METHOD FOR CLEANING A MEMBRANE FILTER SYSTEM

专利摘要:
blend of surfactants for cleaning filtration membranes the present invention relates to the field of membrane separation processes and cleaning-in-place compositions intended for cleaning such membranes. cleaning compositions can remove proteins, grease, and other soils from foods, beverages and fermented products and provide an alternative surfactant system that is more beneficial to the npe environment. according to the invention, surfactants and polymers useful for this process are unpredictable and specific surfactants, polymers and combinations thereof are disclosed for exclusive use as part of a cleaning composition. methods of using these are also included.
公开号:BR112015021560B1
申请号:R112015021560-2
申请日:2014-03-03
公开日:2021-08-10
发明作者:Paul Schacht；Jeffrey Weilage；Eric Schmidt；Joseph P Curran；Ralf Krack；Victor Fuk- Pong Man；Charles Allen Hodge
申请人:Ecolab Usa Inc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to methods and compositions for cleaning membranes used in separation facilities. Cleaning compositions can remove protein and offer an alternative surfactant system more environmentally beneficial to nonylphenol ethoxylate (NPE). The application includes a surfactant additive or enhancer system that can form part of a cleaning composition or can be used alone to improve the cleaning properties of cleaning solutions, as well as improve membrane performance by cleaning the surface and minimizing it. if subsequent protein or dirt fouling during the next processing run. FUNDAMENTALS OF THE INVENTION
[002] Membranes provided within a separation facility can be treated using cleaning-in-place (CIP) methods to provide washing, rinsing, pre-treatment, cleaning, sanitizing and preservation, as filtration membranes have a tendency to fouling during processing. Fouling manifests as a decline in flow with time of operation. Flux decline is typically a reduction in permeation flux or permeation rates that occurs when all operating parameters such as pressure, feed flow rate, temperature and feed concentration are kept constant. In general, membrane fouling is a complicated process and is believed to occur due to a number of factors including electrostatic attraction, hydrophobic and hydrophilic interactions, the deposition and accumulation of feed components, eg suspended particulates, impermeable dissolved solutes, and further normally permeable solutes, on the membrane surface and/or within the membrane pores. It is expected that almost all feed components will encrust membranes to some extent. See Munir Cheryan, Ultrafiltration and Microfiltration Handbook, Technical Publication, Lancaster, Pa., 1998 (Pages 237 to 288). Scale components and deposits can include inorganic salts, particulates, microbial and organic elements.
[003] Filtration membranes typically require periodic cleaning to enable successful industrial application within separation facilities such as those found in the food, dairy and beverage industries. Filtration membranes can be cleaned by removing foreign material from the surface and body of the membrane and associated equipment. The cleaning procedure for filtration membranes may involve a CIP site cleaning process in which cleaning agents are circulated over the membrane to wet, penetrate, dissolve and/or rinse to remove foreign materials from the membrane. Various parameters that can be manipulated for cleaning typically include time, temperature, mechanical energy, chemical composition, chemical concentration, soil type, water type, hydraulic design, and membrane construction materials.
[004] Chemical energy in the form of detergents and cleaners can be used to solubilize or disperse the scale or dirt. Thermal energy in the form of heat can be used to help the chemical cleaners work. In general, the higher the cleaning temperature of the solution, the more effective it is as a cleaning treatment, although most membrane materials have temperature limitations due to the material of construction. Many membranes have additional chemical limitations. Mechanical energy in the form of high-speed flow also contributes to the successful cleaning of membrane systems. See Munir Cheryan, Ultrafiltration and Microfiltration Handbook, Technical Publication, Lancaster, Pa., 1998, pages 237-288.
[005] In general, it was identified that the frequency of cleaning and type of chemical treatment performed on the membrane affect the operational life of a membrane. It is believed that the operational life of a membrane can be reduced as a result of chemical degradation of the membrane over time. Various membranes are provided having temperature, pH, and chemical restrictions to minimize degradation of the membrane material. For example, many polyamide reverse osmosis membranes have chlorine restrictions, as chlorine can have a tendency to attack and oxidatively damage the membrane. Cleaning and sanitizing filtration of membranes are intended to comply with laws and regulations that may require cleaning in certain applications (eg, the food and biotechnology industries), reduce microorganisms to prevent contamination of product streams, and optimize the process when restoring the flow. See Munir Cheryan, Ultrafiltration and Microfiltration Handbook, Technical Publication, Lancaster, Pa., 1998, pages 237-288.
[006] Other exemplary techniques for cleaning filtration membranes are described by Pat. No. U.S. 4,740,308 to Fremont et al.; Pat. No. 6,387,189 to Groschl et al.; Pat. U.S. 6,071,356 to Olsen; and Munir Cheryan, Ultrafiltration and Microfiltration Handbook, Technical Publication, Lancaster, Pa., 1998 (Pages 237-239).
[007] Membrane performance is believed to decrease during processing of milk, whey, and oilier feed streams due to fouling of the membrane surface or membrane pores by protein, fat, minerals and other stream components feed.
[008] Therefore, fouling membranes by high-processing solid feed streams requires that they be regularly cleaned using a cleaning-in-place (CIP) approach in which the use of alkaline, acid and cleaning adjuvants such as surfactants and polymers Water conditioning aids in cleaning fouling and restores the membrane to functional use.
[009] The proper use of alkaline and acidic adjuvants requires an understanding of the functionality of the chemistry used. As an example, too high a pH or too low a pH can damage the polymeric membrane material. The use of solvents or excessive use of surfactants can often result in destruction of the glue line causing the membrane to undergo delamination making it non-functional. Excessive use of oxidizing chemicals such as sodium hypochlorite (chlorine bleach) or hydrogen peroxide can irreversibly damage some types of polymeric membrane.
[010] Conventional cleaning compositions used in CIP protocols, particularly those intended for institutional use, generally contain alkylphenol ethoxylates (APEs). APEs are used in cleaning compositions as a cleaner and degreaser for their effectiveness in removing a variety of soils from a variety of surfaces. Commonly used APEs include nonyl phenol ethoxylates (NPE) surfactants such as NPE 9.5 or nonoxynol-9 which is a 9.5 mol nonyl phenol ethoxylate.
[011]However, although effective, APEs are disadvantaged due to environmental issues. For example, NPEs are formed by combining ethylene oxide with nonylphenol (NP). Both NP and NPEs exhibit estrogen-like properties and can contaminate water, vegetation and marine life. NPE is also not readily biodegradable and remains in the environment or food chain for indefinite periods of time. Therefore, there is a need in the art for an ecological and biodegradable alternative that can replace APEs in membrane cleaners that allow membranes to be properly cleaned of dirt, do not damage membranes or membrane construction materials, and do not encrust into membranes. SUMMARY OF THE INVENTION
[012] The present invention relates to the field of cleaning in place and other membrane cleaning protocols that serve to clean membranes in separation facilities. More specifically, the invention relates to a surfactant system which for use therein offers an alternative surfactant system more environmentally safe than the NPE currently used in many applications.
[013] The present invention comprises a surfactant system, as well as alkaline cleaning compositions that incorporate the same and methods for using it. In one embodiment, the present invention consists of a surfactant component for use alone or in cleaning compositions and methods of using the same. The choice of surfactants that will be useful in cleaning membranes is not easily predictable and typically does not easily follow generic chemical and physical resources such as HLB, degree of ethoxylation, linearity, branching, and the like. In accordance with the invention, Applicants have determined a number of surfactants and polymers, one or more of which can be successfully used in membrane cleaning protocols. The surfactant component of the invention which includes one or more surfactants or polymers selected from the following group: polyethylene glycol (molecular weight range 300 to 4000), linear alcohol ethoxylate (alcohol ranging from C9 to C15 and average moles of ethoxylation of 6 to 8, an alkoxylated C10 branched Guerbet alcohol (such as the Lutensol XP and XL product line available from BASF with 3 to 10 moles of ethoxylation, an alkyl glycoside with a C8 to C10 alkyl group, an alkyl aryl sulfonate (C1 to C10), an alkyl dimethyl amine oxide (C10 to C16).
[014] Another aspect of the present invention is to provide a cleaning composition comprising a source of alkalinity and the surfactant and/or polymeric system of the invention. The alkalinity source comprises approximately 500 ppm to 10,000 ppm of actives in a use solution. The surfactant system comprises from about 0.05 percent by weight to about 1.0 percent by weight of actives in the cleaning solution. Additional functional ingredients such as chelators, preservatives, hydrotopes and the like may also be present. The surfactant system can be used as part of a cleaning composition, can be used as an enhancer composition in combination with standard cleaning compositions, or can be used alone as part of a general CIP process.
[015] In another embodiment, the present invention consists of a method to remove dirt, solutes and proteins from filtration membranes in a cleaning process. The method includes the steps of removing liquid product from the filtration system, contacting the membrane with an alkaline or acidic cleaning composition of the invention, or a surfactant composition. This is typically achieved by circulating through the filtration system with an aqueous cleaning use solution and subsequently rinsing the filtration system.
[016] Membranes that can be treated according to the invention include any membranes that are designed for periodic cleaning, and are generally used in various applications that require a separation by filtration. Exemplary industries using membranes that can be treated in accordance with the invention include the food industry, the biotechnology industry, the pharmaceutical industry, the chemical industry and the water purification industry. In the case of the food and beverage industries, products including milk, whey, fruit juice, beer and wine are generally processed through a membrane for separation. The water purification industry often relies on membranes for desalination, contaminant removal and wastewater treatment. An exemplary use of membranes in the chemical industry includes electrophoretic painting processes. This invention is particularly useful in removing proteins, fats and minerals such as those from whey in a milk or cheese making process.
[017] Although several embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the detailed description below, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. DESCRIPTION OF THE FIGURES
[018] Figure 1 is a graph of a PVDF Membrane Milk Production Performance Flow Diagram showing the different surfactant boosters of the invention compared to traditional cleaners.
[019] Figure 2 is a graph of a PES Membrane Milk Production Performance Flow Diagram showing the different surfactant boosters of the invention compared to traditional cleaners.
[020] Figure 3 is a graph of a PVDF Membrane Milk Production Average Flow Diagram showing the different surfactant boosters of the invention compared to traditional cleaners.
[021] Figure 4 is a graph of a PES Membrane Milk Production Average Flow Diagram showing the different surfactant boosters of the invention compared to traditional cleansers.
[022] Figure 5 is a graph that shows the average production flow of PES membranes. In this case, the four new chemicals tested had a 9-25% higher flow over the course of the entire production cycle than the four in-line chemicals.
[023] Figure 6 is a graph that shows the average production flow of PVDF membranes. Similar to Figure 5, the four highest performing chemicals outperformed the four in-line chemicals by a range of 1 to 36% when analyzing the highest average flow during the course of a simulated production run.
[024]Figure 7 shows the number of alkaline “removal” cycles in PES membranes used to obtain a baseline of 275 LMH before screening the next set of chemicals.
[025]Figure 8 is a graph showing the number of alkaline removal cycles to return to baseline CWF in PVDF membranes.
[026] Figure 9 is a graph that shows the number of removal and rinsing cycles required to reach the baseline of a polyether sulfone (PES) membrane.
[027]Figure 10 is a graph showing the number of removal and rinsing cycles required to reach the baseline of a polyvinylidene difluoride (PVDF) membrane.
[028]Figure 11 is a graph showing the strength glue line test versus displacement of PES membranes.
[029]Figure 12 is a graph showing the strength glue line test versus displacement of PVDF membranes.
[030]Figure 13 is a graph showing PES membranes with milk drip on the membranes with the contact angle versus production.
[031]Figure 14 is a graph showing the top contact angle in PVDF membranes. DETAILED DESCRIPTION OF THE INVENTION
[032] Except in the operating examples, or where otherwise indicated, all numbers expressing amounts of ingredients or reaction conditions used herein will be understood to be modified in all cases by the term "about".
[033] Depending on the use in question, percent by weight (%), percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100 .
[034] Depending on the use in question, the term "about" that modifies the amount of an ingredient in the compositions of the invention or is used in the methods of the invention refers to the variation in the numerical amount that can occur, for example, through procedures measuring and handling typical liquids used to produce concentrates or use real-world solutions; through inadvertent error in these procedures; through differences in the manufacture, origin, or purity of the ingredients used to make the compositions or carry out the methods; and the like. The term about also includes amounts which differ due to different equilibrium conditions of a composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents to amounts.
[035] The term "alkyl" or "alkyl groups", as used herein, refers to saturated hydrocarbons that have one or more carbon atoms, including straight chain alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloeptyl, cyclo- octyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl substituted alkyl groups (e.g., alkyl substituted cycloalkyl groups and substituted alkyl groups by cycloalkyl).
[036]Except where otherwise specified, the term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls". As used herein, the term "substituted alkyls" refers to alkyl groups that have substituents that replace one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxylate, phosphooxylate, alkylthiophosphine cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates, sulfamoyl trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups. In some embodiments, substituted alkyls can include a heterocyclic group. As used herein, the term "heterocyclic group" includes closed ring structures analogous to carbocyclic groups in which one or more carbon atoms in the ring consist of an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups can be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes), thyrane (episulfides), dioxirane, azetidine, oxetane, thiethane, dioxetane, dithiethane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran and furan.
[037] The term “surfactant” or “surface active agent” refers to an organic chemical that when added to a liquid alters the properties of that liquid on a surface.
[038]“Cleaning” means performing or assisting in the removal of dirt, bleaching, microbial population reduction, rinsing, or a combination thereof.
[039] As used, the term "substantially exempt" refers to compositions completely lacking the component or having a small amount of the component that the component does not affect the effectiveness of the composition. The component can be present as an impurity or as a contaminant and should be less than 0.5% by weight. In another embodiment, the amount of component is less than 0.1 by weight, and in yet another embodiment, the amount of component is less than 0.01% by weight.
[040]It should be noted that, as used in this specification and the accompanying claims, the singular forms “a”, “an”, and “o” include plural referents except where the content clearly dictates otherwise. Thus, for example, a reference to a composition containing "a compound" includes a mixture of two or more compounds. It should also be noted that the term “or” is generally used in its sense to include “and/or” except where the content clearly dictates otherwise.
