch sponge paint brush. The coupon was then re-weighed to determine the amount of oil residue on the panel. Solutions of builders, solvents and surfactants were used as cleaning media. Typically, a 1 liter aqueous solution having the following formulation was prepared. The formulation was: 0.1% by weight sodium hydroxide, 0.1% by weight surfactant, 0.1% by weight sodium metasilicate (anhydrous) and 0.1% by weight sodium carbonate. This solution was placed in a beaker in a bath adjusted to the desired temperature (+/- 2 ° C). Typical temperature range is 40,6
0 and 80 ° C. The soiled coupon was hung on a rotating machine and then dipped into the cleaning solution. The coupon rotation was 15 ± 2 rpm. The wash cycle was 5 minutes or less and then rinsed in distilled water. Distilled water was poured into a 1000 mL beaker and the coupon was rinsed in the beaker out of contact with the water stream (this may have helped some additional oil removal). After rinsing, the coupon was again hung vertically and air dried. When dry, the coupons were weighed to determine the amount of oil residue left on the coupons after cleaning. The cleaning effect is measured by dividing the amount of residue by the amount of oil deposited and multiplying by 100 to determine the percentage of oil removal.

Amount of residue / amount of oil deposited × 100 =% oil removed

The results are shown in Table G. As the results show, many of the splittable nonionic surfactants of the present invention are comparable to conventional nonionic surfactants known to be good metal detergents (eg Triton X-100), or It shows better cleaning performance than those.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

[Table 7]

[0074]

[Table 8]

[0075]

[Table 9]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C11D 3/08 C11D 3/08 (72) Inventor Dennis, Christine, Guarantee West Virginia, USA 25314 , Charleston, Freyer Tuck Circle No. 304 (72) Inventor Richard, Charles, Hoy United States, West Virginia 25314, Charleston, Parkwood Road 1944 (72) Inventor Albert, Ferris, Joseph United States of America, West Virginia 25314, Charleston, Ellison Rod 109 (72) Inventor Stephen, Wayne, King West Virginia, USA 25560 Scott Depot, Tee's Meduzu # 120 (72) Inventor Charles, Arnold, Smith United States, West Virginia 25314, Charleston, Freier Tuck Circle # 304 (72) Inventor Cheryl, Mary, Wizda United States , Steps Way 5318, Cross Lanes, West Virginia 25313

Claims (15)

