CN1117849C - Process for producing granular detergent components or compositions - Google Patents
Process for producing granular detergent components or compositions Download PDFInfo
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- CN1117849C CN1117849C CN96193487A CN96193487A CN1117849C CN 1117849 C CN1117849 C CN 1117849C CN 96193487 A CN96193487 A CN 96193487A CN 96193487 A CN96193487 A CN 96193487A CN 1117849 C CN1117849 C CN 1117849C
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- Prior art keywords
- zeolite
- granular detergent
- crystalline zeolite
- detergent component
- alkyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Abstract
The invention relates to a process for the preparation of a granular detergent composition or component having a bulk density greater than 650 g/l which comprises the step of dispersing a liquid binder throughout a powder stream in a high speed mixer to form granular agglomerates, wherein the powder stream comprises crystalline zeolite A having an oil absorbing capacity of at least 40 ml/100g, preferably at least 45 ml/100g and most preferably at least 50 ml/100g.
Description
The present invention relates to continuously, preparation has the granular detergent composition of high-bulk-density and good fluidity or the method for component.In said composition and component, the known use of people is at the known water-soluble crystalline material of detergent applications, and crystalline zeolite A is as washing assistant, and this is particularly suitable for decationize from hard water, for example calcium and magnesium.
Crystalline zeolite A is the powder of very thin pulverizing.Adding final product, before the especially final detergent composition, people are processed into the fine powder pulverized powder larger particles form (400-1000 micron usually) usually.Various prilling process are known, and it comprises spraying drying and agglomeration.Wherein using zeolite A is known as the agglomeration method of the routine of one of component in the prior art:
On April 25th, 1979, disclosed GB2005715 described a kind of agglomeration method based on zeolite A.Zeolite A makes the nonionogenic tenside agglomerate with the carbonate agglomeration.
On December 23rd, 1993, disclosed WO93/25378 described the method for preparing the granulated detergent that contains zeolite A.Zeolite A and high reactivity, neutral surfactant paste in super mixer and moderate-speed mixers/cyclone agglomerator agglomeration with the preparation anionic surfactant agglomerate.
One of the factor that limits the surfactant activity of above-mentioned prior art is the capacity that zeolite A absorbs the liquid organic substance.People have advised replacing zeolite A to address this problem with zeolite P (especially zeolite MAP):
On January 7th, 1993, disclosed EP521635 described the granulated detergent that uses the preparation of 10%-100% zeolite MAP.Zeolite MAP has the chemical constitution that is different from zeolite A.In the embodiment 1 of this patent application, the oily absorptive capacity of having reported zeolite MAP is 41.6ml/100g, and it is higher than the measurement sample of zeolite A, and zeolite A is 26-35.5ml/100g.
Yet the modification of the chemical structure of conventional crystalline zeolite A (being the stoichiometric ratio of modification Si, Al, Na, O, H) is always not desirable, because other character of zeolite and feature are inevitable influenced.
The purpose of this invention is to provide the prilling process for preparing granulated detergent, it adds the high crystalline zeolite that absorbs in particle agglomerates, and does not lose its washing assistant ability, especially calcium exchange capacity and calcium rate of exchange.
The objective of the invention is to use modification crystalline zeolite A to realize with high oil receptivity by disclosed method in claim 1.The oily receptivity zeolite A of 40ml/100g has the physical structure (being degree of crystallinity, surface area feature, moisture content or the like) of modification in order to obtain at least, rather than changes chemical structure.By this way, still can utilize the outstanding washing assistant character of zeolite A.
Another object of the present invention provides the prilling process of the granulated detergent of the amount decline for preparing the oversized particles (or " caking ") that has the processing stability of improvement and form during the course.
Summary of the invention
Purpose of the present invention is achieved greater than the granular detergent composition of 650g/l or the method for component by the preparation tap density, this method is included in the super mixer liquid adhesive is scattered in the powder logistics fully to form the step of particle agglomerates, wherein powder material contains oily receptivity 40ml/100g at least, preferred 45ml/100g at least, most preferably the crystalline zeolite A of 50ml/100g at least.