[041] The term "assets" or "percentage of assets" or "percentage by weight of assets" or "concentration of assets" is used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage less inert ingredients like water or salts.
[042] Depending on the usage in question, the terms "free from alkyl phenol ethoxylate" or "free from NPE" refers to a composition, mixture, or ingredients that do not contain alkyl phenol ethoxylate or compounds containing phenol to which they have not been added. Alkyl phenol ethoxylates or alkyl phenol ethoxylate-containing compound can be present through contamination of a composition, mixture, or ingredients, the amount of which should be less than 0.5% by weight. In another embodiment, the amount is less than 0.1 by weight, and in yet another embodiment, the amount is less than 0.01% by weight.
[043] The term "substantially similar cleaning performance" generally refers to obtaining a replacement cleaning product or replacement cleaning system generally of the same grade (or at least not to a significantly lesser grade) or cleaning or with generally the same expenditure (or at least not significantly less expenditure) or effort, or both, when using the substitute cleaner or substitute cleaning system in place of an alkyl phenol ethoxylate containing cleaner to meet a typical soiled condition on a typical substrate . This degree of cleanliness may, depending on the particular cleaner and particular substrate, correspond to a general absence of visible soiling, or to some lesser degree of cleanliness, as explained in the previous paragraph.
[044]The citation of numeric ranges by evaluation criteria includes all numbers included within that range (eg 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4 and 5) .
[045] The terms "include" and "including" when used in reference to a list of materials refer to, but are not limited to, the materials so mentioned. Surfactant/Polymer System of the Invention
[046] The present invention comprises a surfactant system that can be used as a reinforcer or as part of an alkaline or acidic cleaning composition and methods of using the same. Surfactants can be used as a membrane cleaning adjuvant for improved removal of proteins, grease, and other soils from membranes and in some cases to improve the hydrophilicity properties of membranes and improve the permeation properties of processing. Other considerations of a successful surfactant system include rinse-off characteristics, low foaming, satisfactory soil removal or cleaning properties, biodegradability, and relatively low cost. The use of an incompatible membrane surfactant can cause fouling problems on the membrane surfaces. For example, the use of cationic surfactants is generally associated with irreversible membrane fouling due to the inability to rinse or wash the surfactant from the surface, it is understood that the membrane has a negative surface charge and therefore a cationic surfactant is strongly bound to the surface and cannot be easily removed. This residual surfactant on the surface acts as a scale causing low production rates and water flow resulting in unsatisfactory production performance.
[047]Other surfactants such as anionic surfactants (DDBSA) are considered non-surface bound because both the membrane and the surfactant are negatively charged. This is believed to improve the surfactant's washability while helping to aid in the cleansing of fats and proteins due to their reduction in surface tension.
[048]Non-ionic surfactants have been sparingly used as membrane cleaning adjuvants. They typically have positive properties like decay, low foaming, wetting and surface tension reduction. However, many of the nonionic surfactants can also cause membrane fouling problems due to their poor overall rinseability characteristics. Since nonionics are technically neutral molecules, the predictability of whether they act well as a surfactant booster on a particular membrane type is less certain. Molecular weight, hydrophilic-lipophilic balance (IILB), branching, linearity, alcohol chain length, Draves wetting value, and degree of ethoxylation individually do not adequately predict whether a nonionic surfactant or polymer will or will not operate well on a membrane. In addition, surface type membranes such as polyether sulfone (FES), polyvinylidene difluoride (PVDF) have different surface energies which also affect how a surfactant acts on the surface and how the scale acts on the surface. The molecular weight cut or pore size of a particular membrane will also affect the functionality of a surfactant due to pore fouling, pore penetration for pore cleaning, membrane permeation exclusion due to branching and molecular weight, and ease of permeation due to linearity.
[049] In one embodiment, the present invention is a surface active and polymeric component for use in the cleaning compositions and methods of the invention. The surfactant and polymeric component is preferably a nonionic surfactant or suitable nonionic polymer.Surfactants/Polymers for Use in the Invention
[050] In certain embodiments, the blend of surfactant and polymer includes one or more nonionic surfactants and polymers useful in the invention and are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of a compound aliphatic alkyl or organic hydrophobic polyoxyalkylene with an alkaline hydrophilic oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Virtually any hydrophobic compound that has a hydroxyl, carboxyl, amino or starch group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form an agent non-ionic surface active. The length of the hydrophilic polyalkylene portion that is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-dispersible or water-soluble compound that has the desired degree of balance between hydrophilic and hydrophobic properties. Nonionic surfactants useful in the present invention include:
[051] The condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from 6 to 24 carbon atoms with from 3 to 50 moles of ethylene oxide. The alcohol portion can consist of mixtures of alcohols in the carbon range outlined above, or it can consist of an alcohol that has a specific number of carbon atoms within that range. Examples of commercial surfactants are available under the trade names Neodol® manufactured by Shell Chemical Co. and Alfonic® manufactured by Vista Chemical Co. These include Guerbet alcohols such as those sold under the name Lutensol from BASF.
[052] In addition to ethoxylated carboxylic acids, the commonly named polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin and polyhydric alcohols (saccharide or sorbitan/sorbitol) have application in this invention. All of these ester moieties have one or more reactive hydrogen sites on their molecule that can undergo further acylation or addition of ethylene oxide (alkoxide) to control the hydrophilicity of these substances.
[053] Ethoxylated C6-C18 fatty alcohols and ethoxylated and mixed propoxylated C6-C18 fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are water soluble. Suitable ethoxylated fatty alcohols include C10-C18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 50.
[054] Suitable nonionic alkylpolysaccharide surfactants particularly for use in the present compositions include those described in US Patent No. 4,565,647, Llenado, issued January 21, 1986. Such surfactants include a hydrophobic group containing from 6+ to 30 carbon atoms and a polysaccharide, eg a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl moieties can be substituted for the glycosyl moieties. (Optionally, the hydrophobic group is attached at positions 2, 3, 4, etc., thus generating a glucose or galactose as opposed to a glycoside or galactoside). The linkages between saccharides can be, for example, between the one position of the additional saccharide units and the 2, 3, 4 and/or 6 positions on the above saccharide units.
[055] The Nonionic Surfactants survey, edited by Schick, MJ, Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds commonly employed in the practice of the present invention. A typical listing of nonionic classes, and species of these surfactants, is provided in US Patent No. 3,929,678 issued by Laughlin and Heuring on Dec. 30, 1975. Additional examples are provided in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
[056] In some embodiments, the nonionic surfactant is a Guerbet alcohol ethoxylate of the formula R1--(OC2H4)n--(OH), where R1 is a branched C9-C20 alkyl group and n is from 2 to 10.
[057] In a preferred embodiment, the Guerbet alcohol ethoxylate that is used in the liquid surfactant composition is a Guerbet alcohol ethoxylate of the formula R1--(OC2H4)n--(OH). This includes a Guerbet alcohol ethoxylate where R1 is a branched C10 to C18 alkyl group and is from 5 to 10 preferably 7 to 9 and also those where R1 is a branched C8 to C12 alkyl group preferably , branched C10 alkyl group and n is 2 to 4, preferably 3. Such alcohols from Guerbet are available, for example, under the trade name Lutensol from BASF or Eutanol G from Cognis.
[058]The Guerbet reaction is a self-condensation of alcohols through which alcohols that have branched alkyl chains are produced. The reaction sequence is related to Aldol condensation and takes place at high temperatures under catalytic conditions. The product is a branched alcohol with twice the molecular weight of the reagent minus one mole of water. The reaction proceeds through a number of sequential reaction steps. First, alcohol is oxidized to an aldehyde. Then, Aldol condensation occurs after proton extraction. Then, the aldol product is dehydrated and allelic aldehyde hydrogenation takes place.
[059]These products are called Guerbet alcohols and are further reacted with the non-ionic alkoxylated guerbet alcohols by alkoxylation, that is, with ethylene oxide or propylene oxide. Ethoxylated guerbet alcohols have a lower solubility in water compared to linear ethoxylated alcohols with the same number of carbon atoms. Therefore, the exchange of linear fatty alcohols for branched fatty alcohols makes it necessary to use satisfactory solubilizers that are able to keep the guerbet alcohol in solution and the resulting emulsion stable even over a longer period of storage time.
[060] In certain embodiments, the surfactant compositions include one or more other suitable polymers that can be used in the surfactant compositions of the invention and include alkyl aryl sulfonates. The alkyl aryl sulfonates that can be used in the cleaning composition can have an alkyl group that contains 6 to 24 carbon atoms and the aryl group can be at least one of benzene, toluene and xylene. A suitable alkyl aryl sulfonate includes linear alkyl benzene sulfonate. A linear alkyl benzene sulfonate includes linear dodecyl benzyl sulfonate which can be provided as the sulfonic acid which is neutralized to form the sulfonate. Additional alkyl aryl sulfonates include xylene sulfonate and cumene sulfonate.
[061] Suitable alkane sulfonates that can be used in the cleaning composition can have an alkane group that has 6 to 24 carbon atoms. Suitable alkane sulfonates that can be used include secondary alkane sulfonates. A suitable secondary alkane sulfonate includes C14-C17 sodium secondary alkyl sulfonate commercially available as Hostapur SAS from Clariant.
[062] In a preferred embodiment, the surfactant system includes one or more of the following: a polyalkylene glycol, an alcohol ethoxylate, a polyalkylene glycol ether ethoxylate, an alkyl glycoside, an alkyl aryl sulfonate, an alkyl dimethyl amine oxide , and an alpha olefin sulfonate. In a more preferred embodiment, the invention includes a polyethylene glycol, a linear C9-C11 alcohol ethoxylate, (preferably with 5 to 6 moles of ethoxylation, a Guerbert alcohol alkoxylate, such as those sold under the trade name Lutensol® (eg BASF AG), available in a variety of grades, preferably Lutensol XP-50, a hexyl alkyl glycoside, a linear alkyl benzene sulfonate, a lauryl dimethyl amine oxide and an alpha olefin sulfonate.
[063] The surfactant system can be used individually as a reinforcer, which comprises surfactant and a carrier (such as water) or can comprise from about 0.005 percent by weight to about 5.0 percent by weight of actives, preferably, about 0.01 percent by weight to about 3.0 percent by weight, and more preferably, about 0.05 percent by weight to about 1.0 percent by weight of actives such as part of a cleaning composition. Water
[064] The replenisher and cleaning compositions according to the invention may comprise water in amounts that vary depending on techniques for processing the composition.
[065]Water provides a medium that dissolves, suspends or transports the other components of the composition. Water can also function to distribute and wet the composition of the invention on an object.
[066] In some embodiments, water constitutes a large part of the composition of the invention and can be the balance of the composition in addition to the surfactant blend, alkalinity source, additional ingredients, and the like. The amount and type of water will depend on the nature of the composition as a whole, environmental storage, and method of application which includes the concentration composition, form of composition, and intended delivery method, among other factors. In particular, the carrier must be selected and used in a concentration that does not inhibit the effectiveness of the functional components in the composition of the invention for the intended use, eg bleaching, sanitizing, cleaning.
[067] In certain embodiments, the present composition includes about 5 to about 90% by weight of water, about 10 to about 80% by weight of water, about 20 to about 60%, by weight of water or about 30 to about 40% by weight of water. It will be understood that all values and ranges between those values are encompassed by the present invention. CLEANING COMPOSITIONS
[068] As noted above, the surfactant blend of the composition can be formulated as part of a cleaning composition that includes a source of alkalinity and/or acid. Alkalinity Source
[069]The cleaning composition includes an effective amount of one or more alkaline sources to enhance cleaning and improve dirt removal performance. In general, a concentrated cleaning composition is expected to include the alkaline source in an amount of at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, or at least about 25% by weight. To provide sufficient space for other components in the concentrate, the alkaline source can be provided in the concentrate in an amount less than about 75% by weight, less than about 60% by weight, or less than about 50% by weight. Weight. In another embodiment, the alkalinity source can be between about 0.1% and about 90% by weight, between about 0.5% and about 80% by weight, and between about 1% and about 60% by weight of the total weight of the cleaning composition. The alkalinity source is present in an amount sufficient to provide actives from 500 ppm to about 5000 ppm in an in-use composition.
[070] An effective amount of one or more alkaline sources should be considered as an amount that provides a composition in use that has a pH of at least about 8 and generally between about 9.5 and 13. When the composition is in use has a pH between about 8 and about 10, it can be considered moderately alkaline, and when the pH is greater than about 13, the composition in use can be considered caustic. In some circumstances, the cleaning composition can provide a composition of use that is useful at pH levels below about 8. In such compositions, the alkaline source can be omitted, and additional pH adjusting agents can be used to provide the composition to use at the desired pH.
[071] Examples of suitable alkaline sources of the cleaning composition include, but are not limited to, alkali metal carbonates and alkali metal hydroxides. Exemplary alkali metal carbonates that can be used include, but are not limited to: sodium or potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof. Exemplary alkali metal hydroxides that can be used include, but are not limited to, sodium, lithium or potassium hydroxide. The alkali metal hydroxide can be added to the composition in any manner known in the art, including as solid spheres, dissolved in an aqueous solution, or a combination thereof. Alkali metal hydroxides are commercially available as a solid in the form of solids or pellets having a mixture of particle sizes ranging from about 12 to 100 US mesh, or as an aqueous solution, as per example, as a 45% and 50% solution by weight. In one embodiment, the alkali metal hydroxide is added in the form of an aqueous solution, particularly a 50% by weight hydroxide solution, to reduce the amount of heat generated in the composition due to hydration of the solid alkaline material.
