CN103146505A - Solid block acid containing cleaning composition of cleaning system of normal position cleaning milking machine - Google Patents
Solid block acid containing cleaning composition of cleaning system of normal position cleaning milking machine Download PDFInfo
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Abstract
The invention relates to a solid block acid containing cleaning composition of a cleaning system of a normal position cleaning milking machine. The solid block acid containing cleaning composition comprises, by weight, (A) 10wt%-75wt% of at least one liquid inorganic acid which is selected from phosphoric acid, sulfuric acid, sulphurous acid and nitric acid, (B) 1wt%-60wt% of at least one solid organic acid which is in a range of 1.0-1.1 in prekallikrein activator (pKa) at the temperature of 20DEG C, (C) 15wt%-80wt% of at least one carboxylic acid which is selected from citric acid monohydrate, glycolic acid, maleic acid, succinic acid, glutaric acid and adipic acid, (D) 5wt%-40wt% of urea, (E) 0.1wt%-10wt% of at least one nonionic surfactant, and 100wt% of water, wherein the solid block acid containing cleaning composition comprises less than 1wt% of nonyl phenol ethoxylate and halogen compounds.
Description
It is 200780101383.X that the application of this division is based on application number, and the applying date is on November 5th, 2007, and denomination of invention is divided an application for the original Chinese patent application of " the solid block acid containing cleaning compositions of In-Situ Cleaning milking unit cleaning system ".
Invention field
The present invention relates to the improved sour solid piece cleaning compositions that contains, they can be used for removing the food dirt from typical food or food related manufacturing equipment or finished surface.The invention still further relates to described composition and clean in position purposes in the milking unit cleaning system.In addition, the present invention relates to can be by cleaning enriched material and the applying soln of described composition acquisition.
Background of invention
Cleaned at regular intervals in food-processing industry and sterilization are the systems of legal requirements and implement to keep abnormal high food sanitation and the storage time standard of current human consumer's expection through strictly.Opportunistic pathogen and food spoilage microbial growth may be protected and nourish to the residual food product dirt of staying for a long time on the Food Contact equipment surface, and this opportunistic pathogen and food spoilage microorganism may pollute the food near this residual dirt processing.
Guarantee the human consumer for food with the pathogenic agent potential health hazard relevant with toxin protection and the fragrance of keeping food, nutritive value and quality requirements with directly contact with food or with processing environment relevant any surface make great efforts cleaning and from its decontamination.
The nursing of food preparation surface and equipment and the term in maintenance span " cleaning " refer to give after each operational cycle all food contacting surface basically to remove the processing of (comprise and may protect or nourish any residue of any harmful microbe) of food dirt residue.Yet, remove these residues and do not show equipment is cleaned fully.The large-scale population of microorganism may be present on the food-processing surface, and is even also like this after seeming successfully to clean.The concept of the degree of cleaning of using in food-processing factory is continuuies, and wherein definitely degree of cleaning are dreamboats of striving for all the time; But in practice, the degree of cleaning that reach have than low degree.
Cleaning technique in food-processing industry are experimental traditionally.Deposit and remove the needs to clean that exist before the basic comprehension of mechanism at dirt and develop.Due to Food Quality and public health pressure, food-processing industry has reached high actual degree of cleaning and hygienic standard.Also do not have not reach this point with large expense, and there is sizable interest in more effective and not too expensive technology.Along with the knowledge about the effect of the function of dirt, cleaning chemistry product and cleaning procedure increases, and, along with the improvement of plant design and food processing plant aspect becomes obviously, systematically improved cost effectiveness and the ability of the clean (being cleaning article and program) that is used for removing last trace residue.Food-processing industry and the public's result is more and more higher standard.
Food-processing industry has relied on purification agent efficient to compensate design or operational deficiencies in their cleaning procedures more.This is not to show that industry does not also solve these factors; In fact, due to the exploitation of the technical progress in food processing plant and extraordinary cleaning equipment, cleaning method has had change considerably in recent years.Modern food processing industry has been reformed their decontamination procedure via situ cleaning (CIP) and automatic operation.
In-Situ Cleaning (CIP) system generally appears at the fluidization of producing the human or animal and can absorb in the industry of product, for example dairy industry, pharmaceutical industry and foodstuffs industry.Clean-in-place system is commonly considered as having the big scale production equipment system of reservoir, pipeline, pump and the mixing vessel that can not disassemble to clean.In addition, when for the production of can absorb material the time, the common demanding health of In-Situ Cleaning preparation system.
Typical CIP program can be consisted of by following double teacher (referring to " the Hygiene for Management " of R.A.Sprenger, the 5th edition, p.135):
1. rinse to remove total dirt in advance with cold water
2. purification agent circulates to remove residual adhesion chip and incrustation
3. with rinsing to remove the purification agent of whole traces in the middle of cold water
Sterilization cycles with destroy residual microorganism and
5. finally rinse to remove the sterilant of whole traces with cold water.