In a preferred embodiment of the invention, mixing by about 2 seconds-Yue 30 seconds residence time in super mixer forms particle agglomerates, then in moderate-speed mixers/cyclone agglomerator by being less than about 5 minutes, preferably be less than further blended step of about 2 minutes moderate-speed mixers residence time, wherein optionally add the fine powder pulverized powder.
In different embodiment of the present invention, the liquid washing assistant is surfactant paste, organic polymer or silicone oil.Surfactant paste can contain negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and their mixture; Wherein negatively charged ion and/or nonionogenic tenside are most preferred.
Detailed Description Of The Invention
Granulation in the present invention be defined as preparation this as the method for the granular product of particulate particle agglomerates (according to S.A.Kuti, " selection of agglomeration-practicality ", be disclosed in Journal AmericanOil Chemists ' Society, the 55th volume, in January, 1978).Particle agglomerates is defined as the product of this granulation process in the present invention.Then explanation of Kuti " agglomerate forms by blended solid with as the liquid of tackiness agent usually, not have the liquid-solid mixture that lumps but be difficult to usually prepare ".
" solid " that is called by Kuti will contain the crystalline zeolite A with some physical features of hereinafter describing in detail in the present invention.We find that the selection of " solid " helps preparing the liquid-solid mixture that does not have caking greatly.
The main component of particle agglomerates of the present invention is the crystalline zeolite A of following formula:
(Na2O)·(Al2O3)·x(SiO2)·wH2O
Wherein x is that 1-2 and w are 0-6.
It is preferred that particle size is up to 10 microns hydration or partially hydrated natrolite A.
In especially preferred embodiment, x=2, zeolite A has following formula:
Na
12[(AlO
2)
12(SiO
2)
12]·(6w’)H
2O
Wherein (6w ') is about 30 for about 20-, especially is about 27, and has common less than about 5 microns particle size.The amount of crystalline zeolite A is preferably 20% to 70 weight % of described granulated detergent weight among the present invention.
Zeolite A material of the present invention contains to up to 28% water.Preferred washing assistant material is a hydrated form, contains the water of about by weight 5%-about 28%.Preferred crystalline aluminosilicate ion-exchange material contains the water of the 10%-that has an appointment about 22% in its crystalline matrix.Crystalline zeolite A material be further characterized in that the particle size diameter that about 0.1-is about 10 microns.Preferred ion-exchange material has about 0.2 micron-Yue 4 microns particle size diameter.Term among the present invention " particle size diameter " expression by the routine analysis technology, for example uses electronics to sweep the microscopical measurement microscope method of anchor by the average particle size particle size diameter of the weight of certain ion-exchange material.Another feature of crystalline zeolite A material of the present invention is to be at least about 200mg equivalent calcium carbonate water hardness/g pure aluminium silicate based on the calcium ion exchange capacity that butt calculates, and is generally about 300mg equivalent/g to 352mg equivalent/g.Being further characterized in that based on calcium ion hardness of zeolite A material of the present invention, their calcium ion exchange rate is at least about 2 grain Ca
++/ gallon per minute/gram/gallon (0.13gCa
++/ liter/minute/grams per liter) pure aluminium silicate (butt), be generally 2 grain Ca
++/ gallon per minute/gram/gallon (0.13gCa
++/ liter/minute/grams per liter) to 6 grain Ca
++/ gallon per minute/gram/gallon (0.39gCa
++/ liter/minute/grams per liter).The calcium ion exchange rate that the best pure aluminium silicate that is used for washing assistant shows is 4gCa at least
++/ gallon per minute/gram/gallon (0.26gCa
++/ liter/minute/grams per liter).
It is commercial available being used for zeolite A of the present invention.Suitable zeolite A materials samples is by Soprolit (manufacturers's Ref. No. 94/099/1) and Enichem (the Ref. No. AF1094 of manufacturers).Being used for pure aluminium silicate of the present invention structurally is crystalline, can natural generation pure aluminium silicate or synthetic obtaining.The method for preparing the aluminosilicate ion exchange material is discussed in the people's such as Krummel of promulgation on October 12nd, 1976 US3985669, and this patent is classified this paper reference as.