[072] In addition to the first alkalinity source, the cleaning composition may comprise a secondary alkalinity source. Examples of secondary alkaline sources include, but are not limited to: metal silicates such as sodium or potassium silicate or metasilicate; metal carbonates such as sodium or potassium carbonate, bicarbonate, sesquicarbonate; metal borates such as sodium or potassium borate; and ethanolamines and amines. Such alkalinity agents are commonly available in both aqueous and powder form, each useful for formulating the present cleaning compositions. The cleaning composition can be phosphorus free and/or nitrilotriacetic acid (NTA) free to meet certain standards. Phosphorus-free (also referred to as "phosphorus-free") means a concentrated composition that is less than about 0.5 by weight, more particularly less than about 0.1 by weight, and even more particularly less than about 0 0.01% by weight of phosphorus based on the total weight of the concentrate composition. NTA-free (also referred to as "NTA-free") means a concentrated composition that is less than about 0.5 by weight, less than about 0.1 by weight, and generally less than about 0.01% by weight. weight, of NTA based on the total weight of the concentrate composition. Source of Acidity
[073] The compositions of the invention may also be acidic in nature and may comprise at least one inorganic and/or organic acid in a sufficient amount such that the compositions of the invention have a pH of 4 or less. Generally, useful inorganic acids include water-soluble inorganic acids and minerals. Non-limiting examples of useful acids include hydrochloric acid, phosphoric acid, sulfuric acid, and so forth individually or in combination.
[074]As for organic acids, non-limiting examples include any known organic acid that can be considered effective in the inventive compositions. Generally, useful organic acids are those that include at least one carbon atom and include at least one carboxyl group (--COOH) in their structure. More specifically, useful organic acids contain from 1 to about 6 carbon atoms, have at least one carboxyl group, and are water-soluble. Non-limiting examples include acetic acid, chloroacetic acid, citric acid, formic acid, propionic acid, and so on. Additional Functional Materials
[075] Surfactant enhancer components or cleaning composition can be combined with various additional functional components. In some embodiments, the cleaning composition which includes the alkalinity source, acidity source, the surfactant system of the invention, and water constitutes a large amount, or even substantially the total weight of the cleaning composition, e.g. little or no additional functional material disposed on top of it. In such embodiments, the component concentration ranges provided above for the cleaning composition are representative of those fixed for those same components in the cleaning composition.
[076] Functional materials provide desired properties and functionality to the detergent composition. For the purpose of this application, the term "functional materials" includes a material which when dispersed or dissolved in a use and/or concentrated, such as an aqueous solution, provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are provided by way of example only, and that a wide variety of other functional materials can be used. For example, many of the functional materials discussed below refer to materials used in cleaning applications. However, other modalities may include functional materials for use in other applications. Additional surfactants
[077]The cleaning composition may contain an additional surfactant component which includes a detergent amount of an anionic surfactant or a mixture of anionic surfactants. Anionic surfactants are desirable in cleaning compositions because of their wetting, detergent properties, and often satisfactory membrane compatibility. Anionic surfactants that can be used in accordance with the invention include any anionic surfactant available in the cleaning industry. Suitable groups of anionic surfactants include sulfonates and sulfates. Suitable surfactants which may be provided in the anionic surfactant component include alkyl aryl sulfonates, secondary alkane sulfonates, alkyl methyl ester sulfonates, alpha olefin sulfonates, alkyl ether sulfates, alkyl sulfates and alcohol sulfates.
[078] Suitable alkyl aryl sulfonates that can be used in the cleaning composition can have an alkyl group that contains 6 to 24 carbon atoms and the aryl group can be at least one of benzene, toluene and xylene. A suitable alkyl aryl sulfonate includes linear alkyl benzene sulfonate. A suitable linear alkyl benzene sulfonate includes linear dodecyl benzyl sulfonate which can be provided as an acid which is neutralized to form the sulfonate. Additional suitable alkyl aryl sulfonates include xylene sulfonate and cumene sulfonate.
[079] Suitable alkane sulfonates that can be used in the cleaning composition can have an alkane group that has 6 to 24 carbon atoms. Suitable alkane sulfonates that can be used include secondary alkane sulfonates. A suitable secondary alkane sulfonate includes C14-C17 sodium secondary alkyl sulfonate commercially available as Hostapur SAS from Clariant.
[080] Suitable alkyl methyl ester sulfonates that can be used in the cleaning composition include those having an alkyl group containing 6 to 24 carbon atoms. Suitable alpha olefin sulfonates that can be used in the cleaning composition include those that have alpha olefin groups containing 6 to 24 carbon atoms.
[081] Suitable alkyl ether sulfates that can be used in the cleaning composition include those having between about 1 and about 10 repeating alkoxy groups, between about 1 and about 5 repeating alkoxy groups. In general, the alkoxy group will contain between about 2 and about 4 carbon atoms. A suitable alkoxy group is ethoxy. A suitable alkyl ether sulfate is sodium lauryl ether sulfate ethoxylate and is available under the name Steol CS-460.
[082] Suitable alkyl sulfates that can be used in the cleaning composition include those that have an alkyl group containing 6 to 24 carbon atoms. Suitable alkyl sulfates include, but are not limited to, sodium lauryl sulfate and sodium lauryl/myristyl sulfate.
[083] Suitable alcohol sulfates that can be used in the cleaning composition include those that have an alcohol group containing about 6 to about 24 carbon atoms.
[084] In a preferred embodiment, the co-surfactant component is a lower chain material, preferably less than 12 carbons and most preferably from about 6 to about 10 carbons. The inventive surfactant and any optional co-surfactant combination replace NPE on a 1:1 basis at the asset level.
[085]The anionic surfactant can be neutralized with an alkali metal salt, an amine, or a mixture thereof. Suitable alkali metal salts include sodium, potassium and magnesium. Suitable amines include monoethanolamine, triethanolamine and monoisopropanolamine. If a mixture of salts is used, a suitable mixture of alkali metal salt can be sodium and magnesium, and the molar ratio of sodium to magnesium can be between about 3:1 and about 1:1.
[086] The cleaning composition, when provided as a concentrate, may include the surfactant component in an amount sufficient to provide a composition of use that has desired wetting and detergent properties upon dilution with water. The concentrate may contain about 0.1 wt% to about 0.5 wt% about 0.1 wt% to about 1.0 wt about 1.0% , by weight, to about 5% by weight, to about 5% by weight, to about 10% by weight, to about 10% by weight, to about 20% by weight, 30%, by weight, about 0.5% by weight, to about 25, by weight, and about 1%, by weight, to about 15, by weight, and similar intermediate concentrations of the anionic surfactant.
[087]The cleaning composition may contain an additional nonionic co-surfactant component which includes a detergent amount of an additional nonionic surfactant or a mixture of nonionic surfactants. Non-ionic surfactants can be included in the cleaning composition to improve grease removal properties. Although the additional co-surfactant component may include a non-ionic surfactant component, it should be understood that the non-ionic co-surfactant component may be excluded from the cleaning composition.
[088] Nonionic surfactants that can be used in the composition include polyalkylene oxide surfactants (also known as polyoxyalkylene or polyalkylene glycol surfactants). Suitable polyalkylene oxide surfactants include polyoxypropylene surfactants and polyoxyethylene glycol surfactants. Suitable surfactants of this type are synthetic organic polyoxypropylene (PO)-polyoxyethylene (EO) block copolymers. These surfactants include a diblock polymer comprising an EO block and a PO block, a central block of polyoxypropylene (PO) units, and have polyoxyethylene blocks grafted onto the polyoxypropylene unit or a central block of EO with fixed PO blocks. Furthermore, this surfactant may have additional blocks of both polyoxyethylene and polyoxypropylene in the molecules. A suitable weight average molecular range of useful surfactants can be about 1,000 to about 40,000 and the weight percentage of ethylene oxide content can be about 10 to 80% by weight.
[089]Additional nonionic surfactants include alcohol alkoxylates. A suitable alcohol alkoxylate includes linear alcohol ethoxylates such as Tomadol™ 1-5 which is a surfactant containing an alkyl group having 11 carbon atoms and 5 moles of ethylene oxide. Additional alcohol alkoxylates include alkylphenol ethoxylates, branched alcohol ethoxylates, secondary alcohol ethoxylates (eg Tergitol 15-S-7 from Dow Chemical), castor oil ethoxylates, alkylamine ethoxylates, tallow amine ethoxylates , fatty acid ethoxylates, sorbital oleate ethoxylates, terminated ethoxylates, or mixtures thereof. Additional nonionic surfactants include amides such as fatty alkanolamides, alkyldiethanolamides, coconut diethanolamide, lauramide diethanolamide, cocoamide diethanolamide, polyethylene glycol cocamide (eg, PEG-6 cocamide), oleic diethanolamide, or mixtures thereof. Additional suitable nonionic surfactants include polyalkoxylated aliphatic base, polyalkoxylated amide, glycol esters, glycerol esters, amine oxides, phosphate esters, alcohol phosphate, fatty triglycerides, fatty triglyceride esters, alkyl ether phosphate, esters ethoxylated alkyl phenol phosphate esters, alkyl polysaccharides, block copolymers, alkyl glycosides, or mixtures thereof.
[090] When nonionic surfactants are included in the cleaning composition concentrate, they may be included in an amount of at least about 0.1% by weight and may be included in an amount of up to about 15% , by weight. The concentrate may include about 0.1 to 1.0% by weight, about 0.5% by weight, to about 12% by weight, or about 2% by weight to about 10 % by weight of non-ionic surfactant.
[091] Amphoteric surfactants can also be used to provide desired detergent properties. Suitable amphoteric surfactants that can be used include, but are not limited to: betaines, imidazolines and propionates. Suitable amphoteric surfactants include, but are not limited to: sultaines, amphopropionates, amphodipropionates, aminopropionates, aminodipropionates, amphoacetates, amphodiacetates and amphohydroxypropylsulfonates.
[092] When the cleaning composition includes an amphoteric surfactant, the amphoteric surfactant may be included in an amount from about 0.1% by weight to about 15% by weight. The concentrate may include about 0.1 wt% to about 1.0 wt%, 0.5 wt% to about 12 wt%, or about 2 wt%. , to about 10% by weight of the amphoteric surfactant. Bleaching Agents
[093] The cleaning composition may also include bleaching agents to lighten or whiten a substrate. Examples of suitable bleaching agents include bleaching compounds capable of releasing an active halogen species, such as CI2, Br2, -OCl- and/or -OBr-, under conditions typically encountered during the cleaning process. Suitable bleaching agents for use in the present cleaning compositions include, for example, chlorine containing compounds such as a chlorine, a hypochlorite and chloramine. Exemplary halogen releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochloramine and dichloramine, and the like. Encapsulated chlorine sources can also be used to increase the stability of the chlorine source in the composition (see, for example, US Patent Nos. 4,618,914 and 4,830,773, the descriptions of which are incorporated herein by reference to all purposes). A bleaching agent can also be a source of peroxygen or active oxygen such as hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrate, potassium permonosulphate, and sodium perborate mono and tetrahydrate, with and without activators such as tetra-acetylethylene diamine, and the like. The composition can include an effective amount of a bleaching agent. When the concentrate includes a bleaching agent, it may be included in an amount of from about 0.1% by weight to about 60% by weight about 1% by weight to about 20%. by weight about 3% by weight to about 8% by weight and about 3% by weight to about 6% by weight.
[094] The cleaning composition can include an effective amount of cleaning fillers, which does not act as a cleaning agent per se, but cooperates with the cleaning agent to increase the overall cleaning ability of the composition. Examples of suitable cleaning fillers for use in the present cleaning compositions include sodium sulfate, sodium chloride, starch, sugars, C1-C10 alkylene glycols such as propylene glycol, and the like. When the concentrate includes a cleaning charge, it can be included in an amount between about 1% by weight and about 20% by weight and between about 3% by weight and about 15% , by weight. Stabilizing Agents
[095] Stabilizing agents that can be used in the cleaning composition include, but are not limited to: primary aliphatic amines, betaines, borate, calcium ions, sodium citrate, citric acid, sodium formate, glycerin, malonic acid, organic diacids, polyols, propylene glycol, and mixtures thereof. The concentrate need not include a stabilizing agent, however when the concentrate includes a stabilizing agent, it may be included in an amount that provides the desired level of stability in the concentrate. Exemplary ranges of the stabilizing agent include up to about 20% by weight, between about 0.5% by weight, to about 15% by weight, and between about 2% by weight to about 10 % by weight. Dispersants
[096] Dispersants that can be used in the cleaning composition include maleic acid/olefin copolymers, polyacrylic acid and its copolymers, and mixtures thereof. The concentrate need not include a dispersant, however, when a dispersant is included it may be included in an amount that provides the desired dispersant properties. Exemplary ranges of dispersant in the concentrate can be up to about 20% by weight, between about 0.5% by weight and about 15% by weight, and between about 2% by weight, and about 9% by weight. Weight. Hydrotropes
[097] Compositions of the invention may optionally include a hydrotrope that aids in compositional stability and aqueous formulation. Functionally speaking, suitable hydrotrope couplers that may be employed are non-toxic and maintain the active ingredients in the aqueous solution over the range of temperature and concentration to which a concentrate or any use solution is exposed.
[098]Any hydrotrope coupler can be used, as long as it does not react with the other components of the composition or negatively affect the performance properties of the composition. Representative classes of hydrotropic coupling agents or solubilizers that may be employed include anionic surfactants such as alkyl sulfates and alkane sulfonates, alkyl benzene or naphthalene sulfonates, secondary alkane sulfonates, alkyl ether sulfates or sulfonates, phosphates or phosphonates of alkyl, dialkyl sulfosuccinic acid esters, sugar esters (eg sorbitan esters), amine oxides (mono-, di- or tri-alkyl) and C8-C10 alkyl glycosides. Preferred coupling agents for use in the present invention include n-octane sulfonate, available as NAS 8D from Ecolab Inc., n-octyl dimethylamine oxide, and commonly available aromatic sulfonates such as alkyl benzene sulfonates (e.g., sulfonates of xylene) or naphthalene sulfonates, aryl or alkaryl phosphate esters or their alkoxylated analogues having 1 to about 40 ethylene, propylene or butylene oxide units or mixtures thereof. Other preferred hydrotropes include nonionic surfactants of C6-C24 alcohol alkoxylates (alkoxylate means ethoxylates, propoxylates, butoxylates and co- or terpolymer mixtures thereof) (preferably C6-C14 alcohol alkoxylates) having 1 to about 15 groups of alkylene oxide (preferably about 4 to about 10 alkylene oxide groups); C6-C24 alkylphenol alkoxylates (preferably, C8-C10 alkylphenol alkoxylates) having 1 to about 15 alkylene oxide groups (preferably, about 4 to about 10 alkylene oxide groups); C6-C24 alkylpolyglycosides (preferably, C6-C20 alkylpolyglycosides) having 1 to about 15 glycoside groups (preferably about 4 to about 10 glycoside groups); C6-C24 fatty acid ester ethoxylates, propoxylates or glycerides; and C4-C12 mono or dialkanolamides. A preferred hydrotrope is sodium cumene sulfonate (SCS).
[099] The composition of an optional hydrotrope can be present in the range of from about 0 to about 25 percent by weight.
[0100]Water conditioning agents work to inactivate water hardness and prevent calcium and magnesium ions from interacting with dirt, surfactants, carbonate and hydroxide. Water conditioning agents therefore improve detergency and prevent long-term effects such as insoluble dirt redeposition, mineral scales and mixtures thereof. Water conditioning can be achieved by different mechanisms including sequestration, precipitation, ion exchange and dispersion (threshold effect).
