CN1216578A - Production of anionic detergent particles - Google Patents

Production of anionic detergent particles Download PDF

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Publication number
CN1216578A
CN1216578A CN97194066A CN97194066A CN1216578A CN 1216578 A CN1216578 A CN 1216578A CN 97194066 A CN97194066 A CN 97194066A CN 97194066 A CN97194066 A CN 97194066A CN 1216578 A CN1216578 A CN 1216578A
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China
Prior art keywords
anion surfactant
particle
detergent particles
water
agent
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Granted
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CN97194066A
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CN1156564C (en
Inventor
W·D·埃梅赖
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Unilever PLC
Unilever NV
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Unilever NV
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082Special 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
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/04Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules

Abstract

In a process for producing detergent particles comprising an anionic surfactant, a paste comprising water and the surfactant is fed to a drying zone where it is heated. Subsequently, the paste is cooled in a cooling zone. A layering agent is introduced into the cooling zone to improve granularity.

Description

The production of anionic detergent particles
The present invention relates to anionic detergent particles, its production method and the composition that contains detergent particles.More particularly, the present invention relates to the production method of the high detergent particles of anionic surfactant concentration, this method is to contain the washing composition mashed prod drying of anion surfactant, and relates to the detergent particles that obtains thus.
Usually the detergent active compound that adopts in detergent composition comprises anion surfactant, as linear alkylbenzene sulfonate (LAS), straight chained alkyl ether sulfate (LES) and primary alkyl sulphates (PAS), and nonionogenic tenside are as ethoxylated alcohol.For improving the de-sludging performance, preferably supply with the powder of high-content detergent active material.
Usually, the high-content of the active substance that can mix is limited by the requirement of production method.The detergent composition that tap density is high, its typical production method are all components of said composition and/or the matrix powder that for example obtained by spray-drying process are mixed mutually or to granulate, and compare with the composition that tap density is low, and this brings very big benefit to the human consumer.
It is known that detergent active compound is joined in this liquid detergent compositions.But because ratio that must control liquid phase and solid phase is with the formation detergent particles, so the high-content of the detergent active material that can add like this is conditional.Also having known can be with anion surfactant, and for example LAS or PAS join in the detergent composition by the mode of solid auxiliary, are about to contain other composition of this tensio-active agent and said composition, as the particle adding of yellow soda ash and washing assistant.Up to now, owing to good flowability need be provided and reduce poly-group tendency, the amount of the anion surfactant in this auxiliary is restricted always.
EP-A-506 184 announces a kind of liquid acid precursor substance successive drying neutral method with anion surfactant.Can prepare the detergent particles that activated detergent content is 30-40% (weight) with this method.
A kind of method of producing Powdered anion surfactant of EP-A-572 957 announcements: the aqueous slurry that contains 60-80% solid tensio-active agent is delivered in the vaporizer, formed dry and concentrated these slurries of layer of surface promoting agent film and one side on the reactor wall, simultaneously from wall, it scraped.
What disclose in EP-A-572 957 also has: the reactor wall temperature is 50 to 140 ℃; The highest wall temperature of embodiment is 130 ℃.It is said that higher temperature can cause thermal destruction and tonal variation, is disadvantageous therefore.And document disclosure, the point of a knife speed of scraper preferably 2 arrives 20m/s in the reactor, and the highest point of a knife speed of embodiment is 10.5m/s.Disclosed tap density is up to about 0.5g/cm 3
Yet, opposite with above-mentioned saying, as described in our No. 95/03321, PCT patent application PCT/EP (not delivering before preferential day) in present patent application, the good detergent granules of tap density height, anionic surfactant concentration height and powder property can be with following method production: heating contains the mashed prod of this tensio-active agent in comparatively high temps first area uniformly, then the particle of such formation is cooled down.
In general, aforesaid method comprises: contain water (its amount generally greater than mashed prod weight 10%) and the mashed prod of anion surfactant send into drying zone, this pasty substance of heating then cools off in the cooling zone to form detergent particles to reduce water-content in drying zone.
The method of describing in our the undocumented patent application is particularly suitable for the anionic detergent component as detergent particles with PAS.Regrettably, the amount of PAS is many more in anionic group, and detergent particles just tends to form viscous surface more, and for the requirement that final production goes out the particulate product of uniform drying, this is very deleterious.
Have been found that now a stratification agent introducing cooling zone just can address this problem.
EP-A-390 251 discloses, and when producing detergent particles, available stratification agent is as the granulating auxiliary, and wherein all components are handled in homogenizer, keeps in moderate speed's stirrer then or enters deformation stage.
Therefore, a first aspect of the present invention is to propose the method that a kind of production contains the detergent particles of anion surfactant, this method comprises following step: the pasty substance that contains water and anion surfactant is delivered to drying zone, the heating pasty substance is to reduce their moisture in drying zone, then the cooling pasty substance is characterized in that in cooling step the stratification agent being incorporated in the cooling zone to form detergent particles in the cooling zone.