A principal character of the present invention is that the zeolite A that is used to form particle agglomerates has 40ml/100g at least, preferred 45ml/100g at least, the most preferably oily receptivity of 50ml/100g at least.Measure the middle explanation of method " testing method " hereinafter of oily receptivity.
The zeolite of other form optionally mixes with zeolite A, for example zeolite P, X zeolite and zeolite HS.
Particle agglomerates of the present invention also can contain other detergent component.
The water-soluble salt of higher fatty acid, promptly " soap " is anion surfactant useful in the present composition.It comprises alkali metal soap, for example contains 8-Yue 24 carbon atoms of having an appointment, sodium, potassium, ammonium and the alkylammonium salt of the higher fatty acid of about 18 carbon atoms of preferably about 12-.Soap can be by the direct saponification or the preparation of the neutralization by free fatty acids of fat and oil.What be particularly useful is the sodium and the sylvite of the fatty acid mixt that obtained by Oleum Cocois and Tallow, beef, i.e. sodium or potassium animal oil and Oleum Cocois soap.The neutral anion surfactant is preferred.
Useful anion surfactant also comprises water-soluble salt, preferably contains basic metal, ammonium and the alkanol ammonium salt of the organosulfur acidification reaction product of the alkyl of about 20 carbon atoms of the 10-that has an appointment and sulfonic acid or sulfate group in its molecular structure.(moieties that acyl group is arranged that in term " alkyl ", comprises).The example of synthetic this group tensio-active agent is sodium alkyl sulfate and potassium, especially by sulfation high fatty alcohol (C
8-C
18Carbon atom), the alcohol that obtains of the glyceryl ester by reduction animal or Oleum Cocois for example, the product that obtains; Sodium alkyl benzene sulfonate and potassium, wherein alkyl contains about 15 carbon atoms of the 9-that has an appointment, and is the straight or branched configuration, for example those that describe in US2220099 and 2477383; And methylmesylate.Especially valuable is linear alkylbenzene sulfonate, and wherein average carbon atom number is about 11-13 in alkyl, is abbreviated as C
11-C
13LAS.
Other anion surfactant of the present invention is the alkyl glycerylether sodium sulfonate, especially the ether of the higher alcohols that is obtained by animal and Oleum Cocois; Coco-nut oil fatty acid coconut monoglyceride and sodium sulfate; Per molecule contains the alkylphenol oxyethane ether sodium sulfate or the sylvite of about 10 ethylene oxide units of the 1-that has an appointment, and wherein alkyl contains about 12 carbon atoms of the 8-that has an appointment; Contain the alkyl epoxy ethane ether sodium sulfate or the sylvite of about 10 ethylene oxide units of the 1-that has an appointment with per molecule, wherein alkyl contains about 20 carbon atoms of the 10-that has an appointment.
Other useful anion surfactant of the present invention is included in to contain in the fatty acid group and has an appointment 6 to 20 carbon atoms and contain the water-soluble salt of the α-sulfonated fatty acid ester of 1-10 the carbon atom of having an appointment in ester group; Contain at acyl moiety and to have an appointment 2-9 carbon atom and to contain the water-soluble salt of the 2-acyloxy-alkane-1-sulfonic acid of about 23 carbon atoms of the 9-that has an appointment at paraffin section; The sulfated alkyl ether that contains have an appointment 10-20 carbon atom and about 30 moles of ethylene oxide of about 1-at moieties; The water-soluble salt that contains the alkene sulfonate of 12-24 the carbon atom of having an appointment; Have an appointment 1-3 carbon atom and contain the β-alkoxy alkane sulfonate of about 20 carbon atoms of the 8-that has an appointment at paraffin section with containing at moieties.Although discuss and use acid salt usually, can carry out the neutralization of acid as the part of finely divided mixing step.