[0101]Water conditioning agents that can be used include water soluble inorganic water conditioning agents, water insoluble inorganic water conditioning agents, water soluble organic conditioning agents and water insoluble water conditioning agents Organic. Exemplary inorganic water-soluble water conditioning agents include all physical forms of alkali metal, ammonium and substituted ammonium salts of carbonate, bicarbonate and sesquicarbonate; condensed pyrophosphates and polyphosphates, such as tripolyphosphate, trimetaphosphate and ring-opened derivatives; and glassy polymeric metaphosphates of general structure Mn+2Pn03n+1 which have a degree of polymerization n from about 6 to about 21 in anhydrous or hydrated forms; and mixtures thereof. Exemplary inorganic water-insoluble water conditioning agents include aluminosilicate enhancers. Exemplary water-soluble water conditioning agents include aminopolyacetates, polyphosphonates, aminopolyphosphonates, carboxylates and short-chain polycarboxylates. Organic water-soluble water conditioning agents useful in the compositions of the present invention include aminopolyacetates, polyphosphonates, aminopolyphosphonates, short-chain carboxylates and a wide variety of polycarboxylate compounds.
[0102] Suitable aminopolyacetate water conditioning salts for use herein include the sodium, lithium potassium, ammonium and substituted ammonium salts of the following acids: ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediamine triacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid; and mixtures thereof. Polyphosphonates useful herein specifically include the sodium, lithium and potassium salts of ethylene diphosphonic acid; sodium, lithium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and lithium, potassium, ammonium and substituted ammonium salts of ethane-2-carboxylic acid-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-1-hydroxy-1,1,2-tridiphosphonic acid, ethane-2-hydroxy-1,1,2-tridiphosphonic acid, propane-1,1,3,3-tetradiphosphonic acid, propane-1 ,1,2,3-tetraphosphonic and 1,2,2,3-tetradiphosphonic acid propane; and mixtures thereof. Examples of such polydiphosphonic compounds are disclosed in Patent No. GB 1,026,366. For further examples, see US Patent No. 3,213,030 to Diehl, issued October 19, 1965 and US Patent No. 2,599,807 to Bersworth, issued June 10, 1952. Aminopolyphosphonate compounds are excellent water conditioning agents and can be advantageously used in the present invention. Suitable examples include soluble salts, for example sodium, lithium or potassium salts, of diethylene thiamine pentamethylene diphosphonic acid, ethylene diamine tetramethylene diphosphonic acid, hexamethylenediamine tetramethylene diphosphonic acid and nitrilotrimethylene diphosphonic acid; and mixtures thereof. Water-soluble short-chain carboxylic acid salts are another class of water conditioner for use herein. Examples include citric acid, gluconic acid and phytic acid. Preferred salts are prepared from alkaline metal ions such as sodium, potassium, lithium and from ammonium and substituted ammonium. Suitable water soluble polycarboxylate water conditioners for this invention include the various ether polycarboxylates, polyacetals, polycarboxylates, epoxy polycarboxylates, and aliphatic, cycloalkane and aromatic polycarboxylates. Enzymes
[0103]Enzymes can be used to catalyze and facilitate organic and inorganic reactions. It is well known, for example, that enzymes are used in the metabolic reactions that take place in animal and plant life.
[0104] Enzymes that can be used according to the invention include simple proteins or conjugated proteins produced by living organisms and that function as biochemical catalysts that, in cleaning technology, degrade or alter one or more types of dirt residues found in surfaces of food processing equipment thereby removing dirt or making the dirt more removable by the cleaning system. Both degradation and alteration of dirt residues improve detergency by reducing the physicochemical forces that bind the dirt to the surface being cleaned, ie the dirt becomes more water-soluble. The enzyme can be functional in the acidic, neutral or alkaline pH range.
[0105]As defined in the art, enzymes are referred to as simple proteins when they require only their protein structures for catalytic activity. Enzymes are described as conjugated proteins if they require a non-protein component for activity, called a cofactor, which is a metal or an organic biomolecule often referred to as a coenzyme. Cofactors are not involved in enzyme function catalytic events. Rather, its role appears to be to keep the enzyme in an active configuration. Depending on the use in question, enzymatic activity refers to the ability of an enzyme to perform the desired catalytic function of degrading or altering dirt; and enzyme stability refers to the ability of an enzyme to remain or be maintained in the active state.
[0106]Enzymes are extremely effective catalysts. In practice, very small amounts will accelerate the rate of degradation and dirt alteration reactions without them being consumed in the process. Enzymes also have substrate specificity (dirt) that determines the magnitude of their catalytic effect. Some enzymes interact with only a specific substrate molecule (absolute specificity); while other enzymes have broad specificity and catalyze reactions in a family of structurally similar molecules (group specificity).
[0107] Enzymes exhibit catalytic activity due to three general characteristics: the formation of a non-covalent complex with the substrate, the substrate specificity and the catalytic rate. Many compounds can bind to an enzyme, however, only certain types will lead to the subsequent reaction. The latter are called substrates and satisfy the particular enzyme specificity requirement. Materials that bind, however, do not chemically react can affect the enzymatic reaction in a positive or negative way. For example, unreacted species called inhibitors disrupt enzyme activity.
[0108]Several enzymes can fit into more than one class. A valuable reference on enzymes is "Industrial Enzymes", Scott, D., in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, (editors Grayson, M. and EcKroth, D.) Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980. The disclosure of that reference relating to enzymes is incorporated herein by reference.
[0109] Proteases, a subclass of hydrolases, are further divided into three distinct subgroups that are grouped by optimal pH (ie, optimal enzyme activity over a given pH range). These three subgroups are the alkaline, neutral and acid proteases. These proteases can be derived from plant, animal or microorganism origin; but preferably they are of the latter origin which includes yeasts, molds and bacteria. Examples of suitable alkaline proteases are Alcalase®, Savinase® and Esperase® all available from Novo Industri AS, Denmark; Purafect® from Genencor International; Maxacal®, Maxapem® and Maxatase® all available from Gist-Brocase International NV, The Netherlands; Optimase® and Opticlean® from Solvay Enzymes, USA and so on.
[0110] Commercial alkaline proteases are obtainable in liquid or dry form, are sold as crude aqueous solutions or in assorted purified composite and processed forms, and are comprised of from about 2% to about 80% by weight of active enzyme generally in combination with stabilizers, buffers, cofactors, impurities and inert vehicles. The actual active enzyme content depends on the manufacturing method and is not critical, assuming the cleaning solution has the desired enzyme activity. The particular enzyme chosen for use in the process and the products of this invention depend on the end-use conditions, which include the physical product form, pH of use, temperature of use and types of soils to be degraded or altered. The enzyme can be chosen to provide optimal activity and stability for any given set of utility conditions.
[0111]Of course, mixtures of different proteolytic enzymes can be used. Although a number of specific enzymes have been described above, it is to be understood that any protease which can impart the desired proteolytic activity to the composition can be used and in that embodiment of this invention it is in no way limited to the specific choice of proteolytic enzyme.
[0112] In addition to proteases, it should also be understood, and a person skilled in the art will observe from the above enumeration, that other enzymes that are well known in the art can also be used with the composition of the invention. Other hydrolases are included, such as esterases, carboxylases and the like; and other classes of enzyme.
[0113] Furthermore, in order to increase its stability, the enzyme or enzyme mixture can be incorporated into various non-liquid embodiments of the present invention as a coated, encapsulated, agglomerated, pelletized or marumerized form. Also, to enhance stability, the enzyme or enzyme mixture can be incorporated into various non-aqueous embodiments, such as propylene glycol, glycerin, etc. pH Adjusting Agents
[0114]Various pH adjusting agents can be used to alter the pH of the treatment composition. pH adjusting agents can provide desired buffering systems. Exemplary alkaline pH adjusting agents include carbonate, bicarbonate, sodium hydroxide, tetraborate and boric acid. A buffer system that includes carbonate and bicarbonate can provide an exemplary pH of between about 9 and about 10, a buffer system that includes carbonate and sodium hydroxide can provide an exemplary pH of between about 9 and about 11, and a buffer system that includes sodium tetraborate and boric acid can include a pH between about 7.6 and about 9.2. The pH adjustment agent can include an acid to provide an acidic buffer system. Exemplary acids include citric acid, citrate, acetic acid, acetate, phosphoric acid and phosphate. For example, a buffer system including citric acid and sodium hydroxide can provide an exemplary pH of between about 2.2 and about 6.5, a buffer system that includes sodium citrate and citric acid can provide an exemplary pH of between about 2.2 and about 6.5. from about 3.0 to about 6.2, a buffer system that includes sodium acetate and acetic acid can provide an exemplary pH of between about 3.6 and about 5.6, and a buffer system that includes phosphate of sodium dihydrogen and disodium dihydrogen phosphate can provide an exemplary pH of between about 5.8 and about 8.0. Cleaning on site
[0115] The membrane cleaning compositions and methods of the invention generally consist of on-site cleaning systems (CIP), off-site cleaning systems (COP), textile washing machines, osmosis filtration systems micro, ultra, nano and reverse. COP systems can include readily accessible systems including wash tanks, dip pans, mop buckets, holding tanks, scrub sinks, vehicle parts washers, non-continuous batch washers and systems, and the like. CIP systems include the internal components of tanks, lines, pumps and other process equipment typically used to process liquid product streams such as beverages, milk and juices.
[0116] In general, cleaning of the system on site or other surface (ie, removal of unwanted products on it) is performed with an alkaline cleaning that is introduced with heated water. The compositions of the invention can be introduced during, before, or simultaneously with the cleaning step (as a separate enhancer or as part of the cleaning composition) and are applied or introduced into the system in a concentration of use solution in unheated water in room temperature. Typically, CIP employs flow rates on the order of about 40 to about 600 liters per minute, temperatures from room temperature to about 70°C, and contact times of at least about 10 seconds, for example, about from 30 to about 120 seconds. The present composition may remain in solution in cold water (eg 40°F/4°C) and in warm water (eg 140°F/60°C). Although it is not normally necessary to heat the aqueous use solution of the present composition, under some circumstances heating may be desirable to enhance its activity. These materials are useful at any conceivable temperatures. Membrane Treatment Programs
[0117] Several different treatment programs can be used to treat a membrane according to the invention. The method of treating a membrane can include a plurality of steps. A first step may be referred to as a product removal or displacement step where product (whey, milk, etc.) is removed from the filtration system. The product can be effectively recovered and used as opposed to discharge as plant effluent. In general, the product removal step can be characterized as an exchange step where water, gas or multi-phase flow displaces the product from the membrane system. The product removal step can last as long as product removal and recovery from the filtration system lasts. In general, the product removal step is expected to take at least a few minutes for most dairy filtration systems.
[0118]Another commonly used step may be referred to as a pre-rinse step. In general, water and/or an alkaline solution can be circulated through the filtration system to remove heavy dirt. It should be understood that a large scale filtration system refers to an industrial system having at least about 10 membrane containers, at least about 40 membranes, and a total membrane area of about 200 m2. Industrial filtration systems for use in dairy and brewery applications generally include about 10 to about 200 membrane containers, about 40 to about 1,000 membranes, and a total membrane area of about 200 m2 to about 10,000 m2.
[0119]Several cycles of chemical treatment can be repeated for acid treatment, alkaline treatment and neutral treatment. In general, the various treatments may or may not have an enzyme.
[0120]The liquid component can be provided as an alkaline treatment, an acid treatment, a neutral treatment, a solvent treatment and/or as an enzymatic treatment.
[0121] By way of example, the surfactant system of the invention can be used in several steps in the filter cleaning process. For example, rinsing can be carried out by the surfactant composition of the invention alone or as a neutral, acidic or alkaline solution. Cleaning may be carried out using a cleaning composition which may include alkaline components, acids, enzymes, non-aqueous components and/or the surfactant composition of the invention. Sanitization and/or preservation can be accomplished by a composition that includes chlorine, acids, peracids and/or reducing compositions. In general, a penetrant is considered to be a component that penetrates dirt and softens the dirt for removal. The penetrant can be selected by the particular type of dirt expected on the membrane. In the case of membranes used in the dairy industry, it is expected that the penetrant will be selected to provide penetration into protein and lipid soils. Formation of a concentrate
[0122] The concentrate composition of the present invention may be provided as a solid, liquid or gel, or a combination thereof. In one embodiment, the cleaning compositions can be provided as a concentrate so that the cleaning composition is substantially free of any added water or the concentrate can contain a nominal amount of water. The concentrate can be formulated without any water or it can be provided with a relatively small amount of water in order to reduce the expense of transporting the concentrate. For example, the concentrate composition may be provided as a capsule or compressed powder pellet, a solid, or free-flowing powder, whether contained by a water-soluble material or not. In the case of providing the capsule or pellet of the composition in a material, the capsule or pellet may be introduced into a volume of water, and if present, the water-soluble material may solubilize, degrade or disperse to allow contact of the concentrate composition with the water. For purposes of this disclosure, the terms "capsule" and "pellet" are used for exemplary purposes and are not intended to limit the mode of delivery of the invention to a particular format.
[0123] When provided as a liquid concentrate composition, the concentrate can be diluted through dispensing equipment using aspirators, peristaltic pumps, gear pumps, mass flow meters, and the like. This modality of liquid concentrate can also be distributed in bottles, jars, dosing bottles, bottles with dosing caps, and the like. The liquid concentrate composition can be loaded into a multi-chambered cartridge insert which is then placed in a spray bottle or any delivery device loaded with a pre-measured amount of water.
[0124] In yet another embodiment, the concentrate composition can be provided in a solid form that resists crumbling or other degradation until it is placed in a container. Such a container may be charged with water prior to placing the concentrate composition in the container, or it may be charged with water after the concentrate composition is placed in the container. In either case, the solid concentrate composition dissolves, solubilizes, or otherwise disintegrates upon contact with water. In a particular embodiment, the solid concentrate composition dissolves quickly, thus allowing the concentrate composition to become a wearable composition and further allowing the end user to apply the wearable composition to a surface in need of cleaning . When the cleaning composition is provided as a solid, the compositions provided above can be altered so as to solidify the cleaning composition by any means known in the art. For example, the amount of water can be reduced or additional ingredients can be added to the cleaning composition, such as a solidifying agent.
[0125] In another modality, the solid concentrate composition can be diluted through a dispensing equipment whereby water is sprinkled on the solid block forming the use solution. Water flow is distributed at a relatively constant rate using mechanical, electrical or hydraulic controls, and the like. The solid concentrate composition can also be diluted through dispensing equipment whereby water flows around the solid block, creating a use solution as the solid concentrate dissolves. The solid concentrate composition can also be diluted through pellet, tablet, powder and paste dispensers, and the like.
