WO2001094510A1 - Compositions de nettoyage recyclables - Google Patents

Compositions de nettoyage recyclables Download PDF

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Publication number
WO2001094510A1
WO2001094510A1 PCT/US2001/018546 US0118546W WO0194510A1 WO 2001094510 A1 WO2001094510 A1 WO 2001094510A1 US 0118546 W US0118546 W US 0118546W WO 0194510 A1 WO0194510 A1 WO 0194510A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
surfactants
composition
cleaning
membrane
Prior art date
Application number
PCT/US2001/018546
Other languages
English (en)
Inventor
Steven A. Bolkan
Mark Ventura
Bruce Strasser
Stephen W. Barrow
Michael Endres
Original Assignee
Church & Dwight Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Church & Dwight Company, Inc. filed Critical Church & Dwight Company, Inc.
Priority to US10/296,777 priority Critical patent/US20040014624A1/en
Priority to EP01946175A priority patent/EP1303581A4/fr
Priority to CA002411705A priority patent/CA2411705A1/fr
Publication of WO2001094510A1 publication Critical patent/WO2001094510A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to recyclable cleaning compositions. More
  • the invention relates to cleaning compositions including an alkaline solution of
  • Hard surface articles cleaned by such a process include metal, glass, plastic and ceramic articles. Soils typically present on hard surface articles include contaminants such as oils, mineral salts and suspended particulates.
  • contaminants are removed from the articles by contact between a cleaning solution and the articles. As these contaminants are removed from the articles and introduced into the aqueous cleaning solution, the aqueous cleaning solution may become too concentrated with contaminants to perform adequately.
  • Contaminants that reduce the effectiveness of the cleaning solution include organic components, such as free floating and emulsified oils, and inorganic materials including mineral salts or suspended particulates. Other materials, which are inherent to the cleaning chemistry, may also concentrate over time and decrease the effectiveness of the cleaning solution.
  • Aqueous based cleaning solutions that have been used to clean soiled articles may contain from 1 to 5% emulsified oils and up to 50% free floating oils, depending upon the articles being cleaned and the effectiveness of the solutions. A greater amount of the oils may also be present in the solutions.
  • These "used” solutions are hereafter referred to as soiled cleaning solutions.
  • the prior art discloses methods of treating the soiled cleaning solutions to remove the contaminants contained therein. Treatment of such soiled cleaning solutions, however, can be impractical for small waste generators and costly for large waste generators.
  • Classical treatment methods for soiled aqueous based cleaning solutions include decanting, skimming, and coalescing. These treatment methods are useful for removing large amounts of free floating oil contaminants, but are not effective for removing emulsified oil contaminants.
  • Emulsified oil as well as free floating oil may be removed from soiled cleaning solutions via membrane filtration.
  • the act of removing contaminants from the aqueous cleaning solution via membrane filtration is known as cleaner recycling.
  • An aqueous cleaning solution is considered recyclable if the contaminants contained therein can be removed in a sufficient proportion such that the cleaning solution may be effectively reused in the cleaning process.
  • a recycling process using membranes will trap solids, free floating oils, and emulsified oils while passing some surfactant, alkalinity builders, other adjuvants and water back into the aqueous cleaning solution.
  • Recycling by membrane filtration therefore, not only reduces or eliminates the discharge of contaminated water into the environment, but it also allows the aqueous cleaning solution to be used for an extended time frame.
  • An effective recycling process therefore, results in economic and environmental advantages for the user.
  • Membrane filtration typically involves a pressure driven process that will remove particles and oil from the soiled cleaning solutions.
  • Several types of membrane processes are used in the industry, including ultrafiltration and microfiltration.
  • the major problems with membrane filtration involve cost, chemical fouling, scaling and membrane compatibility.
  • active cleaning components are often removed via membrane filtration resulting in a less effective permeate.
  • prior art membrane filtration processes are limited to lower temperatures since higher temperatures detrimentally affect cleaning, foaming and anti-corrosion properties of the cleaning solutions. The effectiveness of the prior art recycled compositions as well as their length of use, therefore, are substantially reduced.
  • the invention that is described below overcomes these prior art limitations.
  • high surfactant permeability is required for the effective recycling of soiled cleaning solutions.
  • High surfactant permeability is defined as the ability of the surfactant to maintain 50% by weight (or greater) of its starting value upon recycling in unsoiled conditions and to maintain 30% by weight (or greater) of its starting value upon recycling in soiled conditions.
  • the identification of surfactants with high surfactant permeability may be attained by known methods. However, the known methods of measuring surfactant permeability are very time consuming and considerable analytical effort is required to support these permeability measurements. Given the large number of available surfactants, an alternative approach is needed to identify surfactant candidates likely to have high surfactant permeability. The invention that is described herein provides this identification
  • Ventura, et al. claim improved surfactant recovery upon ultrafiltration of surfactant containing aqueous solutions.
  • the degree of recycling and recovery in these patents was determined by comparing the surface tension of permeate and feed streams. This method of measurement, however, is qualitative and raises technical issues on the validity of the results. For example, any soil introduced into the system could effect the nature of the surface tension curve in the area between critical micelle concentration (CMC) and infinite dilution.