During this cleaning procedure foam be that these highly stir, the main concern of pump in following recirculation system.Too much foam reduces flow velocity, makes the recirculating pump cavitation erosion, suppresses peace and quiet solution and contacts with contaminated surface, and extend discharging.These events during CIP adversely affect clean-up performance.
Therefore low foaming is descriptive purification agent characteristic, and it is defined as the foam volume that does not show any problem listed above when time in the cleaning procedure of purification agent being introduced the CIP system largo.Because non-foam is ideal situation, what is measured is the maximum foam level or the amount that do not cause observable machinery or peace and quiet destruction that can allow in the CIP system so problem becomes, then only foam is distributed at least this below maximum value (still, more practically, far away from this below maximum value) formula put goods on the market to guarantee best cleansing performance and CIP system operation.
The main challenge of the purification agent exploitation of food-processing industry is successfully to remove anti-processed conventionally dirt and eliminate not compatible with food-processing chemical.A kind of such dirt is protein, and one group of such chemical is halogen or halogen-generating compound, and they can be introduced in the purification agent compound or add to individually in cleaning procedure so that except deproteinize.
Protein dirt residue (so-called albuminous membranae) is present in all food-processing industries, but the problem of dairy industry (comprising milk and milk products maker) is maximum, because milk-product belong to the most perishable Main Foods and any dirt residue has serious quality consequence.It is undoubtedly that protein dirt residue is common in liquid milk and milk by product industry (comprising the dairy farm), because protein accounts for about 27%(" Milk Components and Their Characteristics " of crude milk solid substance, Harper, W.J., Diary Technology and Engineering(editor Harper.W.J. and Hall, C.W.), p.18-19, The AVI Publishing Company, Westport, 1976).
Because biofluid for example milk is complex mixture, so the kinetics of protein adsorption process is disturbed by the concurrent event of the interior dividing surface of bulk solution and equipment surface place's generation.Temperature, pH value, protein population and concentration and other existence inorganic and the organic structure part are influential to speed kinetics.Yet, unanimously think, under less than 50% mark surface coverage, protein adsorption is rapid, reversible and random alignment, and speed is mass transfer limited, namely all absorption and desorption process depend on that the body solute travels to and fro between the transmission at interface.When coverage surpasses 50%, surperficial ordering generation, and if arranged enough duration of contact, adsorbed protein experience conformation and orientation change and optimization interfacial interaction and system stability.The protein of non-optimal adsorption experiences desorb or exchanges with the more larger protein with more combining sites.It is (the mass action control) of surface reaction restriction that this process rate becomes.With residence time increase, it is irreversible that protein adsorption becomes.
Chlorine makes protein degradation by oxicracking and the hydrolysis of peptide bond, and this makes the larger protein molecule split into less peptide chain.The conformational structure of protein decomposes, and reduces significantly in conjunction with energy, and carries out desorb from the surface, then dissolves or is suspended in scavenging solution.
Use chlorination purification agent solution in food-processing industry is not no problem.Corrosion is to give more sustained attention, and the degraded of polymkeric substance packing ring, sebific duct and apparatus is also.Practice shows, removes for the optimum protein plasma membrane, and effective chlorine density is 75ppm at least originally, preferred 100ppm.Under the effective chlorine density less than 50ppm, because formation insoluble, adhesivity chloralbacid matter is strengthened the gathering of protein dirt (referring to " Cleanability of Milk-Filmed Stainless Steel by Chlorinated Detergent Solutions ", Jensen, J.M., Journal of Dairy Science, Vol.53, No.2, pp.248-251(1970).
Cl concn in peace and quiet solution is not easy to keep or differentiates with analytical method.Available chlorine by the dirt residue dissipate be well-known and chlorine can with the unsettled chloro amido derivative of Protein formation, this chloro amido derivative titration is available chlorine.The validity that chlorine is removed the protein dirt is along with solution temperature and pH value reduce and weaken: reducing temperature affect speed of reaction, and reduction pH value is conducive to the additional structure part of chlorination.
Recent decades, using and using these relevant problems with the chlorine releasing agent in food-processing industry is known and allow.Chlorine has improved cleaning efficiency and improved health, causes the improved products quality.Purification agent manufacturers does not also advance safety and effective low-cost replacement scheme.
Yet new problem forces food-processing industry and purification agent manufacturers to make change: the increasing public worries health and the environmental influence of halogen and organic halogen.No matter about the value of the academic evidence of carinogenicity where, lasting and be biological accumulation for the organic halogen compound effect, and many this compounds mainly cause larger non-cancer healthy effect (internal secretion, immunity and neurological problem) there is no what dispute under extremely low exposure level to the people that contacts and the offspring of Wildlife.Therefore, the purification agent supplier of food-processing industry and they will to concentrate on to find the alternative of the use of Halogen releasing agent in cleaning compositions be safe.Still strongly need to be applied to food-processing industry and have that improvement is described so far and at present the cleanser compositions of the versatility of open question with non-halogen albuminous membranae stripper.