[0126]The water used to dilute the concentrate (dilution water) may be available at the locality or dilution site. Dilution water can contain varying levels of hardness depending on the location. Service water available from various municipalities has varying levels of hardness. It is desired to provide a concentrate that can handle the hardness levels found in the service water of various municipalities. The dilution water that is used to dilute the concentrate can be characterized as hard water when it includes at least a hardness of 1 grain. It is expected that the dilution water can include at least a 5 grain hardness, at least a 10 grain hardness, or at least a 20 grain hardness.
[0127] The concentrate is expected to be diluted with the dilution water in order to provide a use solution having a desired level of detergent properties. If it is necessary for the use solution to remove stubborn or heavy soils, it is expected that the concentrate can be diluted with the dilution water in a weight ratio of at least 1:1 and up to 1:8. If a light duty cleaning use solution is desired, it is expected that the concentrate can be diluted to a weight ratio of concentrate to dilution water of up to about 1:256.
[0128] In an alternative embodiment, the cleaning compositions can be provided as a ready-to-use (RTU) composition. If the cleaning composition is provided as an RTU composition, a more significant amount of water is added to the cleaning composition as a diluent. When the concentrate is provided as a liquid, it may be desired to provide it in a flowable form so that it can be pumped or aspirated. It has been found that it is often difficult to precisely pump a small amount of a liquid. It is generally more effective to pump a larger amount of a liquid. Correspondingly, while it is desirable to provide the concentrate with as little water as possible in order to reduce transportation costs, it is also desirable to provide a concentrate that can be accurately dispensed. In the case of a liquid concentrate, water is expected to be present in an amount of up to about 90% by weight, particularly between about 20% by weight, and about 85% by weight, more particularly between about 30% by weight and about 80% by weight, and most particularly between about 50% by weight and about 80% by weight.
[0129] In the case of an RTU composition, it should be noted that the cleaning composition disclosed above may, if desired, be further diluted with up to about 96% by weight of water, based on the weight of the composition of cleaning.
[0130]The cleaning composition can be produced using a blending process. The surfactant enhancing composition and/or cleaning composition comprising the same and other functional ingredients are mixed for a sufficient amount of time to form a final homogeneous composition. In an exemplary embodiment, the components of the cleaning composition are mixed for approximately 10 minutes.
[0131] A solid cleaning composition as used in the present disclosure encompasses a variety of forms including, for example, solids, pellets, blocks, tablets and powders. By way of example, pellets can have diameters between about 1 mm and about 10 mm, tablets can have diameters between about 1 mm and about 10 mm or between about 1 cm and about 10 cm, and blocks can have diameters of at least about 10 cm. It is to be understood that the term "solid" refers to the state of the cleaning composition under the expected conditions of storage and use of the solid cleaning composition. In general, the cleaning composition is expected to remain a solid when supplied at a temperature of up to about 37.77°C (100°F) or less than about 48.88°C (120°F).
[0132] In certain embodiments, the solid cleaning composition is provided as a unit dose. A unit dose refers to a unit of solid cleaning composition sized so that the entire unit is used during a single cycle. When the solid cleaning composition is provided as a unit dose, it can have a mass of from about 1 g to about 50 g. In other embodiments, the composition can be a solid, pellet or tablet having a size from about 50g to 250g, about 100g or larger, or about 40g to about 11,000g.
[0133] In other embodiments, the solid cleaning composition is provided in the form of a multi-use solid, such as a block or a plurality of pellets, and can be repeatedly used to generate aqueous cleaning compositions for multiple wash cycles. . In certain embodiments, the solid cleaning composition is provided as a solid having a mass from about 5 g to about 10 kg. In certain embodiments, a multi-use form of the solid cleaning composition has a mass of from about 1 to about 10 kg. In other embodiments, a multi-use form of the solid cleaning composition has a mass from about 5 kg to about 8 kg. In other embodiments, a multi-use form of the solid cleaning composition has a mass of from about 5 g to about 1 kg, or from about 5 g to about 500 g.
[0134]Components can be mixed and extruded or cast to form a solid such as pellets, powders or blocks. Heat can be applied from an external source to facilitate the processing of the mixture.
[0135] A mixing system provides for a continuous mixing of ingredients in high shear to form a substantially homogeneous liquid or semi-solid mixture in which the ingredients are distributed throughout its mass. The mixing system includes means for mixing the ingredients so as to provide effective shear to maintain the mixture in a flowable consistency, with a viscosity during processing of about 1,000 to 1,000,000 cP, preferably about 50,000 to 200,000 cP. The mixing system can be a continuous flow mixer or a single or double screw extruder apparatus.
[0136]The mixture can be processed at a temperature to maintain the physical and chemical stability of the ingredients, such as at ambient temperatures of about 20 to 80°C, and about 25 to 55°C. Although limited external heat can be applied to the mixture, the temperature reached by the mixture can become elevated during processing due to friction, variances in ambient conditions, and/or an exothermic reaction between the ingredients. Optionally, the temperature of the mixture can be increased, for example, at the inlets or outlets of the mixing system.
[0137] An ingredient may be in the form of a liquid or a solid, such as a dry particulate, and may be added to the mixture separately or as part of a premix with another ingredient, such as the control component of scale can be separated from the rest of the cleaning composition. One or more premixes can be added to the mix.
[0138]The ingredients are mixed to form a substantially homogeneous consistency in which the ingredients are substantially evenly distributed throughout the dough. The mixture can be discharged from the mixing system through a mold or other shaping means. The profiled extrudate can be divided into useful sizes with a controlled mass. The extruded solid can be wrapped in film. The temperature of the mixture when discharged from the mixing system can be low enough to allow the mixture to be melted or extruded directly into a packaging system without first cooling the mixture. The time between extrusion discharge and packaging can be adjusted to allow the cleaning block to harden for better handling during processing and additional packaging. Mixing at the discharge point can be about 20 to 90°C, and about 25 to 55°C. The composition can be allowed to harden to a solid form which can range from a low density, sponge-like, malleable, caulking consistency to a high density, cast solid, concrete-like block.
[0139]Optionally, heating and cooling devices can be mounted adjacent to the mixing apparatus to apply or remove heat to obtain a desired temperature profile in the mixer. For example, an external heat source that can be applied to one or more drum sections of the mixer, such as the ingredient input section, the final output section, and the like, to increase the fluidity of the mix during processing. Preferably, the temperature of the mixture during processing, including at the discharge port, is preferably maintained at about 20 to 90°C.
[0140]When the processing of the ingredients is complete, the mixture can be discharged from the mixer through a discharge die. The solidification process can last from a few minutes to about six hours, depending, for example, on the size of the melted or extruded composition, the ingredients of the composition, the temperature of the composition, and other similar factors. Preferably, the molten or extruded composition "sets" or begins to harden to a solid form within about 1 minute to about 3 hours, preferably about 1 minute to about 2 hours, most preferably, about 1 minute to about 1.0 hour.
[0141]The concentrate can be provided in the form of a liquid. Various liquid forms include gels and pastes. Naturally, when the concentrate is provided in the form of a liquid, it is not necessary to harden the composition to form a solid. In fact, the amount of water in the composition is expected to be sufficient to prevent solidification. In addition, dispersants and other components can be incorporated into the concentrate in order to maintain a desired distribution of components.
[0142] In certain embodiments, the cleaning composition can be mixed with a water source before or at the point of use. In other embodiments, cleaning compositions do not require the formation of a wearing solution and/or further dilution and can be used without further dilution.
[0143] In aspects of the invention employing solid cleaning compositions, a source of water contacts the cleaning composition to convert solid cleaning compositions, particularly powders, into use solutions. Additional dispensing systems that are more suitable for converting alternative soda cleaning compositions into in-use solutions can also be used. The methods of the present invention include the use of a variety of solid cleaning compositions, including, for example, extruded blocks or "capsule" packaging types
[0144] In one aspect, a dispenser can be employed to spray water (eg in a spray pattern from a nozzle) to form a cleaning use solution. For example, water can be sprayed towards an apparatus or other containment vessel with the cleaning composition, wherein the water reacts with the solid cleaning composition to form the wearing solution. In certain embodiments of the methods of the invention, a use solution may be configured to drip downward due to the action of gravity until the dissolved solution of the cleaning composition is dispensed for use in accordance with the invention. In one aspect, the use solution can be dispensed into a wash solution from a utensil washing machine. EXAMPLES Purpose/Fundamentals:
[0145] The purpose of this invention was to find a suitable replacement for the surfactant of nonyl phenol ethoxylate (NPE 9.5) and tridecyl alcohol ethoxylate (TDA-9), also known as Ultrasil 01 (U01) and Ultrasil 06 ( U06), respectively. Surfactants and polymers are used as a membrane cleaning adjunct to improve removal of grease, protein and other dirt and, in some cases, improve wettability or permeation properties. Other considerations for successful replacement chemistry are good rinsing characteristics, low foaming, good cleaning properties of stainless steel, and relatively low costs.
[0146] This change is necessary due to environmental concerns of the Environmental Protection Agency (EPA) regarding the use of ethoxylated alkyl phenols (APEs). TDA-9 (U06) was an attempt to replace NPE 9.5 (U01) in the Ultrasil product line with cleaning process membrane systems, but growing consumer questions and supporting data suggested some negative effects on membrane performance. when replacing NPE 9.5 with TDA-9. Initial questions were confined to ultrafiltration (UF) brine systems using polyvinylidene fluoride (PVDF) membranes, but more recent questions have also pointed to problems with milk and whey UF systems using polyether sulfone (PES) membranes. The questions are related to how the membrane works or flows during production after being cleaned with a particular surfactant. Production performance after a particular cleaning sequence likely needs to do membrane cleaning, the amount of cleaning components that soil the membrane due to poor rinsing, surface modification of the membrane to achieve a more hydrophilic surface that reduces attraction of hydrophobic solids . Procedure: Membrane and Rinse Performance
[0147] Surfactant candidates for NPE 9.5 replacement were evaluated in the following categories: Membrane Production Performance, Rinsing Characteristics, Foaming, Cleaning and Costs. A smooth membrane sheet tester was used to evaluate surfactants and polymers and document the interaction with various types of membrane. Initially, all surfactant concentrations were tested at 0.6% w/w active surfactant. Typically, this concentration is the highest of recommendations used in the field of application and was used to create the worst case scenario for rinsing membrane surfactants.
[0148]The following information compares the rinse and production data of the flat sheet equipment to an exemplary production membrane system. As the data indicate, it is difficult to minimize the rinse volume with water per membrane area to match the rinse volume per membrane area of a production system due to differences in equipment setup, membrane area, and retention volumes associates. This is why the protocol requires occasional short rinse cycles to ensure that the effect of the surfactant solution on membrane performance is properly evaluated.Flat Sheet Tester Information:• Each membrane sheet = 0.018 m2• Area per permeate plate (must have two sheets of membrane) = 0.036 m2• Rinse volume (Minimum Rinse) 3 min @ 4 Hz pump speed = 2.5 L = 69 L/m2 = 18.3 gal/ m2• Rinse volume (Maximum Rinse) 10 min2 @ 9-10 Hz pump speed = 13.0 L = 361 L/m2 = 95.4 gal/m2Exemplary Production System• 3.8" element = 7.2 m2 • 100 elements = 720 m2 • CIP retention volume = 1,134 liters (300 gal) • 3 X rinse retention volume = 3,402 liters (900 gal) • Estimated rinse per membrane area = 1.25 gal/m2 = 4 .7 L/m2
[0149] The Membrane Production Performance test and was performed in a flat sheet membrane apparatus at 26.66°C (80°F), 18 Hz pump speed, 0.27 MPa (40 psig) in, 0.20 MPa (30 psig) out. The steps for testing are outlined in Table 1. The first step is to wash or condition the membrane with Ultrasil 110 that contains no surfactants at a pH of 11.0 to 11.1 for a period of 10 minutes under the conditions listed in the table. After the alkaline wash conditioning step, the DI water rinse step is followed by a cleaning water flow (CWF) reading. Reading CWF is important at this step to ensure the membrane does not become dirty from previous tests and is flowing within specifications for the particular membrane. Generally, there is a +/- 20% range for CWFs per manufacturer's specifications. For this protocol, the CWF was expected to be +/-10% in order to conclude that the surfactant or polymer was adequately rinsed and was not fouling the membrane. The next step involves treating the membrane with an active surfactant solution at 0.6% w/pa 18 Hz, 47.77°C (118°F), 0.17 MPa (25 psig) in, 0.10 MPa (15 psig) out and pH 11.0 to 11.1 using Ultrasil 110 (no surfactant). This alkaline/surfactant solution is allowed to circulate under the conditions set forth above for 20 minutes and the flow is measured at 10 and 20 minutes. The flux measurements serve two purposes, first to ensure that the membranes are properly conditioned with the surfactant being tested, and second to measure the early and delayed effects on flux due to the addition of the surfactant to the system. The surfactant solution is then rinsed with 2.5 L of DI water at a pump speed of 4 Hz to eliminate alkalinity in the system and achieve DI water conductivity. With 2.5 L of DI water, there is likely to be a residual surfactant in the system other than that found in the field samples. After the surfactant treatment and rinsing, 7.56 liters (two gallons) of 2% milk are added to the system and allowed to circulate for at least 5 to 10 minutes under the established conditions. This step serves to ensure a more comprehensive study of how membranes behave under simulated production conditions. The milk is then concentrated until a concentration factor (CF) of 2.00 is reached. Flow measurements are taken at CF = 1.00, 1.07, 1.15, 1.36, 1.66 and 2.00. Achieving a CF of 2.00 is believed to provide enough meaningful data regarding surfactant treatment in the shortest amount of time. After the milk production cycle ends, a “dirty flow” is measured using DI water under the conditions listed in the table. The additional DI water rinse and alkaline removal steps are again repeated as shown at the top of Table 1. These consist of “removal” cycles of Alkaline Ultrasil 110 (no surfactant) until a flow of clean line water base (CWF) of 275 LMH +/-10 is achieved. As previously noted, the purpose of this step is to make sure that as much of the residual grease and surfactant dirt as possible is removed from the membranes and to ensure that the next surfactant under test is not interacting with previous surfactants in an inexplicable way. If CWF of 275 LMH +/-10 is not achieved, another cycle of alkaline “scrap” and DI water rinse is conducted until a baseline is reached. In summary, the steps are outlined below in tabular format.