  • CMC critical micelle concentration
  • surfactant systems are comprised of a variety of oligomers and selective partitioning of some oligomers will effect the CMC resulting in possible significant error. In this case, CMC measurements to determine surfactant concentration would be invalid.
  • this prior art is silent on determining recyclability in the presence of soil.
  • HLB hydrophobic/lipophobic balance
  • HLB surfactant components will naturally be eliminated due to the higher partitioning of these materials into the rejected oil phase. Thus, the presence of soil must be considered in the identification of optimum and unique systems for recycle use.
  • the literature references referred to in this disclosure are incorporated herein in their entirety.
  • An object of the invention is to provide a recyclable cleaning composition and process for removing contaminants from hard surface articles where a membrane system is employed to treat the soiled cleaning solution whereby the membrane will rej ect hydrophobic oily contaminants contained in the soiled cleaning solution while allowing the active ingredients of the cleaning solution to permeate the membrane for reuse.
  • a second object of the invention is to provide an aqueous waste cleaning system for removing contaminants from hard surface articles where a membrane system is used to treat the soiled cleaning solution, the permeate retains a high degree of active cleaning constituents and where the membrane used therein has a pore size range from about 0.05 to about 5 microns.
  • a third object of this invention is to provide a method for rapidly screening surfactants for permeability.
  • the recyclable cleaning compositions of the present invention comprise an aqueous alkaline solution containing from 1% to 20% by weight of a synthetic detergent comprising at least one surfactant, and a high degree of permeability through a membrane having a pore size of about 0.05 to about 5.0 microns after the composition has been used in the cleaning process.
  • the cleaning composition may optionally contain builders, corrosion inhibitors, anti-scaling materials, alkalinity electrolytes, hydrotropes, antifoam materials, wetting agents, solvents and other adjuvants and these adjuvants are also permeable through the membrane for recycling and reuse.
  • the cleaning composition also can be used at low concentrations while imparting good cleaning and low foaming profiles.
  • the present invention also provides a process for the filtration of contaminants from an aqueous surfactant containing composition by passing the soiled cleaning solution through a membrane having a pore size of about 0.05 to about 5.0 microns where the contaminants are filtered off and the permeate contains a high level of cleaning agents and is recycled for reuse.
  • the present invention also provides a method for rapidly screening surfactants for permeability.
  • Fig. 1 is a schematic representation of the recycle system of the present invention.
  • Fig. 2 is a graph showing membrane pore size versus percent recyclability for Formula A versus Formula B in unsoiled condition at 80°F.
  • Fig. 3 is a graph showing membrane pore size versus percent recycliability for Formula A versus Formula B in unsoiled condition at 140°F.
  • Fig.4 is a graph showing membrane pore size versus percent recycliability for Formula A versus Formula B in soiled conditions at 80°F.
  • Fig. 5 is a graph showing membrane pore size versus percent recyclability for
  • Fig. 6 is a graph showing the HPLC Log P Calibration Curve (alkyl benzene standards).
  • Fig. 7 is a graph showing HPLC Profiles of Neodol ® 91-6 and of Poly- Tergent ® SL-92.
  • Fig. 8 is a graph showing Calculated vs. Estimated Surfactant Log P Results.
  • Fig. 9 is a graph showing Permeability Results in unsoiled conditions.
  • Fig. 10 is a graph showing Neodol ® 91-6 Hydrophobe Permeability Results in unsoiled conditions.
  • Fig. 11 is a graph showing Poly-Tergent ® SL-92 Hydrophobe Permeability Results in unsoiled conditions.
  • Fig. 12 is a graph showing Surfactant Permeability vs. Log P in unsoiled conditions.
  • Fig. 13 is a graph showing Surfactant Permeability vs. Cloud Point in unsoiled conditions.
  • Fig. 14 is a graph showing Permeability vs. Log P for all hydrophobes in unsoiled conditions.
  • Fig. 15 is a graph showing Permeability vs. Log P for unsoiled conditions at
  • Fig. 16 is a graph showing permeability results of surfactants in the presence of Cosmoline ® 1102.
  • Fig. 17 is a graph showing permeability results of Neodol ® 91 -6 in the presence of Cosmoline 1102.
  • Fig. 18 is a graph showing permeability results of Polytergent ® SL-92 the presence of Cosmoline 1102.
  • Fig. 19 is a graph showing Permeability vs. Cloud Point for Cosmoline ® 1102 Soil at 140 °F.
  • Fig. 20 is a graph showing Permeability vs. Log P for Cosmoline ® 1102 soil at 140° F for all hydrophobes.
  • Fig. 21 is a graph showing Permeability vs. Cloud Point for Pennzoil ® 4096 Gear Lubericant S AE 80W90 GL5 soil at 140 °F.
  • Fig. 22 is a graph showing Permeability vs. Log P for Pennzoil ® 4096 Gear
  • Fig. 23 is a graph showing Permeability vs. Log P for Pennzoil ® 4096 Gear Lubericant SAE 80W90 GL5 soil at 140°F for all hydrophobes.
  • Fig.24 is a graph showing Permeability Results - Unsoiled vs. Pennzoil ® 4096 Gear Lubericant SAE 80W90 GL5 soil.
  • Fig. 25 is a graph showing permeability result of Barlox ® 12i Multiple Oil Addition Study
  • Fig. 26 is a graph showing Temperature Effect on Permeability Results - Cosmoline ® 1102 Soil.