The hard surface cleaner that can be used for communal facility and non-communal facility environment can be many forms.Usually, these sanitising agents are to have anhydrous, organic detergent formulations of neutrality, acidity or alkaline pH value or the liquid preparation of aqueous cleaning agent formulation for being when being diluted to applying soln.Organic detergent formulations is for example prepared in solvent or tensio-active agent base-material at organic base mateiral usually.In addition, these preparations can comprise various compositions such as sequestering agent, rust-preventive agent etc.
But usually use the aqueous diluent of main ratio and tensio-active agent, solubility promoter and the sequestering agent of minor proportions significant quantity to prepare moisture neutrality, acidity or alkaline cleansing agent by applying soln concentration.To a great extent, these sanitising agents can be waterborne liquid enriched material form to be used, and this waterborne liquid enriched material forms applying soln through the water dilution.These rare liquid cleaning formulations can be used for many cleaning ambients.Yet the dilute liquid cleaning formulation that contains the water-based of suitable vast scale or organic thinner causes the large transportation cost of mobile solvent or water usually.In addition, the cleaning enriched material that is liquid form usually may be contaminated or may be degenerated in some cases, be separated, thereby becomes useless.In addition, fluent material may overflow, sputter or misuse, and causes the safety hazard of user's and alkalescence or acid enriched material storeroom in contacting.
Although the liquid waterborne sanitising agent successfully removes crude removal from various crusts, is based on economy and security consideration, the waterborne liquid material still causes sizable defective to the user.Therefore, still strongly need to provide effectively, the effective and safe solid cleaning agent of cost more.
US-B-5,310,549 disclose and have been applied to food mfg and source mill, particularly are applied to the solids-enriched iodine cleaning compositions in the clean-in-place system of dairy industry, and it comprises propiodal and complexing agent, peptizer and dispensable souring agent.Propiodal is iodine complex, and it is organic halogen compound, also may keep lastingly in human body and biological accumulation.This concentrate composition provides the applying soln of the foaming with horizon adjustable according to the ratio of iodine/complexing agent.The low bubble character that provides for the subtend composition and the consideration of complex stability, said composition relies on the nonyl phenol ethoxylate of the ethoxylate mole value with about 6 moles-15 moles.Yet due to the negative healthy effect of nonyl phenol ethoxylate, they are more and more abandoned.Should contain the necessary supplementary component of helpful froth breaking by concentrated iodine composition.Have been found that useful defoamer comprises lipid acid for example fatty acid distribution of coconut oil, Fatty Alcohol(C12-C14 and C12-C18) and phosphoric acid ester.These defoamers are pressed preferably approximately 0.05wt%-0.5wt%, and most preferably approximately the concentration range of the about 0.50wt% of 0.10wt%-exists.
US-B-6,432,906 disclose the solid piece acid sanitising agent that is applied to crust, it generally comprises solid matrix (blend that comprises sour detergent components), be selected from the tensio-active agent cleanser compositions of anion surfactant, nonionogenic tenside or its mixture, and binding agent or solidifiability compound.Equally, preferred nonionogenic tenside included in all working embodiment that provides in specification sheets is nonyl phenol ethoxylate.
Summary of the invention
Therefore the purpose of this product invention is to provide from environment and sanitation point and sees the harmless sour cleaning compositions that contains, and it can form stable solid piece, only produces the foam that minimum being fit to is applied to the CIP system, and shows excellent clean-up performance.
the technology of the present invention purpose solves by the solid block acid containing cleaning compositions, this solid block acid containing cleaning compositions comprises A by composition) 10-75wt%, preferred 20-50wt%, at least a phosphoric acid that is selected from of 25-30wt% most preferably, sulfuric acid, the liquid mineral acid of sulfurous acid and nitric acid, preferably phosphoric acid, B) 1-60wt%, preferred 5-20wt%, most preferably 7-16wt% is at least a at the solid organic acid of 20 ℃ of lower pKa between 1.0 and 1.1, preferred thionamic acid, C) 15-80wt%, preferred 20-40wt%, at least a citric acid monohydrate compound that is selected from of 25-35wt% most preferably, oxyacetic acid, toxilic acid, succsinic acid, the carboxylic acid of pentanedioic acid and hexanodioic acid, the optimization citric acid monohydrate, D) 5-40wt%, preferred 10-20wt%, 14-15wt% urea most preferably, E) 0.1-10wt%, preferred 0.5-5wt%, at least a nonionogenic tenside of 1-2wt% most preferably, be preferably selected from alcohol ethoxylate, alcohol alkoxylate, the ethylene oxide/propylene oxide multipolymer, the aliphatic amide ethoxylate, aliphatic ester derivatives and amine oxide, add to the water of 100wt% with all the other, wherein said composition contains less than 1wt%, preferably less than 0.1wt%, most preferably less than 0.01wt% nonyl phenol ethoxylate and halogen compounds.