Table 1. Membrane Production Wash Protocol Performance Results and Membrane Rinse
[0150]Tables 2 and 3 show some of the chemicals tested for membrane production yield for both PES and PVDF membranes, respectively, ranked according to the highest mean flux during a simulated production. Flow measurements are taken at CF= 1.00, 1.07, 1.15, 1.36, 1.66 and 2.00. CF=1.5 in the table means the average between the CF 1.36 and CF 1.66 flow measurements during a simulated production. AVG stands for the average flow over the course of all six flow measurements during simulated production. Flux values are reported in liters per membrane area in square meters per hour (LMH). Note that surfactants and abbreviations are listed in greater detail in Table 4.





Table 3. PVDF Membrane Milk Production Performance
[0151]After considering Tables 2 and 3, as well as Figures 1 to 4, for the highest average flow in the total simulated milk production cycle, the following chemicals were chosen due to their high performances in PES and PVDF membranes : PEG 1450, LAEO 91-6, Guerbet XP-50, and C6 Alkyl Glycoside. For comparison purposes, the following in-line chemicals were also selected for further evaluation: NPE 9.5 (UOl), TDA-9 (U06), AO/AOS (U02), and LAS (U83).
[0152] Table 4 below shows the structures and physical properties of the chemicals that were selected for further evaluation. The list of surfactants contains both branched and unbranched structures, all of which have different properties. Highly branched surfactants like Guerbet XP-50 produce less foam and have a lower dynamic surface tension than surfactants with less branching. Some of the branching structures are believed to work better in membranes. Present theories of functionality based on molecular structure are as follows: • Large molecules and extensive branching can clog or clog membranes depending on the molecular weight cutoff of the particular membrane • Small molecules with little branching can allow these molecules to be easily rinsed and do not affect the surface characteristics of the membrane, such as the zeta potential or reduced surface tension which can improve the wettability characteristics • Molecules with a certain amount of branching and weight can interact with the membrane surface modifying it to improve the wettability characteristics and permeation.
[0153]As an example, PEG 1450 is a food grade polymer that has been found to have a positive effect on membrane production performance and can be dictated in part by its molecular weight. It is also possible that the higher molecular weight PEG 4000, which during the test did not have a positive effect like PEG 1450, could be too large and clog the membrane surface and thus slow down the permeation rate. Conversely, the PEG 300 that was tested may have been very small and therefore permeated across the membrane at a faster rate than PEG 1450, thus negating any positive effects that PEG compounds may have on performance. of the membrane, how to improve the hydrophilic characteristics of the surface. Table 4. Properties of selected chemicals