  • the recyclable cleaning compositions of the present invention are useful in the cleaning of hard surface articles such as metal, glass, plastic, ceramic or other hard surface articles.
  • the recyclable cleaning compositions of the present invention are designed to clean hard surface articles by lifting soil and contaminants from the articles and preventing redeposition of said soils and contaminants.
  • the cleaning compositions of the present invention are designed to be used in a variety of cleaning machines including, but not limited to, hand parts washers, immersion dip baths, power spray systems, ultrasonic baths, and spray wands.
  • the recyclable cleaning compositions of the present invention comprise an aqueous alkaline solution containing a detergent comprising certain classes of individual surfactants and their mixtures, that when combined with other formulation ingredients, such as builders, corrosion inhibitors, antiscaling materials, alkalinity electrolytes, hydrotropes, antifoam materials, wetting agents and other adjuvants, provide unique cleaning compositions that demonstrate improved recycling capabilities as well as high utility in terms of cleaning, foaming and surface protection.
  • formulation ingredients such as builders, corrosion inhibitors, antiscaling materials, alkalinity electrolytes, hydrotropes, antifoam materials, wetting agents and other adjuvants.
  • surfactants which allow the present invention to provide a high degree of cleaning and also provide a high degree of permeability when tested with various membranes ranging in pore size from 0.05-5.0 microns.
  • a high degree of permeability means that at least 50%o by weight of the surfactant in the solution permeates a membrane having a pore size of about 0.05 to 5.0 microns in unsoiled conditions, and at least 30% by weight of the surfactant in the detergent permeates the same sized membrane, after the solution is contaminated or soiled under at least one set of soiled conditions.
  • a preferred set of soiled conditions would include the use of Cosmoline ® 1102 from Houghton International, Inc. of Valley Forge, PA, as the soil with the operating temperature of 140 degrees F.
  • the recyclable cleaning compositions of the present invention comprise a detergent that includes one or more surfactants that have an estimated Log P, as defined below, of less than 4.5.
  • the compositions of the present invention are designed for use at temperatures below about 90°C.
  • Membranes of all types can be used with this invention including but not limited to those made of ceramic, polysulfone, polyacrylnitrile (PAN), and cellulose.
  • the formulations of the present invention employ certain classes of individual surfactants and their mixtures, which when combined with other formulation ingredients such as builders, corrosion inhibitors, alkalinity electrolytes, antiscaling materials, hydrotropes, antifoam materials, wetting agents, solvents, other adjuvants and mixtures therof, provide unique cleaning compositions with useful properties of recyclability and waste water clean-up as well as providing high utility in terms of cleaning, foaming and surface protection.
  • the formulations of the present invention may also contain water which dilutes the aqueous alkaline solution of the present invention.
  • the recyclable industrial cleaning compositions of the present invention are an improvement over the prior art at least because the compositions of the present invention may be freed of contaminants via filtration over a wide range of temperatures while retaining a significant amount of their cleaning components under soiled conditions. Moreover, the cleaning compositions may be used at low concentrations and also provide excellent cleaning, low foaming and corrosion protection upon recycle and reuse.
  • a practical family of formulations which are based on a combination of surfactants and builders and other adj uvants which meet a technical criteria for permeabilities to specific membrane pore sizes are disclosed herein.
  • Fig. 1 depicts a schematic view of one type of recycle system process.
  • the original cleaning composition is contained in an initial tank, called a customer tank, and is pumped to a holding tank where soiled articles are present.
  • the soiled cleaning solution is then pumped from the holding tank and through a membrane.
  • the soiled cleaning solution then flows across the membrane and the components that are too large to permeate the pores of the membrane are separated from the
  • the separated material is called the retentate.
  • the retentate is returned to the
  • the permeate passes through the membrane is called the permeate.
  • the permeate is returned to the
  • the permeability of surfactant containing compositions may be measured by
  • test solution is placed in a test solution container.
  • test solution is fed into a standard cross flow membrane of pore size and material of
  • active components e.g., surfactants
  • the % permeability of surfactant containing compositions is
  • the % permeability is defined as
  • % permeability concentration (permeate) * 100 concentration (initial)
  • surfactant system for the aqueous cleaning composition depends upon the behavior of the surfactant system in water as a function of temperature. As the temperature increases, surfactants generally tend to become insoluble and ineffective for recycling. The point at which a surfactant becomes insoluble and precipitates or "clouds out” is called its cloud point.
  • Table A shows that Poly-Tergent ® E- 17 A, an ethylene oxide-propylene oxide-ethylene oxide (EO-PO-EO) block copolymer made by BASF Corp. of Mt. Olive, N. J., has roughly the same permeability (based on total organic carbon) of Poly- Tergent ® SL92, a linear alcohol alkoxylate, at room temperature (68°F) despite the wide difference in cloud point.
  • EO-PO-EO ethylene oxide-propylene oxide-ethylene oxide
  • HBL hydrophobic/lipophobic balance
  • the surfactants of this invention allow the disclosed formulations to
  • compositions contain from 1% to 20% by weight of a synthetic detergent.
  • the detergent is 1% to 20% by weight of a synthetic detergent.