The present invention also comprises the using method of the present composition.This solids composition can be from Solid state allocation to form the water-based enriched material.This enriched material has the cleaning compositions of 1:50-1:100 and the ratio of water.This kind enriched material material further dilute with water to form applying soln.This applying soln has 1:50-1:10000, the cleaning compositions of preferred 1:100-1:2000 and the ratio of water.Perhaps, also can directly produce applying soln by the water dissolution solid piece with necessary amount.This kind applying soln can put on various crusts in communal facility or industrial market in order to remove various dirt types.They can be used in particular for the application in interior In-Situ Cleaning (CIP) cleaning system of food-processing facility and can be used in particular for dairy farm and liquid milk and the milk by-product producer.This contains sour solid piece can also be used for cleaning in the more Large-scale Dairy Product processing units in automatic processing system, namely in automatic CIP cleaning system.
With the pickling that replaces and alkali cleaning step cleaning diary processing system.This alkali cleaning step is used for removing degrease and protein from this system, and this acid pickling step is used for removing hard water residue or calcium salt residue.Can be used for according to solid piece of the present invention the system that this kind has alternately pickling and alkali cleaning step.In this kind technique, use the acidic composition by acid block preparation to clean the diary processing system until this block dissolves (desolve) fully.Then, can use the alkali solid piece for the preparation of the soda-wash solution of alkali cleaning step in same equipment.
Detailed Description Of The Invention
Be surprisingly found out that, can obtain from environment and health viewpoint see harmless, can form stable solid piece, only produce the minimum solid block acid containing cleaning compositions that is suitable for being applied to the foam of CIP system and shows excellent clean-up performance, and need not to use any halogen and organic halogen compound and any alkylphenol ethoxylate.
The acid material of preparing solidifies and can solidify in one-trip container, film, water soluble package material and maybe can be packaged in other suitable wrapping material via having a mind to the interaction of component of blend.Concerning for the manufacture of the material and acid cleaner of the present invention of acid cleaner of the present invention, " solid " is the moving composition of shape that consequently can significantly not change when standing without the composition that supports of enough anti-currents under use temperature.But this kind solid can be lump body or building block form or deformable be rigidity water dispersion or rigid gel.For purpose of the present invention, liquid is to flow with sizable speed under use temperature so that will be at the material less than 1 minute its shape of internal loss when standing without the material that supports (shifting out from container).
Composition of the present invention generally comprises nonionogenic tenside.The function of tensio-active agent is the surface tension that changes resulting composition, by dirt emulsification is also allowed to remove via follow-up flushing or rinsing to help dirt remove and suspend.
Nonionogenic tenside (Non-ionic Surfactants), by Schick, M.J. edit, Vol.1of the Surfactant Science Series, Marcel Dekker, Inc., New York, the 1983rd, the excellent reference relevant with the various non-ionic compounds that usually adopt in the present invention's practice.Can be used for nonionogenic tenside of the present invention generally to have organic hydrophobic group and organic hydrophilicity group as feature and usually to prepare by organic aliphatic series or polyoxy alkylidene hydrophobic compound and the condensation of wetting ability basic oxide structure division, this wetting ability basic oxide structure division is ethylene oxide or its polymerization hydrated product, i.e. polyoxyethylene glycol in practice commonly used.
In fact, have hydroxyl, carboxyl, amino or amide group and hydrogen atoms any hydrophobic compound can with ethylene oxide, or its polywater closes adducts, or itself and oxyalkylene for example propylene oxide the mixture condensation and form the non-ionic surface activator.Can easily regulate and the length of the wetting ability polyoxy alkylidene structure division of any specific hydrophobic compound condensation to be created in water-dispersible or the water-soluble cpds that has the required balance degree between wetting ability and hydrophobic properties.Useful ionic surfactant pack is drawn together in the present invention:
1. based on propylene glycol, ethylene glycol, glycol, TriMethylolPropane(TMP) with as the block polyoxytrimethylene-polyethylene oxide polymer of the quadrol of initiator for reaction hydrogen compound.The example of the polymkeric substance of being made by propoxylation in turn and the ethoxylation of initiator can trade(brand)name Pluronic and Tetronic(made by BASF Corp.) be purchased.
The Pluronic compound is that this hydrophobicity base-material is by forming on two hydroxyls that propylene oxide added to propylene glycol by Bifunctionalized (two reactive hydrogen) compound that ethylene oxide and the condensation of hydrophobicity base-material are formed.The great approximately 1.000-about 4.000 of this hydrophobic parts of this molecule.