[0154]Figure 5 shows the average production flow for PES membranes. In this case, the four new chemicals tested had a 9-25% greater flow over the course of the entire production cycle compared to the four in-line chemicals. A 9-25% increase in flow rates could result in an improved production time of 2-5 hours assuming a 20-hour production day. It is believed that a difference greater than 10% in flow rates can be considered significant for industrial applications.
[0155]Figure 6 shows the average production flow for PVDF membranes. Similar to Figure 6, the four highest performing chemicals outperformed the four in-line chemicals by a range of 1 to 36% when observing a maximum average flow over the course of a simulated production cycle. However, in the case of PVDF membranes, PEG 1450 performed best and Alkyl C6 Glucoside was fourth best. These are opposed to PES membranes where Alkyl C6 Glucoside and PEG 1450 are the first and second highest performing chemicals, respectively.
[0156] Figure 7 shows the number of alkaline “removal” cycles used to achieve a baseline of 275 LMH before screening the next set of chemicals. Alkyl C6 Glycoside lasted nine cycles, the last cycle also consisting of using a 0.6% w/w active solution of LAEO 91-6. This allowed for the removal of the Alkyl C6 Glycoside from the membranes and the return of the CWF to baseline values using a surfactant to clean up a surfactant in essence. NPE-9.5, TDA-9, and LAS take multiple cycles to reach a baseline again, while AO/AOS, LAEO 91-6, Guerbet XP-50 and PEG 1450 require only one alkaline cycle to reach the CWF baseline required. An increase in wash cycles indicates poor rinse characteristics in this particular surfactant/membrane combination and should be used with caution.
[0157]It is possible that poor rinse characteristics could result in two scenarios:1. Too much residual surfactant could act as a scale causing weak permeation during production and/or CWF or the other way around2. Residual surfactant could have a positive impact on production and/or CWF due to a positive surface modification, such as modifying to a more hydrophilic surface.
[0158]It is possible that good rinse characteristics result in two scenarios:1. A surfactant-free membrane works well in CWF production as there is no “fouling” remaining.2. A surfactant-free membrane works poorly in CWF production as there is no surface modification due to a lack of residual surfactant.
[0159]Figure 8 shows the number of alkaline removal cycles to return baseline CWF in PVDF membranes. This shows that NPE-9.5 and TDA-9 are the only chemicals that require more than one alkaline wash cycle to return the membrane to the baseline level of CWF. This is likely due to the low surface tension of the PVDF surface and a possible indication as to why PVDF is generally used to minimize clogging in high grease applications. Stainless Steel Coupon Cleaning of Greasy Dirt
[0160]This protocol is directly adopted from the F&B Standard Protocol for Thin Film Milk-Based Dirt Removal. The following adjustments were made for this study: Cleaning Temperatures were set at 47.77°C (118°F) and allowed to clean for 30 minutes to encourage membrane cleaning. Surfactants were used at a concentration of 0.6% w/w with the addition of 0.1% w/w of U131 to provide alkalinity as in previous tests. The results in Table 7 indicate that the best chemicals for removing dairy buritin dirt from stainless steel coupons are NPE 9.5, TDA-9, LAEO 91-6, Guerbet XP-50, and AO/AOS . The weakest performers in this particular test were LAS, APG, and PEG 1450. Due to the importance of milky dirt removal properties of any NPE 9.5 substitution, it is obvious from this screening list that any substitution would be beneficial containing LAEO 91- 6, Guerbet XP-50, and any number of other surfactants/polymers that properly clean these coupons. It is surprisingly shown that weakly cleaning surfactants and polymers do not predict that they will have a negative effect on the membrane. Interestingly, some surfactants/polymers that clean poorly worked very well on the membrane. An example is PEG 1450 polymer which does not act as a surfactant and does not effectively clean greasy dirt, but allows the membrane to work very well after coming in contact with the membrane.
Table 7. Removal of Stainless Steel Coupon Butyrin for Various Surfactants and AlkalinityConclusions:
[0161] It is critical that any possible replacement for use of NPE 9.5 in membrane systems must have a performance equal to or less than NPE 9.5 in membrane production, cleaning performance, rinsing properties, foaming properties, costs, stability formulation, ease of use, and membrane compatibility. The ideal replacement for U01 (NPE 9.5) will have all of these properties, which as well as the data presented will require a blend of multiple surfactants and chemicals that are designed to achieve a complex combination of benefits.EXAMPLE 2
[0162]Attempts to generalize various surfactants capable of performing the membrane cleaning functions of the invention have shown that there appears to be no clear generalizations and a particular surfactant's ability to function is unpredictable.
[0163]For example, attempts have been made to generalize surfactants based on the ability to rinse from the membrane. Figure 9 shows that for PES polysorbate 20 and LAEO 12-15 (7EO) membranes they had poor rinsing characteristics (greater number of rinse/removal cycles) and performed poorly the membrane cleanliness test, (Figure 2). Figure 10 shows that this trend also exists for PVDF membranes, see also Figure 1. However, the hexyl glycoside worked well on the membrane during production, but the rinse was poor. This is a likely candidate as a co-active agent unique to this enhancing system.
[0164]There are a number of theories of functionality based on the molecular structure of the surfactant/polymer and membrane. The greater the molecular weight and the extensive branching of the surfactant and polymer, the greater the propensity to clog or clog the membranes depending on the molecular weight cutoff of the particular membrane and the surface energy of the particular mold surface being treated. However, the data demonstrate that molecule size and degree of branching does not consistently provide predictive results. The PES membrane tested has a Molecular Weight Cutoff (MWCO) of 5,000 to 10,000 and therefore it is believed that FEGs are likely not to permeate well in these membranes compared to IJF PVDF membranes that have a MWCO of 50,000 to 10,000. Small molecules with minimal branching can allow these molecules to rinse off easily and not affect membrane surface characteristics such as zeta potential or reduced surface tension which can improve wettability and hydrophilicity characteristics. Molecules with a certain amount of branching and molecular weight can interact with the membrane surface modifying it to improve the wettability and permeation characteristics.
[0165] As an example, PEG 1450 has a positive effect on membrane production performance that could occur in part due to its molecular weight, it is also possible that PEG with molecular weight greater than 4000, which during testing had an effect weaker, it can be too large and “clogs” the membrane and therefore slows down the permeation rate. Conversely, the PEG 300 that was tested may have been very small and thus permeated across the membrane at a faster rate than PEG 1450, thus negating any positive effects that PEG compounds might have on performance. of the membrane. See Figures 1 and 2. PEG 1450 had the best membrane performance while PEG 4000 had the worst membrane performance, while PEG 300 was the least effective.EXAMPLE 3Glue line and contact angle test
[0166]Polymer membranes have glue lines that may be susceptible to penetration by aggressive surfactants and/or solvent solutions. Applicants tested the compositions of the invention in this scenario. The results are shown in Figures 11 and 12 (the bigger the better). From the Figures, it can be seen that KX-7030 is better in this FES membrane (Figure 11) in Figure 12 for the PVDF membrane, it can be seen that KX-7030 is approximately equal. This suggests that KX-7030 is acceptable and, in some cases, better than Ultrasil 01 (NPE) or Ultrasii 06 (TDA) Next, the contact angle was investigated.
[0167]Contact angles were also used to predict performance. During the PES test, contact angles greater than 25, such as the case with low-performance U06 (TDA), and lower contact angles of less than 25, such as good-performing PEG and NPE, were found to adequately predict performance on the membrane. . For PVDF membranes with higher molecular weight cut-off, the contact angles did not adequately predict the membrane
[0168]Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, although the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the features described. Accordingly, the scope of the present invention is intended to cover all such alternatives, modifications and variations that fall within the scope of the claims, together with all equivalents thereof.