  • a surfactant or surfactants selected from amine oxide surfactants, nonionic
  • ethoxylated surfactants ethoxylated surfactants, anionic surfactants, alkyl polyglucoside surfactants, amphoteric
  • the octanol/water partition coefficient is a common measure of hydrophobicity
  • octanol/water partition coefficients are typically reported as Log K ow , also known as Log P.
  • the preferred amine oxide surfactants are those with an alkyl chain length of
  • the preferred nonionic ethoxylated surfactants include capped alkyl ethoxylates, alcohol ether carboxylates and alkoxylated amine surfactants.
  • Commercially available alkyl ethoxylates of this type include Neodol ® 91-6 manufactured by Shell Chemical
  • Triton ® RW100 Triton ® SP-190 by Union Carbide of Washington, SC.
  • the preferred anionic surfactants include sodium dodecylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl phosphate esters, sodium alkyl ether sulfates, and others.
  • a commercially available surfactant of this type is Avanel ® S74 from BASF Corp. of Mt.
  • the alkylpolyglucoside surfactants are commercially available such as Glucopon ® 425 manufactured by Henkel Corp. in Ambler, PA and Triton ® CGl 10 by Union Carbide of Washington, SC.
  • the preferred amphoteric surfactants include sultaines, betaines, imidazole derivatives, alkylaminoproprionate and diproprionates.
  • Commercially available examples of amphoteric surfactants are Mirataine ® JC-HA manufactured by Rhodia, Inc., Foamtaine ® CAB-A by Alzo, Inc. of Sayerville, NJ and Amphoteric ® 400 from Tomah Products of Milton, WL.
  • the present invention may also contain adjuvants as described below.
  • the present invention may contain builders such as alkali earth metal and/or ammonium salts of carbonate, bicarbonate, hydroxides, phosphates, and silicates or mixtures thereof for the purpose of providing a builder system, and to provide buffering and/or pH adjustability.
  • builders such as alkali earth metal and/or ammonium salts of carbonate, bicarbonate, hydroxides, phosphates, and silicates or mixtures thereof for the purpose of providing a builder system, and to provide buffering and/or pH adjustability.
  • Other optional ingredients that provide buffering and pH adjustability include potassium hydroxide, sodium hydroxide and simple amines such as triethanolamine and 2-(2- aminoethyl)-ethanol.
  • a preferred embodiment of the present invention contains a blend of potassium carbonate and potassium bicarbonate.
  • a preferred range of this blend is a ratio of 1/20 to 20/1 and the preferred weight percent of this blend is about 2 to 15 weight percent of the composition.
  • a more preferred blend ratio is 1/2 to 2/1 and a more preferred weight percent is about 7 to 12 weight percent.
  • corrosion inhibitors such as borax, benzotriazole or carboxylic acid amine mixtures may be included to protect the soiled hard surface articles from flash rusting.
  • the preferred weight % of corrosion inhibitors is 0.1 to 8 weight percent of the composition.
  • Cobratec ® TT-100 a benzotriazole, by PMC Specialties in Rocky River, OH, is an example of a corrosion inhibitor.
  • Anti-scaling materials such as acrylic acid, gluconates and phosphonates, in both acid and salt form, may be included to help prevent hard water interference. Hard water interference is manifested in scale formation. These materials also act as sequestering agents.
  • the preferred weight percent of the gluconates and phosphonates is 0.5-5 weight percent of the composition.
  • Commercially available phosphonates include Belcore ® 577 and Dequest ® from the FMC Corp., Princeton, NJ and Solutia Inc. of St. Louis, MO, respectively.
  • Anti-foam materials such as block copolymers having an HLB of 6 or below, capped alcohol alkoxylates and specialty high molecular weight polymers, such as polysiloxane polymers, can be used to minimize foaming.
  • Preferred weight % of such components range from 0.01 to 5 weight percent of the composition.
  • Commercially available components of this type are Antarox ® L-61 of Rhodia, Inc. and T Zap ® MC-2 by Trico
  • Hydrotropes such as neodecanoic acid and isononanoic acid , may also be added to keep the composition from separating.
  • the preferred weight percent of this ingredient is from about 5 to 25 weight percent of the composition.
  • a preferred hydrotrope is Detrope ® SA-45 manufactured by DeForest Chemicals of Boca Raton, FL.
  • wetting agents may also be used in the compositions.
  • the preferred weight percent of this ingredient is from about 1 to 10 weight percent.
  • a preferred wetting agent is
  • Surfadone ® LP100 from ISP in Wayne, NJ. Solvents such as methyl, butyl, and propyl glycol ethers and diethers in their ethylene, diethylene, propylene and dipropylene form, as well as alcohols, such as isopropyl, methyl and ethyl alcohol, may also be used to improve the cleaning performance.
  • the preferred weight percent of this component is 1-15 weight percent.
  • Dow Chemical is a commercially available product of this type.
  • the present invention may also contain additional surfactants such as Nonidet
  • Triton ® SP-190 and Triton ® DF20 by Union Carbide of
  • the present invention also includes a diluted cleaning composition comprising the cleaning composition and additional water where the additional water is present up to
  • Tables B-D set forth preferred formulations of the present invention.