Then add ethylene oxide so that this hydrophobic part is clipped between hydrophilic group, control to account for the about 80wt% of about 10wt%-of final molecule by length.
The Tetronic compound is to be added in turn on quadrol and four functionalized block Copolymers that obtain by propylene oxide and ethylene oxide.The molecular weight of propylene oxide hydrophobic parts (hydrotype) is about 500-about 7,000 and adds hydrophile (ethylene oxide) to account for the about 80wt% of about 10wt%-of molecule.
2.1 mole contain about 24 carbon atoms of about 6-saturated or unsaturated, straight or branched is pure or uncle or secondary aliphatic amide and the about condensation product of about 50 mole ethylene oxides of 3-and/or propylene oxide.This alcohol structure division can be made of the mixture of the alcohol in above-mentioned carbon range or it can be made of the alcohol of the carbon atom that is contained in the given number in this scope.The example of commercial surfactant can trade(brand)name Noedol(be made by Shell Chemical Co.) and Alfonic(made by Vista Chemical Co.) acquisition.
3.1 mole contain saturated or unsaturated, the straight or branched carboxylic acid of about 18 carbon atoms of about 8-and the about condensation product of about 50 mole ethylene oxides of 6-.This acid structure division can be made of the mixture of the acid in above-mentioned carbon atom scope or it can be made of the acid of the carbon atom that is contained in the given number in this scope.Example with commercial compound of this chemistry can be on market be made by Henkel Corporation with trade(brand)name Nopalcol() and Lipopeg(made by Lipo Chemicals Inc.) acquisition.
Except ethoxylation carboxylic acid (so-called macrogol ester), also can be applicable to specific embodiments of the present invention by other alkanoates with glyceryl ester, glycerine and polyhydroxy-alcohol (sugar or sorbitan/Sorbitol Powder) reaction formation, foodstuff additive are used especially indirectly.All these ester structures part has one or more reactive hydrogen positions on their molecule, these reactive hydrogen positions can experience further acidylate or ethylene oxide (alkoxide) addition to control the wetting ability of these materials.
Low foaming alkoxylate nonionic is preferred, if but can use other the more senior foaming alkoxylate nonionic that does not break away from spirit of the present invention when being combined with low foaming nonionic, so that control the foam distribution of this mixture in whole cleanser compositions.Can be according to the method evaluation lathering property of describing in embodiment.The example of the low lathering surfactant of nonionic comprises:
4. derive from the compound through following modification (substantial reverse) of (1.): ethylene oxide is added on ethylene glycol so that the hydrophile with appointment molecular weight to be provided; Then, the propylene oxide addition is upward obtained the hydrophobicity block with the outside (end) at molecule.The great approximately 1.000-of the hydrophobic parts of this molecule is about 3.100, and wherein the center hydrophile accounts for the about 80wt% of 10wt%-of final molecule.These reverse Pluronics are made with trade(brand)name Pluronic R tensio-active agent by BASF Corporation.
Equally, Tetraonic R tensio-active agent is prepared by ethylene oxide and propylene oxide are added on quadrol in turn by BASF Corporation.The hydrophobic parts of this molecule is great approximately 2, and 100-is about 6,700, and wherein the center hydrophile accounts for the about 80wt% of 10wt%-of final molecule.
5. derive from the compound through following modification of group (1.), (2.) and (3.): by with little hydrophobic molecule for example propylene oxide or oxybutylene and contain the short chain fatty acid of about 5 carbon atoms of 1-or pure and mild its mixture reaction and with terminal hydroxy group (terminal hydroxy group of multiple functionalized structure division) " end-blocking " or " end closure ".These modifications to terminal hydroxy group can obtain full block, block-mixing, mix-block or entirely mix nonionic.
6. useful water-soluble amine oxides tensio-active agent is selected from cocounut oil or tallow alkyl two (low alkyl group) amine oxide, their specific examples has dimethyl dodecyl amine oxide, tridecyl dimethyl oxidation amine, CH3-(CH2)13N(CH3)2-O, pentadecyl dimethyl oxidation amine, cetyl dimethyl amine oxide, heptadecyl dimethyl oxidation amine, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, two (2-hydroxyethyl) dodecyl amine oxide, two (2-hydroxyethyl)-3-dodecyloxy-l-hydroxypropyl amine oxides, dimethyl (2-hydroxyl dodecyl) amine oxide and 3, 6, 9-three-octadecyl dimethyl amine oxide.
Above-named nonionogenic tenside can be used for practice and application of the present invention alone or in combination.Above-mentioned example is only the concrete example explanation that can obtain within the scope of the present invention many tensio-active agents of using.