Also useful as surfactants of water soluble nonionic surfactant in composition of the present invention.In fact, preferable methods is used the anionic/nonionic mixture.This non-ionic material comprises by alkylene oxide group (wetting ability) and the compound of condensation prepared that is organic hydrophobic compound of aliphatic series or alkylaromatic hydrocarbon in nature.Can easily regulate to obtain having required hydrophilic and hydrophobic part equilibrated water-soluble cpds with the length of the polyalkylene oxide groups of any specific hydrophobic group condensation.
Suitable ionic surfactant pack is drawn together the polyethylene oxide condensation compound of alkylphenol, for example has the alkylphenol of alkyl of the straight or branched configuration that contains about 6-16 carbon atom and the condensation product of every mole of about 4-25 moles of ethylene oxide of alkylphenol.
Preferred nonionic is fatty alcohol and the every mol of alcohol 1-25 moles of ethylene oxide that contains the straight or branched configuration of 8-22 carbon atom, the water-soluble condensation product of especially every mol of alcohol 2-7 moles of ethylene oxide.Especially preferred is the condensation product with alcohol of the alkyl that contains about 9-15 carbon atom; Condensation product with propylene glycol and oxyethane.
Other preferred nonionic is a polyhydroxy fatty acid amide, and it is by making fatty acid ester and N-alkyl polyhydroxy amine prepared in reaction.Being used for preferred amine of the present invention is that N-(R1) CH2 (CH2OH) 4-CH2-OH and preferred ester are the C12-C20 fatty acid methyl esters.The condensation product of N-methylglucosamine (it is obtained by glucose) and C12-C20 fatty acid methyl ester most preferably.
The method for preparing polyhydroxy fatty acid amide was described among the disclosed WO9206073 on April 16th, 1992.This application has been described the method for preparing polyhydroxy fatty acid amide in the presence of solvent.In the preferred embodiment of this invention, N-methylglucosamine and the reaction of C12-C20 methyl ester.Say also that wherein the makers-up of granular detergent composition can find containing alkoxylate, can easily carry out amidate action (the 15th page, 22-27 is capable) under especially ethoxylation (EO 3-8) C12-C14 alcohol exists.It directly obtains being applicable to nonionic surfactant system of the present invention, and for example it contains the C12-C14 alcohol of N-methyl glucose amide and 3 ethoxylation groups of per molecule.
Semi-polar nonionic surfactants comprises that the alkyl that contains about 10-18 carbon atom and two are selected from the water-soluble amine oxides of the group of the alkyl that contains about 3 carbon atoms of 1-and hydroxyalkyl; Contain the water soluble oxidized phosphine that the alkyl of about 10-18 carbon atom and two are selected from the group of the alkyl that contains about 3 carbon atoms of 1-and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the group of the alkyl that contains about 3 carbon atoms of 1-and hydroxyalkyl with the alkyl that contains about 10-18 carbon atom and one.
Amphoterics comprises aliphatic derivatives or heterocycle is secondary and the aliphatic derivatives of tertiary amine, wherein aliphatic group can be a straight or branched, wherein one of aliphatic substituting group contains have an appointment 8-18 carbon atom and at least one aliphatic substituting group and contains from the anionic water solubilizing group.
Zwitterionics comprises aliphatic quaternary ammonium, Phosphonium and sulfonium compound derivative, and wherein one of aliphatic substituting group contains 8-18 the carbon atom of having an appointment.
Useful cats product comprises formula R
4R
5R
6R
7N
+X
-Water-soluble quaternary ammonium compound, R wherein
4Be 10-20, the alkyl of preferred 12-18 carbon atom, R
5, R
6And R
7Be respectively C
1-C
7Alkyl, preferable methyl; X-is a negatively charged ion, for example chlorion.This trimethyl ammonium examples for compounds comprises C
12-14Alkyl trimethyl ammonium chloride and coconut alkyl trimethyl N-ammonium methyl sulfate.
Granulated detergent of the present invention can contain neutrality or basic salt, and it has 7 or bigger pH in the aqueous solution, can be inorganic or organic in nature.Builder salt helps to provide required tap density to detergent particles of the present invention.Although some salt is inert, many salt also play the detergent builder compound material in laundry solution.