  • compositions of the present invention provide excellent cleaning, very little foaming and excellent compatibility with varying degrees of water hardness. Studies showing these properties are described below. Cleaning results, foaming results and compatibility with water hardness for Formula 2 (Table C) are set forth below in Tables E, F, and G.
  • Formula 2 was also tested for its foaming characteristics. The results of this study are set forth below in Table F. A quantity of Formula 2 was placed in a INTERCONT ® Top Loading Parts Washer and heated to 140 ° F. It was run for ten minutes at a spray pressure of 40 psi. This test was run on three different fresh solutions with the average result set forth below in Table F.
  • compositions of the present invention provide excellent compatibility with varying degrees of water hardness, as can be seen from the results of the following study.
  • Water samples of varying water hardness were prepared.
  • Formula 2 was diluted to 10%) and combined with the water samples and the resulting mixture was allowed to stand for 24 hours.
  • the formation of a precipitate indicates an unstable product.
  • the results are set forth on Table G.
  • the ability of a surfactant or surfactants to be recycled is assumed to be affected by the ability of the surfactant to depart the micelle of soil and migrate across the membrane. Without being bound to any theory, the factors that influence migration include stability of the micelle and the ability of the surfactant to permeate through the membrane. The stability of the micelle may to depend both on the surfactant system and the type of soil being dispersed.
  • Membranes of all types can be used with this invention including but not limited to those made of ceramic, polysulfone, polyacrylonitrile (PAN), and cellulose. Membranes that are slightly hydrophobic are preferred.
  • the PAN membrane with a 0.05 micron pore size is most preferred, such as Part #0567 manufactured by Osmonics Corp., Minnetonka, MR
  • compositions of the present invention have a high degree of permeability
  • the octanol/water partition coefficient is a common measure of hydrophobicity
  • octanol/water partition coefficients are typically reported as LogK ow , also known as Log P.
  • the permeability of a surfactant may be measured by its Log P or its
  • % permeability is defined as
  • % permeability concentration permeate * 100. concentration ⁇ mt ⁇ al
  • Log P values can be determined by a variety of techniques, such as the
  • Log P values may be estimated from reverse phase HPLC retention data
  • HPLC HPLC
  • the present invention shows that surfactant Log P values indicate the tendency of a surfactant to distribute from the micelle to the aqueous phase and permeate the membrane.
  • a low octanol/water partition coefficient indicates a higher permeability whereas a higher octanol/water partition coefficient indicates lower degree of permeability.
  • Surfactants having a Log P of greater than 4.5 have a low permeability and will be retained in the retentate and will not be recycled back into the cleaning solution.
  • Prior art cleaning compositions typically contain surfactants the have a Log P of greater than 4.5. The recyclability of those compositions, therefore, is not adequate.
  • composition of the present invention contains at least one surfactant having a Log P value of less than 4.5. Therefore, they have greater penneability than the prior art compositions as well as significantly improved recyclability over the prior art.
  • Log P as an indication of recyclable, other physical properties such as critical micelle concentration (CMC) may also indicate recyclability.
  • inorganic materials are permeable regardless of the temperature of operation.
  • the temperature of operation significantly limits the surfactants that may be used in the cleaning process since temperature affects the cleaning ability and recyclability of surfactants.
  • the presence of soil will have a significant impact on the recyclability of a given surfactant system.
  • An aqueous cleaning formulation is defined as being useful for recycling if its surfactant component does not fall below about 50%> by weight of its starting value, upon recycling in unsoiled conditions.
  • An aqueous cleaning formulation is defined as being useful for recycling if its surfactant component does not fall below 30 % by weight of it starting value upon recycling in at least one set of soiled conditions.
  • the product of this invention due to its unique formulation, allows the surfactant component to permeate a membrane filter by at least 50%> of its starting value in unsoiled condition and at least 30%) of its starting value in soiled conditions.
  • Results may be obtained by the following equation which shows the results as a percent of actives found in permeate versus the starting solution.
  • Example 1 The materials and method used for Example 1 are set forth in that section. The materials and methods for Examples 2-7 follow.
  • Nonionic surfactants and ionic surfactants were chosen for their range of structures, cloud points, and expected Log P values.
  • the following surfactants were chosen: Neodol ® 91-6, a mixture of primary C 9 , C 10 and C n alcohol ethoxylates with an average ethylene oxide (EO) content of 6.0 moles, was obtained from Shell Chemical Co. (Houston, TX).
  • Surfonic ® L-l 08/85-5 a mixture of C 6 , C 8 and C 10 (C 8 major) alcohol ethoxylates with an average EO content of 5.0 was obtained from Huntsman Corporation (Houston, TX).
  • Poly-Tergent ® SL-92 and Poly-Tergent ® S505-LF both proprietary primary alcohol alkoxylates, were obtained from Olin Corporation (Stamford, CT).
  • Naxel ® AAS-98S a linear alkyl benzene sulfonic acid (LAS)
  • Ruetgers-Nease Corporation State College, PA
  • Foamtaine ® CAB-A cocamidopropyl betaine ammonium salt (45%> aqueous solution), was obtained from Akzo Inc. (Sayreville, NJ).
  • Barlox ® 12 (30% solution), dodecyl dimethyl amine oxide, and Barlox ® 12i (30%> solution), a proprietary branched alkyl dimethyl amine oxide, were obtained from Lonza, Inc. (Fairlawn, NJ).