It is to comprise those of Oxyerhylene part, propylene oxide structure division and their mixture that general discovery especially can be used for nonionogenic tenside of the present invention.Except the cleaning that necessity is provided and dirt suspension effect, have been found that also these nonionic are the pH value stabilizations in sour environment.Can be used for ionic surfactant pack of the present invention and draw together polyoxy alkylidene nonionogenic tenside for example C8-22 normal fat alcohol-ethylene oxide or propylene oxide condenses (they are 1 mole and contain the Fatty Alcohol(C12-C14 and C12-C18) of 8-22 carbon atom and the condensation product of 2-20 mole ethylene oxide or propylene oxide), have general formula HO(C2H4O)
x(C3H6O)
yThe polyoxytrimethylene of H-polyoxyethylene alkene condensate, wherein (C2H4O)
xEqual at least 15% of polymkeric substance, (C3H6O)
yEqual the 20-90% of compound gross weight, have general formula R O-(C3H6O)
x(C2H4O)
yThe alkyl polyoxytrimethylene of H-polyoxyethylene alkene condensate, wherein R is the C1-15 alkyl, x and y represent the integer of 2-98 separately, polyether polyols, and have general formula R (OC2H4)
y(OC4H9)
xThe alcohol ethoxylate of the oxybutylene end-blocking of OH, wherein R is the C8-18 alkyl, and y is about 3.5-10, and x is the integer of about 0.5-1.5.
Tensio-active agent or surfactant system will account for about 10wt% at the most of total acid cleaning compositions.Usually, the tensio-active agent weight percent will be in the scope of about 0.1%-10%, or more preferably, for improved cleaning efficacy, at about 0.5%-5%, most preferably approximately in the scope of 1%-2%.Concrete tensio-active agent or the surfactant mixture selecting to be used for method of the present invention and product depend on final application conditions, comprise manufacture method, product physical form, use pH value, application of temperature, foam control and dirt classification.
In practice, compare with conventional chlorination, high alkalinity CIP sanitising agent, the present invention allows the tensio-active agent in conjunction with high density.Some preferred tensio-active agent of the present invention or surfactant mixture and habitual alkaline substance and chlorine is also chemically stable not of physical compatibility not generally.It is essential that this meticulous foam distributional analysis that not only makes plan be included in the tensio-active agent in the present composition with main difference this technology becomes, and need to examine modestly the cleansing performance that their dirts are removed and suspended.The present invention rely on to be used for the slave unit surface and to remove total dirt and be used for surfactant system at peace and quiet solution suspension pollutant.Dirt is suspended in CIP peace and quiet system be surfactant properties important as dirt is removed with prevent in recirculation and be used further to after a while the CIP system during dirt be deposited on again on the clean surface, this save peace and quiet solution and will same peace and quiet solution again for several cleaning cycles.
Use peptizer so that liquid purification agent premixture is changed into solid in desired invention.Have been found that urea (NH2CONH2) can be used in particular for composition of the present invention as peptizer with souring agent and surfactant composition in conjunction with and provide that water-based is solvable, assignable solid piece.
The solid piece cleaning compositions can comprise about 5-40wt% urea.Have been found that for the consideration to economy, required hardness and solubleness, preferred composition comprises about 10wt%-20wt% urea.Most preferably, composition generally comprises about 14wt%-15wt% urea.Equally, change the physics-chem characteristic that the concentration of urea peptizer in the present composition will change said composition.Therefore, increase the concentration of urea stiffening agent in the present composition and generally will tend to improve the hardness of this solids composition.As stark contrast, reduce the concentration of peptizer and will tend to make this concentrate composition lax or softening.
Urea can obtain from various chemical supplier.Usually, urea can particle form obtain, and can use the urea of any technical grade in scope of the present invention.
Solid piece cleaning compositions of the present invention also contains souring agent or acid source.The function of souring agent is to reduce the pH value of composition.In addition, exist with regard to it, the function of souring agent is to promote in pipeline and the removing of salt aggregation in other application surface that contacts with composition.
According to the present invention, the souring agent source that is used for this solid piece cleaning compositions will comprise at least a liquid mineral acid source, at least a SOLID ORGANIC acid source between 1.0 and 1.1 and the combination of at least a carboxylic acid sources at 20 ℃ of lower pKa.Described acid usually will be at about 25-95wt% by the concentration of the percentage of whole composition, and preferably approximately 65-90wt% most preferably approximately changes between 70-85wt%.In the middle of this composition, at least aly account for about 1-60wt% at the solid acid of 20 ℃ of lower pKa between 1.0 and 1.1, preferably approximately 5-20wt%, about 7-16wt% most preferably, at least a carboxylic acid sources accounts for about 15-80wt%, preferably approximately 20-40wt%, about 25-35wt% most preferably, at least a liquid mineral acid source accounts for about 10-75wt%, preferably approximately 20-50wt%, most preferably about 25-30wt%.
Equally, change the chemical property that the concentration of souring agent in the present composition will change resulting composition.Specifically, the concentration of souring agent is brought up to over certain point and may be produced system to groove and corrosive pipeline.