权利要求:
Claims (8)
[0001]
1. A method for cleaning a membrane filter system, CHARACTERIZED in that it comprises: washing said membrane with a composition comprising a surfactant enhancer comprising at least three or more of the following surfactants; nonionic polymers, surfactant blends, or surfactant/nonionic polymeric blends: PEG 1450 blend/hexyl glycoside (50/50); hexyl glycoside; PEG 1450; a lauryl dimethyl amine oxide; a linear C9-11 alcohol with 6 moles of ethoxylation; an alkoxylated Guerbet alcohol; PEG 4000; polycarboxylated alcohol; PEG 1450/Alkoxylated Guerbet (50/50) blend; PEG 1450/hexyl glycoside (50/50); hexyl glycoside/alkoxylated Guerbet blend (50/50); a linear PEG 1450/C9-C11 alcohol blend with 6 moles of ethoxylation (50/50); Guerbet XL-70; a blend of linear C9-C11 alcohol with 6 moles of ethoxylation and a linear C9-11 alcohol with 8 moles of ethoxylation (50/50); PEG 300; a PEG 1450/hexyl glycoside/alkoxylated Guerbet blend (40/40/20); linear alkyl benzene sulfonate; linear C9-C11 alcohol with 8 moles of ethoxylation; Polysorbate 20; linear C9-C11 alcohol blend with 6 moles of ethoxylation/hexyl glycoside (50/50); dioctyl sulfosuccinate; linear C12-C15 alcohol with 7 moles of ethoxylation; linear C9-C11 alcohol with 6 moles of ethoxylation/alkoxylated Guerbet (50/50); and alpha olefin sulfonate; wherein said surfactant enhancer contains less than about 0.5% by weight of nonyl phenol ethoxylate.
[0002]
2. Method according to claim 1, CHARACTERIZED by the fact that the membrane is soiled with a food, water, drink or fermentation-based product.
[0003]
3. Method according to claim 1, CHARACTERIZED by the fact that the membrane is soiled with a dairy product.
[0004]
4. Method according to claim 1, CHARACTERIZED by the fact that said composition further comprises water.
[0005]
5. Method according to claim 1, CHARACTERIZED by the fact that said surfactant enhancer creates a contact angle of less than 30 degrees on the PES membranes.
[0006]
6. Method according to claim 1, CHARACTERIZED by the fact that said surfactant enhancer creates a contact angle of less than 35 degrees in PVDF membranes.
[0007]
7. Method according to claim 1, characterized in that it further comprises washing said membrane with a source of alkalinity.
[0008]
8. Method according to claim 7, CHARACTERIZED by the fact that said washing occurs before, simultaneously or after said washing step of the surfactant enhancer.

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BR112015021560A2|2017-07-18|

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US8933009B2|2015-01-13|

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WO2014164024A1|2014-10-09|

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EP2969150B1|2018-04-25|

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NZ710988A|2019-12-20|

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CN105705220A|2016-06-22|

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CA2902321C|2021-05-18|

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DK2969150T3|2018-08-06|

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EP2969150A1|2016-01-20|

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EP2969150A4|2016-12-14|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/796,473|US8933009B2|2013-03-12|2013-03-12|Surfactant blends for cleaning filtration membranes|

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US13/796.473|2013-03-12|

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PCT/US2014/019971|WO2014164024A1|2013-03-12|2014-03-03|Surfactant blends for cleaning filtration membranes|

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