The example of neutral aqueous solution salt comprises muriate, fluorochemical and the vitriol of the ammonium of basic metal, ammonium or replacement.Above-mentioned an alkali metal salt, especially sodium salt are preferred.Sodium sulfate is generally used in the detergent particles, be especially preferred salt, citric acid and usually any other organic or inorganic acid can add in the granulated detergent of the present invention, as long as other component chemical is compatible in it and the agglomeration composition.
Other useful aqueous solution salt comprises the compound of common known detergent builders material.Washing assistant is selected from phosphoric acid salt, poly-phosphate, phosphonate, polyphosphonate, carbonate, silicate, borate and the polyhydroxy sulfonate of the ammonium of various water miscible basic metal, ammonium or replacement usually.Preferably above-mentioned an alkali metal salt, especially sodium salt.
The specific examples of inorganic phosphate builders is that tri-polyphosphate, pyrophosphate salt, the polymerization degree are the polymer metaphosphate of about 6-21 and the sodium and the sylvite of orthophosphoric acid salt.The example of poly-phosphate washing assistant is second di 2 ethylhexyl phosphonic acid sodium and sylvite, ethane, 1-hydroxyl-1, the sodium of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane, 1,1, the sodium of 2-tri methylene phosphonic acid and sylvite.Other phosphorus washing-aid compound is at US3159581; US3213030; US3422021; US3422137; US3400176; Open among the US3400148, classify this paper reference as.
The example of non-phosphorus inorganic builders is that the mol ratio of carbonate, supercarbonate, sesquicarbonate, ten water tetraborates and silicon-dioxide and alkalimetal oxide is about 4.0 for about 0.5-, the sodium and the sylvite of the silicate of preferably about 1.0-about 2.4.In order to operate, the composition that is prepared by method of the present invention does not need excessive carbonate, and needs not exceed the broken lime carbonate of 2% fine powder described in the people's such as Clarke of preferred as promulgation on April 1st, 1980 the US4196093, and does not preferably have the latter.
Equally usefully various organic polymers, wherein some also can be used as washing assistant to improve washability.This polymkeric substance comprises carboxyl-low alkyl group sodium cellulosate, low alkyl group sodium cellulosate and hydroxyl low-grade alkyl sodium cellulosate; for example; Xylo-Mucine, sodium carboxymethylcellulose pyce and HPMC; polyvinyl alcohol (it also contains some polyvinylacetate usually), polyacrylamide, polyacrylic ester and various multipolymer, for example toxilic acid and acrylic acid multipolymer.The molecular weight of these polymkeric substance can extensively change, but great majority are in the 2000-100000 scope.Other suitable polymers is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazole or their mixture of polyamine N-oxide pllymers, N-vinyl miaow pyrrolidone and N-vinyl imidazole.
Polymeric polycarboxylate washing assistant is described in the US3308067 of the Diehl of promulgation on March 7th, 1967.This material comprises aliphatic carboxylic acid, for example toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid all-and the water-soluble salt of multipolymer.
Silicone oil
The particulate froth suppressor also can directly add in the agglomerate of the present invention or by doing additive process by the powder logistics is added the agglomeration unit and add in the final composition.The foam inhibition activity of these particulate is preferably based on lipid acid or siloxanes.
In one embodiment of the invention, silicone oil (the preferably silicone oil of at least 30 weight %) is absorbed on the special zeolite A.
Optional ingredient
Other component that is generally used for detergent composition can be included in the composition of the present invention.It comprises flow promotor, color spot, SYNTHETIC OPTICAL WHITNER and bleach activator, whipping agent or suds suppressor, anti-tarnishing agent and sanitas, soil-suspending agent, soil releasing agent, dyestuff, filler, white dyes, sterilant, pH regulator agent, non-washing assistant alkali source, solubilizing agent, enzyme, enzyme stabilizers, sequestrant and spices.
These are component optionally, and white dyes especially can directly add in the agglomerate of the present invention or can be used as the independent particulate component that is suitable for dried addition method and adds in the component of agglomerate of the present invention.