In addition, have been found that, 5wt%-20wt%, preferred 7wt%-16wt% be at the solid acid of 20 ℃ of lower pKa between 1.0 and 1.1, preferred thionamic acid, with 20wt%-50wt%, preferred 25wt%-30wt% liquid mineral acid source, preferably phosphoric acid, and 20wt%-40wt%, preferred 25wt%-35wt% carboxylic acid, the combination that the optimization citric acid monohydrate combines provides most preferred solid block acid containing cleaning compositions.
Useful carboxylic acid comprises oxyacetic acid (oxyacetic acid), toxilic acid, succsinic acid, pentanedioic acid and hexanodioic acid according to the present invention.Can also use any combination of these organic acids.
Useful liquid mineral acid comprises phosphoric acid, sulfuric acid, sulfurous acid and nitric acid according to the present invention.These acid also can be used in combination.
As at the solid organic acid of 20 ℃ of lower pKa between 1.0 and 1.1, thionamic acid is useful.
The combination of phosphoric acid, citric acid monohydrate compound and thionamic acid is particularly useful for the present composition.
Further describe the present invention with the following examples, these embodiment only are used for illustrating the present invention, and do not limit its scope.
Embodiment
1. foam behavior
Below carrying out, the foam behavior is described in test in detail.
Pack into 250ml graduated cylinder and use plug closes of the composition that 50ml is to be tested.This graduated cylinder is put into swivel arrangement.Start this swivel arrangement and make cylinder round its axle rotation 200 times.Then, rotating generator automatically stops.After stopping immediately with in the amount of reading the foam of generation of the ml scale from the cylinder again after 10 and 30 seconds.The 50ml product of the initial filling of deduction from total lather volume.
For this test, each composition uses at least 4 cylinders.Be recorded in the amount of the foam that produces in each cylinder and compare with the mean vol of each composition.In addition, how soon must compare foam breaks.
Fewer curling and lather collapse are faster, and the froth breaking ability of composition is better, and this froth breaking ability is an important characteristic for the sanitising agent of automatic cleaning.
Following table 1 shows all the components of the composition of testing in following examples.All concentration in this table provide with weight percent.Embodiment 1 is according to composition of the present invention.Comparative example 2 also is used for automatic cleaning.For foam test, Application and preparation solution (0 of correspondent composition, the aqueous solution of 2wt%).Table 2 shows the result of foam test.
Table 1: composition
Table 2a: the foam test result under 20 ℃
Table 2b: the foam test result under 50 ℃
Can find out, in embodiment 1 according to the foam behavior of composition of the present invention with compare according to the foam behavior of the composition of prior art (comparative example 2) much better, although the latter is contained silicone defoamer.In addition, advantage is to break with comparing after the time of much shorter according to the composition of prior art according to the foam of composition of the present invention.As a result, composition according to the present invention is more suitable in automatic cleaning.
2. cleaning behavior
Below carrying out, cleaning validity is described in test in detail.
Following preparation is used for the stainless steel plate (5 * 10cm): the 0.1-0.2g standart soil is applied to a side of this test board, the material that allows subsequently this deposition under 25 ℃ dry 24 hours of test.Use the mixture of grease and protein as standart soil.
Immerse in the cleaning compositions of 900ml in being present in the 1000ml beaker by the sample that will so prepare at the temperature of 40 ℃ in full-automatic impregnating equipment and carried out this cleaner assay in 20 minutes.Removing of the material that the operating weight assay deposits.
By be diluted to working concentration (0.2wt%) with hard water, the composition of stipulating in table 1 is changed into applying soln, by their clean-up performance of test determination.Table 3 shows the result of cleaner assay.
Table 3: the result of cleaner assay
Can find out, according to the cleaning efficacy cleaning efficacy that surpasses according to the composition of prior art far away of composition of the present invention.
Claims (10)
1. solid block acid containing cleaning compositions, it comprises by composition
A) at least a liquid mineral acid that is selected from phosphoric acid, sulfuric acid, sulfurous acid and nitric acid of 10-75wt%,
B) thionamic acid of 5-60wt%,
C) at least a carboxylic acid that is selected from citric acid monohydrate compound, oxyacetic acid, toxilic acid, succsinic acid, pentanedioic acid and hexanodioic acid of 15-80wt%,
D) 5-40wt% urea,
E) at least a nonionogenic tenside of 0.1-10wt%, and all the other add to the water of 100wt%,
Wherein said composition contains less than 1wt% nonyl phenol ethoxylate and halogen compounds.