  • Glucopon ® 425N (50%) solution a mixture of C 8 , C 10 , C 12 , and C 14 alkyl mono- and di-glucosides, was obtained from Henkel Corporation (Ambler, PA).
  • Tomah AO-405 a proprietary alkyl etheramine alkoxylate, was obtained from Tomah Products (Milton, Wl).
  • Triton ® RW100 an ethoxylated alkyl amine, was obtained from Union Carbide of Charleston, SC.
  • Cosmoline ® 1102 was obtained from Houghton International, Inc. (Valley Forge, PA). Cosmoline ® 1102 was developed for use by the United States military, and is in common commercial use for surface protection of metal parts. It consists primarily of low to moderate molecular weight mineral spirits (boiling point of 157 °C) and contains protective agents for metals. Pennzoil ® 4096 Gear Lubricant SAE 80W90 GL-5 grade (Pennzoil
  • SAE 80W-90, API GL-5 oil is one of the most popular gear oils in use, and is considered to be a universal gear oil for car and light truck rear axles.
  • Pennzoil ® Multi-purpose White Grease 705 (Pennzoil Corporation, Houston, TX) was obtained from an automotive supply store. It is a lithium type petroleum grease with a National Lubricating Grease Institute (NLGI) #2 grade viscosity. It has a stated operating temperature of up to 260 °F. Typical applications include lubrication of conventional brakes, wheel bearings and chassis for passenger cars, trucks, etc.
  • NLGI National Lubricating Grease Institute
  • House de-ionized water was generated with a Milli-Q Water System (Millipore Corporation, Milford, MA).
  • HPLC grade methanol and HPLC grade ammonium acetate were obtained from Fisher Scientific (Pittsburgh, PA).
  • Toluene, ethylbenzene, butyl benzene, hexyl benzene, and octyl benzene were obtained from Sigma- Aldrich Corp. (Milwaukee, Wl).
  • a Sievers 800 Portable Total Organic Carbon analyzer was used for the TOC measurement of aqueous samples (Sievers Instruments, Denver, CO). Analysis is based on oxidation with ammonium persulfate and UV light. Reported results are the average of triplicate measurements.
  • a Hewlett-Packard 1050 series HPLC (Palo Alto, CA) consisting of a quaternary pump and autosampler was used for analysis of surfactants. Reversed phase HPLC was performed on all samples. Samples were filtered through Gelman 0.45 um PVDF filters and analyzed. Almost all separations were utilized the following conditions:
  • Detection was achieved with either a Hewlett-Packard series UV detector set at 275nm, or a Sedere Sedex 55 (Richard Scientific, Novato, CA) evaporative light scattering detector (ELSD).
  • the ELSD was operated at 40°C, with a nitrogen flow rate of 1.8 1/min.
  • a Chromeleon Chromatography Data system (Dionex Corp. Sunnyvale, CA) was used to collect and process the HPLC data. Determination of Log P
  • the determination of the Log P value which includes both calculated and estimated, for surfactants is set forth below.
  • the Log P values of the present invention are calculated according to the estimated Log P determination.
  • the column void time was determined from the elution time of unretained salt.
  • aplot of Log k' vs. Log P yields a straight line; the plot exhibits curvature under the gradient mobile phase program that was used. (Fig. 6).
  • a quadratic curve results in an acceptable fit of the calibration data, permitting estimates of the surfactant Log P values from the retention data.
  • This method is based on the concept that the various fragments of a molecule contribute additively to its Log P value.
  • the molecule is conceptually divided into fragments.
  • the fragment Log P contributions can be found in published tables.
  • Factors are used to adjust the fragment results, based on the manner in which the fragments are put together to make the molecule.
  • Calculated Log P values are included in Table H for alkyl monoglucosides, linear alkyl benzene sulfonates, and for alcohol ethoxylates. It may be seen that there is a bias between the calculated Log P values and the corresponding HPLC estimated Log P values. The relationship between calculated and estimated Log P values is shown graphically in Fig.
  • Membrex Benchmark GX (Fairfield, NJ) lab-scale rotating membrane filtration unit was used for all permeability studies.
  • Membrane cartridges were made of polyacrylonitrile with a 0.05um pore size (Part #0567, Osmonics Corp., Minnetonka, MR).
  • Cloud Points Surfactant cloud point values were obtained from manufacturer literature as reported for 1% aqueous solutions and are reported on Table H.
  • compositions of the present invention comprising at least one surfactant having a Log P of less than about 4.5.
  • This Example demonstrates how specific formulas would perform in a range of membrane systems.
  • the study was designed to test specific recyclability factors including formula components (surfactant systems), temperature, membrane pore size, membrane material compatibility and soiled systems versus unsoiled systems.
  • the original cleaning composition solution was contained in an initial tank (customer tank) and pumped to a holding tank where soiled articles were present.
  • the contaminated cleaning solution was then pumped from the holding tank through a membrane.
  • the contaminated cleaning solution then flowed across the membrane.
  • the retentate was returned to the holding tank.
  • the permeate was returned to the (initial) customer tank for reuse.
  • the two formulas tested included Formula A which has a surfactant system that is phase stable up to 180°F and Formula B which has a surfactant system that is phase stable up to 105°- 110°F.