Processing
Useful agglomeration method disclosed among the disclosed WO93/25378 on October 28th, 1992 disclosed EP-A-510746 and on December 23rd, 1993.These applications are described in solid and the high reactivity and the agglomeration of surfactant paste.Yet people can understand, can be wholly or in part by other tensio-active agent in the high reactivity with slurry, and especially nonionogenic tenside replaces (as disclosed EP643130 on March 15 nineteen ninety-five), or is replaced by organic polymer or silicone oil.The preferred embodiments of the invention are described in detail in following embodiment.
Testing method
The oil absorption value can be by following British Standards, and BS3483:part7:1982 (corresponding to ISO 787/5-1980) measures.Use contains free alkali and is less than 0.5% 5g zeolite A sample.Oil absorption value (OAV) is expressed from the next:
Embodiment
All values % is by weight represented.Zeolite content is in the benchmark of hydration (comprise 15% by weight combination water).
Embodiment 1 embodiment 2 embodiment 3 Comparative Example A An
Zeolite A
*32 22 52-
Zeolite A#---32
C12-15AS 24 31 - 24 C12-15AE3S 6 8 - 6
Yellow soda ash 25 12 13 25
Multipolymer-12--nonionogenic tenside--30-
Water 5 5-5
A small amount of component 8 10 58
Zeolite A
*By Industrial Zeolites (UK) Ltd.of Thurrock, Essex, England provides, oily receptivity 45.5ml/100g.
Zeolite A# is provided with trade(brand)name Wessalith by Degussa, oily receptivity 36ml/100g.
C12-15AS is a sodium alkyl sulfate, and alkyl chain mainly contains C12-C15.
C12-15AE3S is a sodium alkylether sulphate, and alkyl chain mainly contains C12-C15 and average 3 oxyethyl groups of per molecule.
Multipolymer is the multipolymer of vinylformic acid and toxilic acid.
Nonionogenic tenside contains 7 parts of ethoxylated alcohols, and wherein alkyl chain mainly contains C12-C15 and average 3 oxyethyl groups of per molecule and 3 parts of C12-14 polyhydroxy fatty acid amides.
A small amount of component mainly is vitriol and some other a spot of impurity.
The particle agglomerates that contains the component of embodiment 1 prepares by the following method.Powder stock (zeolite A and yellow soda ash) is added in the pot of the Eirich mixing tank that rotates with 64rpm, mixed for 10 seconds.Stop the mixing tank pot then, with the surfactant paste (50 ℃) of preheating, 80% surfactant activity composition in the aqueous solution adds the space of powder intermediate formation with the form of sheet.The loose powder that takes out is placed on the slurry so that it is covered fully.Then, mixing tank rotates again, and pot is with the 64rpm rotation, and knife mill is set at 2500rpm.When particle agglomerates begins to form, stop to mix (at this moment, the electric current by Eirich control rises to 3 amperes by 2.8).
The particle agglomerates that obtains is free-pouring, contains to be less than by weight particle on 25% the sieve (particle is considered to have the particle greater than 1600 microns particle size on the sieve).
The particle agglomerates that contains the component of embodiment 2 prepares by the following method.
Prepare the slurry that contains tensio-active agent by sulfation and the suitable alcohol of neutralization, the water content of the slurry that obtains is 18%.With pump slurry is sent into high-shear mixer (Loedige CB ), in high-shear mixer, add simultaneously zeolite A and yellow soda ash, thoroughly mix with wherein highly viscous slurry.The mixture that obtains directly is transferred to low shear mixer (Loedige KM ), forms agglomerate.After from low shear mixer, discharging, agglomerate is sieved to remove oversize " caking " and particulate.At last agglomerate is cooled off in fluidized-bed, before mixing with the preparation final product, store with other detergent powder is dried.The residence time in high-shear mixer is about 8 seconds, and the residence time in low shear mixer is about 35 seconds.
Contain embodiment 3 composition particle agglomerates by with the preparation of the same procedure of embodiment 2,70 ℃ the nonionogenic tenside of remaining on that anion surfactant oar material is used as the viscosity slurry replaces.