[Claims] 1. A method for removing impurities associated with a fissile nonionic surfactant in an aqueous stream, comprising: (a) separating the surfactant into a relatively water-insoluble fraction and a relatively water-soluble fraction. By adjusting the pH of the aqueous stream to a pH that is acidic enough to cause irreversible fragmentation, the surfactant is inactivated and impurities are released from association with the surfactant and released. Impurities and the water-insoluble fraction of the surfactant form a relatively water-insoluble phase, then (b)
Removing at least a portion of the water insoluble phase from the aqueous stream, wherein the splittable nonionic surfactant is of the formula: Or {In the above formula, R is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 8 to about 20 carbon atoms) (substituted or Unsubstituted); X is hydrogen or a hydrophobic endcap residue; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl, or ethyl M is 0 or 1; and n is an integer from 1 to about 40}, or a mixture thereof. 2. A method of laundering a fabric carrying hydrophobic contaminants, comprising the step of: (a) subjecting the fabric to basic conditions of the formula: Or {In the above formula, R is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 12 to about 18 carbon atoms) (substituted or Unsubstituted) residues; X is hydrogen or a hydrophobic endcap residue; Y is hydrogen or methyl; Z is hydrogen, methyl or ethyl; m
Is 0 or 1; and n is an integer from 1 to about 40} or a mixture thereof, and (b) an aqueous emulsion together with the surfactant. Removing the effluent stream containing at least some of the hydrophobic contaminants in the following conditions: (c) treating the effluent stream with an acidic substance to adjust its pH.
Is sufficient to cause irreversible splitting of the surfactant into aldehydes and polyols, thereby releasing the hydrophobic contaminants from the emulsion and the water-insoluble and relatively contaminant-free aqueous phases. And (d) separating at least some of the water-insoluble phase from the water phase. 3. The method of claim 2 wherein step (c) is carried out in the substantial absence of phosphate. 4. The aldehyde is C ₁₂ to C ₁₃ , or C _14.
A process according to claim 2 which is a mixture of aldehydes from C ₁₅ to C ₁₅ . 5. Formula (a): Or {R in the above formula is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 12 to about 15 carbon atoms) (substituted or X is hydrogen or a residue of a hydrophobic end cap; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl or ethyl; m is 0 or 1; and n is an integer from 1 to about 40}, or a mixture of at least about 5% by weight of the non-ion-splitting surfactant; (b) about 5 % To about 80% builder; and (c) the balance of the inactive ingredients; a laundry detergent composition consisting essentially of: 6. The composition of claim 5, wherein the builder comprises a silicate and / or a metasilicate. 7. The composition of claim 5, wherein the builder comprises carbonate and / or bicarbonate. 8. The formula: Or {In the above formula, R is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 8 to about 20 carbon atoms) (substituted or X is hydrogen or a residue of a hydrophobic end cap; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl or ethyl; m is 0 or 1; and n is an integer from 1 to about 40} or a mixture thereof, a hard surface cleaning composition comprising an aqueous solution of a non-ion-splitting surfactant. 9. (a) Contacting a hard surface with the composition of claim 8; (b) removing the effluent stream containing at least some of the hydrophobic contaminants in the form of an aqueous emulsion with a surfactant. (C) treating the effluent stream with an acidic substance to adjust its pH
Is sufficient to cause irreversible splitting of the surfactant into aldehydes and polyols, thereby releasing the hydrophobic contaminants from the emulsion and the water-insoluble and relatively contaminant-free aqueous phases. And (d) separating at least some of the water-insoluble phase from the water phase, a method of cleaning a hard surface contaminated with hydrophobic contaminants. 10. The formula: Or {R in the above formula is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 8 to about 20 carbon atoms) (substituted or X is hydrogen or a residue of a hydrophobic end cap; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl or ethyl; m is 0 or 1; and n is an integer from 1 to about 40} or a mixture thereof, the metalworking composition comprising an aqueous solution of a non-ion-splitting surfactant. 11. (a) Contacting a metal carrying a hydrophobic material with the composition of claim 10; (b) an effluent containing at least some of said hydrophobic material in the form of an aqueous emulsion with a surfactant. Removing the liquid stream; (c) treating the effluent stream with an acidic substance to adjust its pH.
Is reduced sufficiently to irreversibly split the surfactant into an aldehyde and a polyol, thereby releasing the hydrophobic material from the emulsion and a water-insoluble phase and an aqueous phase relatively free of hydrophobic material. And (d) separating at least some of the water-insoluble phase from the water phase. 12. The formula: Or {In the above formula, R is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 8 to about 20 carbon atoms) (substituted or X is hydrogen or a residue of a hydrophobic end cap; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl or ethyl; m is 0 or 1; and n is an integer from 1 to about 40} or an admixture of an aqueous solution of a non-ion-splitting surfactant. 13. (a) Mixing wastepaper having various types of deposited ink particles with water to form an aqueous wastepaper slurry; (b) removing the wastepaper slurry from the wastepaper, and then ink particles. Treating the wastepaper slurry with the composition of claim 12 with sufficient agitation to associate with the composition, thus forming a pulp and an ink / surfactant / water mixture. ) Concentrating the pulp from the aqueous emulsion; then (d) irreversibly splitting the pH of the solution into a relatively water insoluble fraction and a relatively water soluble fraction of the surfactant,
Treating the effluent stream by thus adjusting the acidic pH sufficient to separate the ink from water;
And (e) a method of removing ink, characterized in that at least some of the ink is separated from the aqueous phase. 14. Irreversible fission is possible by lowering the pH of the aqueous solution to about 6 or lower, and of the formula: Or {In the above formula, R is hydrogen and R'is represented by the formula: An organic compound derived from an aldehyde (wherein R is hydrogen and R ′ is the residue of an organic compound (substituted or unsubstituted) having a total of about 12 to about 15 carbon atoms) (substituted or Unsubstituted); X is hydrogen or a hydrophobic endcap residue; Y is hydrogen, methyl, ethyl or a mixture thereof; Z is hydrogen, methyl, or ethyl M is 0 or 1; and n is an integer of 1 to about 40}, or a mixture thereof. 15. The method of claim 1, wherein the impurities include an emulsion of a hydrophobic material.