  • the formulations for Formula A and B are set forth below on Tables I and J. The formulations were prepare by combining the ingredients listed and mixing at room temperature.
  • microns 0.10 microns, 0.20 microns, 0.45 microns and 0.50 microns.
  • % recyclability permeate TOC value feed TOC value
  • Figures 2-5 illustrate the percent recyclability versus membrane pore size for Formula A versus Formula B the in unsoiled and soiled conditions at 80°F and 140°F.
  • the surfactants of Table H were evaluated for permeability, both in the absence and in the presence of soil.
  • the surfactants studied were chosen based on their range of cloud points and Log P values.
  • the objective of this work was to determine the relationship between surfactant permeability behavior, cloud points, and octanol/water partition coefficients and Log P.
  • Example 2 was run in the absence of soil. Results for all samples of Example 2 are included in Table K.
  • FIG. 1 A diagram for the experimental setup is given in Fig 1.
  • oil was added at a 1% level to both tanks.
  • the tanks were heated with magnetic stirring on hotplates to either 140 °F or 100 °F.
  • the temperature was maintained throughout each experiment with RTD temperature probes interfaced to the hotplates.
  • the rotation rate of the membrane filtration unit was 3000 RPM. Material from the holding tank was pumped into the membrane filtration unit at a flow of 600 ml/min.
  • the outlet pressure was adjusted to achieve a 5 psi pressure drop across the membrane, resulting in permeate flows of approximately 100-300 ml/min depending on the soil and the operating temperature.
  • the transfer line from the customer tank to the holding tank was adjusted to equal the permeate flow rate in order to maintain a constant level in both customer and holding tank.
  • One cycle or turnover is defined to be the time at which the cumulative volume of permeate equals the initial volume of the customer tank. Permeate samples were collected at 1, 5 and/or 10 cycles.
  • a 0.05 um PAN membrane was used in the filtration.
  • a sample of the initial cleaning solution was collected before addition of oil (if added) and before starting membrane operation.
  • This initial cleaning soultion sample is defined to be the 100% permeable concentration.
  • Serial dilutions of the 100% permeable sample were made to obtain calibration samples for the HPLC analysis. Point-to-point calibration curves were used for HPLC quantitation due to the non-linear nature of the ELSD response.
  • TOC analysis the initial cleaning solution sample was used for the single point calibration.
  • surfactants with multiple surfactant oligomers individual oligomer permeability and overall surfactant permeability were determined. The overall surfactant permeability was calculated from the average of the oligomer results, except for Surfonic ® L108/85-5 where the result for major C8 hydrophobe was used.
  • the TOC results and the HPLC results are listed in Table K for permeability studies conducted in the absence of soil. In general, there is good agreement between TOC results and HPLC results. The one exception are the results for the Pluronic ® EO-PO-EO block co-polymer for which the TOC result is about twice that of the HPLC result. The HPLC results are believed to more reliable as any contamination sources would not be included.
  • FIG. 9 A plot of the HPLC detennined permeability results vs. cycle number is shown in Fig. 9. All surfactants evaluated had no significant change in permeability after Cycle 5. Plots of individual hydrophobe results vs. cycle number are given in Figs. 10-11 and listed in Table L for Neodol ® 91-6 and for Poly-Tergent ® SL-92 (see Fig. 7 for hydrophobe identifications). The results for the individual hydrophobes are consistent with the lower alkyl size/lower Log P estimate hydrophobes exhibiting greater permeability behavior. For example, the C 9 hydrophobe of the Neodol ® 91-6 had a much larger permeability than the C n hydrophobe.
  • Ave overall surfactant permeability based on average oligomer results, except for Surfonic ® LI 08 for which the C8 oligomer result is used.
  • FIG. 14 A plot of permeability vs. Log P estimates for all surfactants including the individual hydrophobes is given in Fig. 14.
  • Fig. 15 shows the same plot, but with labels to identify the different classes of surfactant. There appears to be a reasonable correlation between Log P estimate (or hydrophobe size) and %> Permeability.
  • Example 3 was performed in the same way as Example 2 but in the presence of soil. The method described in Example 2 was followed in Example 3.
  • the permeability performance of surfactants in soiled systems is of interest given the desire to separate the aqueous cleaning materials from soil.
  • Two oils were evaluated in this study: Cosmoline ® 1102 and Pennzoil ® 80W90 oil. Observationally, the Cosmoline ® oil formed stronger emulsions with the surfactants and exhibited poorer oil/water splitting than the Pennzoil ® oil.
  • samples in the Cosmoline ® oil studies tended to have some visible oil observed in the permeates, while no significant oil was observed in the permeates for the Pennzoil ® system.
  • the permeability results determined at 140 °F for the soiled systems are listed in Table N.
  • the Cosmoline ® 1102 system initially was evaluated for a small set of surfactants, with permeate samples obtained from Cycles 1, 5, and 10. Of the surfactants studied there was essentially no difference in Cycle 5 vs. Cycle 10 results; the exception is Neodol ® 91-6. Based on these results, only Cycle 5 samples were collected and analyzed for the remaining studies reported in Table N.
  • *Ave overall surfactant permeability based on average oligomer results, except for Surfonic ® L108 for which the C8 oligomer result is used.