Contain Comparative Example A An component particle agglomerates by with the identical method preparation of embodiment 1, use and the identical mixed powder described in the embodiment 1 and the time of slurry.The particle agglomerates that obtains contains greater than particle on 25% the sieve by weight (particle is considered to have the particle greater than 1600 microns particle size on the sieve).
Claims (9)
1. preparation has the method for tap density greater than the granular detergent component of 650g/l, this method is included in the super mixer liquid adhesive is scattered in the powder logistics fully to form the step of particle agglomerates, wherein the powder logistics contains oily receptivity and is the crystalline zeolite A of 40ml/100g at least, and this granular detergent component comprises the silicone oil of crystalline zeolite A and at least 30 weight %.
2. the process of claim 1 wherein that described granular detergent component comprises:
(a) the oily receptivity of 20% to 70 weight % is the crystalline zeolite A of 40ml/100g at least; And
(b) silicone oil of at least 30 weight %.
3. the process of claim 1 wherein that the formation step of particle agglomerates is as follows:
In super mixer, mix with 2 seconds-30 seconds the residence time;
In moderate-speed mixers/cyclone agglomerator, further mix then, wherein, randomly add the fine powder pulverized powder with the residence time that is less than 5 minutes by described moderate-speed mixers.
4. the method for claim 3, wherein the residence time by described moderate-speed mixers is less than 2 minutes.
5. the process of claim 1 wherein that described granular detergent component also contains through the neutral anion surfactant.
6. the process of claim 1 wherein that described granular detergent component also contains the tensio-active agent that is selected from negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and their mixture.
7. the method for claim 2, wherein said granular detergent component also contains the tensio-active agent that is selected from negatively charged ion, nonionic, positively charged ion, both sexes, zwitterionics and their mixture.
8. the process of claim 1 wherein that the oily receptivity of described crystalline zeolite A is 45ml/100g at least.
9. the process of claim 1 wherein that the oily receptivity of described crystalline zeolite A is 50ml/100g at least.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95302859.4 | 1995-04-27 | ||
| EP95302859 | 1995-04-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1183798A CN1183798A (en) | 1998-06-03 |
| CN1117849C true CN1117849C (en) | 2003-08-13 |
Family
ID=8221174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96193487A Expired - Lifetime CN1117849C (en) | 1995-04-27 | 1996-03-27 | Process for producing granular detergent components or compositions |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0870008B2 (en) |
| JP (1) | JPH11504364A (en) |
| KR (1) | KR100258542B1 (en) |
| CN (1) | CN1117849C (en) |
| AR (1) | AR001718A1 (en) |
| AT (1) | ATE342955T1 (en) |
| AU (1) | AU5324596A (en) |
| BR (1) | BR9608445A (en) |
| CA (1) | CA2216816C (en) |
| DE (1) | DE69636644T3 (en) |
| ES (1) | ES2275274T3 (en) |
| MX (1) | MX9708236A (en) |
| TW (1) | TW323303B (en) |
| WO (1) | WO1996034082A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19753310A1 (en) * | 1997-12-02 | 1999-06-10 | Henkel Kgaa | Raw material compounds with high bulk density |
| DE19855676A1 (en) * | 1998-12-02 | 2000-06-08 | Henkel Kgaa | Detergent and cleaning agent additive and process for its production |
| BR0213432A (en) | 2001-10-25 | 2004-11-09 | Unilever Nv | Process for the preparation of detergent granules |
| GB0125653D0 (en) | 2001-10-25 | 2001-12-19 | Unilever Plc | Process for the production of detergent granules |