2. according to claim 1 composition, wherein said composition comprises by whole compositions
A) at least a liquid mineral acid that is selected from phosphoric acid, sulfuric acid, sulfurous acid and nitric acid of 20-50wt%,
B) thionamic acid of 5-20wt%,
C) at least a carboxylic acid that is selected from citric acid monohydrate compound, oxyacetic acid, toxilic acid, succsinic acid, pentanedioic acid, hexanodioic acid of 20-40wt%,
D) 10-20wt% urea,
E) at least a nonionogenic tenside of 0.5-5wt%, and all the other add to the water of 100wt%.
3. according to claim 1 and 2 composition, wherein said composition comprises by whole compositions
A) 20-50wt% phosphoric acid,
B) 5-20wt% thionamic acid,
C) 20-40wt% citric acid monohydrate compound,
D) 10-20wt% urea,
E) at least a nonionogenic tenside of 0.5-5wt%, and all the other add to the water of 100wt%.
4. one or more composition according to claim 1-3, wherein said composition comprises by whole compositions
A) 25-30wt% phosphoric acid,
B) 7-16wt% thionamic acid,
C) 25-35wt% citric acid monohydrate compound,
D) 14-15wt% urea,
E) at least a nonionogenic tenside of 1-2wt%, and all the other add to the water of 100wt%.
5. one or more composition according to claim 1-4, wherein said nonionogenic tenside is selected from alcohol ethoxylate, alcohol alkoxylate, ethylene oxide/propylene oxide multipolymer, aliphatic amide ethoxylate, aliphatic ester derivatives, amine oxide.
6. one or more composition according to claim 1-5, wherein be contained in described composition in one-trip container, film or water soluble package material.
7. enriched material comprises composition one or more according to claim 1-6 and water in the ratio of 1:50-1:100.
8. applying soln comprises composition one or more according to claim 1-6 and water in the ratio of 1:50-1:10000.
9. use the method for solid block acid containing cleaning compositions cleaning milking unit one or more according to claim 1-6, comprise the following steps: make said composition be arranged in divider, said composition is dissolved in aqueous diluent to obtain enriched material, the use thinner dilutes this enriched material and obtains applying soln, and described applying soln is applied on milking unit dirt with the surface of removing contaminated.
10. according to claim 9 method, wherein make said composition arrange near waterworks and distribute by allowing it contact with the formation enriched material with the water-based spraying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100409837A CN103146505A (en) | 2007-11-05 | 2007-11-05 | Solid block acid containing cleaning composition of cleaning system of normal position cleaning milking machine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100409837A CN103146505A (en) | 2007-11-05 | 2007-11-05 | Solid block acid containing cleaning composition of cleaning system of normal position cleaning milking machine |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780101383A Division CN101848982A (en) | 2007-11-05 | 2007-11-05 | Solid block acid containing cleaning composition for clean-in-place milking machine cleaning system |
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| CN103146505A true CN103146505A (en) | 2013-06-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100409837A Pending CN103146505A (en) | 2007-11-05 | 2007-11-05 | Solid block acid containing cleaning composition of cleaning system of normal position cleaning milking machine |
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| CN (1) | CN103146505A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479699A (en) * | 2016-09-22 | 2017-03-08 | 长兴净安环保科技有限公司 | A kind of CIP acidic cleaning and preparation method thereof |
| CN106479705A (en) * | 2016-09-22 | 2017-03-08 | 长兴净安环保科技有限公司 | A kind of CIP acidic cleaning for food production line and preparation method thereof |
| US11214763B2 (en) | 2018-01-26 | 2022-01-04 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
| US11377628B2 (en) | 2018-01-26 | 2022-07-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| US12006488B2 (en) | 2021-11-29 | 2024-06-11 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
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| US6432906B1 (en) * | 1995-02-01 | 2002-08-13 | Ecolab Inc. | Solid acid cleaning block and method of manufacturing |
| US6472358B1 (en) * | 2001-11-15 | 2002-10-29 | Ecolab Inc. | Acid sanitizing and cleaning compositions containing protonated carboxylic acids |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432906B1 (en) * | 1995-02-01 | 2002-08-13 | Ecolab Inc. | Solid acid cleaning block and method of manufacturing |
| US6472358B1 (en) * | 2001-11-15 | 2002-10-29 | Ecolab Inc. | Acid sanitizing and cleaning compositions containing protonated carboxylic acids |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479699A (en) * | 2016-09-22 | 2017-03-08 | 长兴净安环保科技有限公司 | A kind of CIP acidic cleaning and preparation method thereof |
| CN106479705A (en) * | 2016-09-22 | 2017-03-08 | 长兴净安环保科技有限公司 | A kind of CIP acidic cleaning for food production line and preparation method thereof |
| US11214763B2 (en) | 2018-01-26 | 2022-01-04 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
| US11377628B2 (en) | 2018-01-26 | 2022-07-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| US11834628B2 (en) | 2018-01-26 | 2023-12-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| US11976255B2 (en) | 2018-01-26 | 2024-05-07 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| US12006488B2 (en) | 2021-11-29 | 2024-06-11 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
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