  • Pennzoil ® system results appear to be similar to those obtained for the unsoiled system (Fig. 14).
  • a plot of surfactant permeability results in the unsoiled system vs. those obtained in the Pennzoil ® 80W90 system is shown in Fig. 24.
  • Example 4 The Barlox ® 12i surfactant was evaluated further to study the effect of surfactant concentration and multiple oil additions on permeability results.
  • the initial bath surfactant concentration was increased to two and one half (2.5) times that of the standard diluted conditions (i.e., 0.375%, not corrected for solids level).
  • Cosmoline ® 1102 oil was added at 1%, temperature was equilibrated to 140 °F and the membrane operation was started. A permeate sample was collected at Cycle 5. Then, 1% additional Cosmoline ® 1102 was added to the customer bath (based on total customer and feed bath volumes). A second permeate sample was collected after 5 additional cycles (i.e., Cycle 10). Again, 1% more Cosmoline ® oil was added and the process repeated for Cycles 15 and 20.
  • the permeability results are given in Table O and plotted in Fig. 25.
  • the simplest explanation for these results is that the Cosmoline ® 1102 exhaustively extracts about 65% of the Barlox ® 12i.
  • the permeability of four surfactants was evaluated at 100 °F in the presence of 1%) Cosmoline ® 1102 oil.
  • Two of the surfactants have cloud points (Neodol ® 91-6 and Poly-Tergent ® SL-92) while the other two surfactants do not have cloud points (Barlox ® 12i and Naxel ® AAS-98S).
  • the results are listed in Table N and are plotted in Fig. 26 with a comparison to the 140 °F results.
  • the Barlox ® 12i and Naxel ® AAS-98S exhibit good water solubility at both temperatures and thus, the permeability results are less temperature sensitive.
  • Example 7 involves a fully formulated composition, Formula 3, as described in Table B and was tested in a soil system comprising a 1:1:1 ratio of Cosmoline ® 1102, Pennzoil ® 4096 SAE 80W90 GL-5 Multipurpose Gear Lube and Pennzoil ® Multipurpose White Grease 705 (Pennzoil Corp., Houston, TX) and was run according to Example 1. The purpose of this test was to determine the recyclability of Barlox 12i.

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Abstract

L'invention concerne une composition de nettoyage recyclable comportant une solution alcaline d'au moins un tensioactif. La composition de nettoyage présente un degré accru de récupération de tensioactif par filtration sur membrane.
PCT/US2001/018546 2000-06-06 2001-06-06 Compositions de nettoyage recyclables WO2001094510A1 (fr)

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US10/296,777 US20040014624A1 (en) 2001-06-06 2001-06-06 Recylable cleaning compositions
EP01946175A EP1303581A4 (fr) 2000-06-06 2001-06-06 Compositions de nettoyage recyclables
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2010060408A3 (fr) * 2008-11-03 2010-10-07 Koenig Thomas Procédé et installation de décapage
US10793809B2 (en) 2017-02-28 2020-10-06 Ecolab Usa Inc. Alkaline cleaning compositions comprising a hydroxyphosphono carboxylic acid and methods of reducing metal corrosion
US11136529B2 (en) 2016-09-07 2021-10-05 Ecolab Usa Inc. Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants
EP3913041A1 (fr) * 2020-05-20 2021-11-24 Beratherm AG Solution aqueuse de nettoyage permettant d'éliminer des restes de protéines, d'enzymes, d'huile de silicone et de gras ainsi que son utilisation
US11198837B2 (en) 2017-02-28 2021-12-14 Ecolab Usa Inc. Alkaline cleaning compositions comprising an alkylamino hydroxy acid and/or secondary amine and methods of reducing metal corrosion

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Publication number Priority date Publication date Assignee Title
WO2010060408A3 (fr) * 2008-11-03 2010-10-07 Koenig Thomas Procédé et installation de décapage
EP2352859B1 (fr) * 2008-11-03 2018-06-27 Thomas König Procédé et installation de décapage
US11136529B2 (en) 2016-09-07 2021-10-05 Ecolab Usa Inc. Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants
US11820962B2 (en) 2016-09-07 2023-11-21 Ecolab Usa Inc. Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants
US10793809B2 (en) 2017-02-28 2020-10-06 Ecolab Usa Inc. Alkaline cleaning compositions comprising a hydroxyphosphono carboxylic acid and methods of reducing metal corrosion
EP3589778A4 (fr) * 2017-02-28 2020-12-09 Ecolab USA Inc. Composition de nettoyage alcaline comprenant un acide hydroxyphosphono-carboxylique et procédés de réduction de la corrosion métallique
US11198837B2 (en) 2017-02-28 2021-12-14 Ecolab Usa Inc. Alkaline cleaning compositions comprising an alkylamino hydroxy acid and/or secondary amine and methods of reducing metal corrosion
US11725162B2 (en) 2017-02-28 2023-08-15 Ecolab Usa Inc. Alkaline cleaning compositions comprising an alkylamino hydroxy acid and/or secondary amine and methods of reducing metal corrosion
EP3913041A1 (fr) * 2020-05-20 2021-11-24 Beratherm AG Solution aqueuse de nettoyage permettant d'éliminer des restes de protéines, d'enzymes, d'huile de silicone et de gras ainsi que son utilisation

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