| CN102459555B (en) * | 2009-06-30 | 2014-05-07 | 花王株式会社 | Method for producing high bulk density detergent granules |
| AU2010320064B2 (en) * | 2009-11-18 | 2014-04-24 | Kao Corporation | Method for producing detergent granules |
| US20110166370A1 (en) | 2010-01-12 | 2011-07-07 | Charles Winston Saunders | Scattered Branched-Chain Fatty Acids And Biological Production Thereof |
| CA2827627C (en) | 2011-02-17 | 2016-10-11 | The Procter & Gamble Company | Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994003568A1 (en) * | 1992-08-01 | 1994-02-17 | The Procter & Gamble Company | Low gelling detergent compositions and a process for making such compositions |
| US5366652A (en) * | 1993-08-27 | 1994-11-22 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8329880D0 (en) * | 1983-11-09 | 1983-12-14 | Unilever Plc | Particulate adjuncts |
| EP0229671B1 (en) * | 1986-01-17 | 1991-03-13 | Kao Corporation | High-density granular detergent composition |
| JP3192469B2 (en) * | 1991-05-17 | 2001-07-30 | 花王株式会社 | Method for producing nonionic detergent particles |
| GB9113675D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Particulate detergent composition or component |
| ATE223301T1 (en) * | 1992-06-15 | 2002-09-15 | Procter & Gamble | METHOD FOR PRODUCING COMPACT DETERGENT COMPOSITIONS |
| TW244358B (en) * | 1992-10-12 | 1995-04-01 | Kao Corp | |
| US5486303A (en) * | 1993-08-27 | 1996-01-23 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
| EP0739977B1 (en) * | 1995-04-27 | 1998-12-23 | The Procter & Gamble Company | Process for producing granular detergent components or compositions |
-
1996
- 1996-03-27 MX MX9708236A patent/MX9708236A/en not_active IP Right Cessation
- 1996-03-27 CN CN96193487A patent/CN1117849C/en not_active Expired - Lifetime
- 1996-03-27 AT AT96909881T patent/ATE342955T1/en not_active IP Right Cessation
- 1996-03-27 AU AU53245/96A patent/AU5324596A/en not_active Abandoned
- 1996-03-27 EP EP96909881.3A patent/EP0870008B2/en not_active Expired - Lifetime
- 1996-03-27 JP JP8532521A patent/JPH11504364A/en not_active Ceased
- 1996-03-27 KR KR1019970707598A patent/KR100258542B1/en not_active IP Right Cessation
- 1996-03-27 CA CA002216816A patent/CA2216816C/en not_active Expired - Fee Related
- 1996-03-27 DE DE69636644.4T patent/DE69636644T3/en not_active Expired - Lifetime
- 1996-03-27 ES ES96909881T patent/ES2275274T3/en not_active Expired - Lifetime
- 1996-03-27 WO PCT/US1996/004225 patent/WO1996034082A1/en active IP Right Grant
- 1996-03-27 BR BR9608445A patent/BR9608445A/en not_active Application Discontinuation
- 1996-04-26 AR AR33629996A patent/AR001718A1/en unknown
- 1996-06-27 TW TW085107776A patent/TW323303B/zh active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994003568A1 (en) * | 1992-08-01 | 1994-02-17 | The Procter & Gamble Company | Low gelling detergent compositions and a process for making such compositions |
| US5366652A (en) * | 1993-08-27 | 1994-11-22 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0870008B1 (en) | 2006-10-18 |
| KR100258542B1 (en) | 2000-06-15 |
| AU5324596A (en) | 1996-11-18 |
| CA2216816C (en) | 2001-08-21 |
| ATE342955T1 (en) | 2006-11-15 |
| CA2216816A1 (en) | 1996-10-31 |
| CN1183798A (en) | 1998-06-03 |
| TW323303B (en) | 1997-12-21 |
| DE69636644T3 (en) | 2014-11-13 |
| JPH11504364A (en) | 1999-04-20 |
| EP0870008A1 (en) | 1998-10-14 |
| DE69636644D1 (en) | 2006-11-30 |
| EP0870008B2 (en) | 2014-07-02 |
| KR19990008074A (en) | 1999-01-25 |
| MX9708236A (en) | 1997-12-31 |
| WO1996034082A1 (en) | 1996-10-31 |
| DE69636644T2 (en) | 2007-08-23 |
| ES2275274T3 (en) | 2007-06-01 |
| AR001718A1 (en) | 1997-11-26 |
| BR9608445A (en) | 1999-01-05 |
| EP0870008A4 (en) | 1999-10-13 |
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