Without the stratification agent, the pasty substance that adopts cooling gas to handle in the cooling zone also can reach same effect.Therefore, a second aspect of the present invention is to propose the method that a kind of production contains the detergent particles of anion surfactant, this method comprises following step: the pasty substance that contains water and anion surfactant is delivered to drying zone, the heating pasty substance is to reduce their moisture in drying zone, then in the cooling zone, cool off pasty substance, to form detergent particles, it is characterized in that with the pasty substance in the cooling draught processing cooling zone.
Cooling gas needs drying in general, for example can be air or nitrogen, for example below 0 ℃.This cooling gas can the counter-current flow mode use.
But the present invention is not limited only to the composition that anionic group contains LAS or is made of LAS.Comprise the situation of other anionic group of PAS or LES for employing, the present invention also is very useful.
The stratification agent can be anyly can give the particle coating to improve the material of its granularity at cooling stages.For this reason, preferably inactive relatively material reaches this purpose, and particularly any has the inert material of good result in washing soln, for example, and silico-aluminate, silica mica and clay.Can use these mixtures of material.Hereinafter will narrate the example of silico-aluminate and silica in more detail.This material is not got rid of this material as the coating of finished particle and is existed in this particulate body yet.
The consumption of coated fertilizer is with respect to the ratio of the total amount of this other material of particulate in cooling stages, and preferably 1: 3 to 1: 20, further preferred 1: 9 to 1: 20.
Drying zone can be chosen wantonly under rough vacuum to help to remove moisture and volatile matter.Vacuum can be high to normal atmosphere from 100 Torr, and very big production method handiness is provided like this.But, cross 500 Torr and help when vacuum operating is provided, reducing investment to atmospheric vacuum.
Stirring material can ensure control and the increase output to residence time and granular size in drying zone and/or cooling zone.
This method is preferably carried out continuously, because this is convenient to carry continuously detergent particles.In continuous processing, the flow velocity of mashed prod with 10 to 25kg/m 2/ hr the order of magnitude is advisable, and preferred 17 to 22kg/m 2/ hr, for example 20kg/m 2/ hr.
Average retention time is to be advisable less than 5 minutes in drying zone.The preferred especially residence time is less than 4 minutes, and the most preferably short as far as possible residence time decomposes the possibility of (particularly PAS) and increases product production to greatest extent reducing.
In general, mashed prod will provide the inner net heat of mashed prod to shift in the stirring heating district, thereby help removing moisture.Stirring can reduce the duration of contact between pasty state particle and the drying zone wall, adds that effective heat shifts, and just can reduce " hot spot " that may cause decomposing and form possibility.In addition, drying process is improved, and this just can make, and residence time shortening/output increases in the drying zone.
For PAS, for avoiding thermolysis, preferred pasty substance heating is no more than 170 ℃.
Method of the present invention makes might form the tap density height, for example surpasses 550g/cm 3Particle.
At the cooling zone internal cooling, its service temperature that is fit to is no more than 50 ℃, preferably is no more than 40 ℃, as 30 ℃ paste-like material.Be preferably in have in the cooling zone stir so that wherein material effectively cool off.Compare with previous public technology, the employing particle initiatively cools off, and can reduce owing to particle is heated to comparatively high temps the pyrolysated possibility to occur, and can reduce particulate viscosity.This active cooling can be by (for example the using cooling jacket) of surrounding cooling zone cold water or realize through the circulation of refrigerative water (the ethylene glycol water about as-5 ℃) for example.
Preferred pasty substance contains the mixture of anion surfactant and water, though if having a mind to add or from upstream process, for example bring into also as impurity in the production of tensio-active agent and may have other component.Preferred pasty substance contains at least 60% (weight), and more preferably at least 65%, the especially preferred anion surfactant of at least 70% (weight).Correspondingly, mashed prod contains and is no more than 50% and preferably be no more than the water of 30% (weight).The temperature of pasty substance when being admitted to drying zone should be that available pump is smoked, and this may limit the maximum of the tensio-active agent that wherein exists.
When anionic agent contained PAS, correspondingly mashed prod should be sent into drying zone under 50 ℃ to 70 ℃ temperature, preferred 50 to 65 ℃.
Method of the present invention can be implemented in any suitable device.But preferably use the scraping surface moisture eliminator, particularly the quick response device.Suitable quick response device for example comprises the dehumidification system rapidly that can buy from VRVSPAProcessi Impianti Industriali company.The drying zone heat transfer area generally is 3: 1 to 1: 1 with the ratio of cooling zone heat transfer area, for example about 2: 1.
Can optionally before the cooling zone, select to adopt two or more drying zones when needing.Can adopt individual equipment as required with drying zone and cooling zone are provided, perhaps change a kind of method, also the equipment that can adopt moisture eliminator and cooling bed to separate.
Suitable drying zone cross section is circular substantially, and therefore, it is limited by columniform wall.Preferred above-mentioned wall heats with the heating jacket that can inject water, steam or oil.Described wall is inner preferably to keep at least 130 ℃, particularly at least 140 ℃.The vaporator rate of preferred drying zone is every m 2Heating surface per hour 3 arrives 25kg water, and particularly 5 to 20kg water.
Preferred cooling zone is limited by cylindrical wall.When production process is carried out continuously, be suitable for equipment drying zone and cooling zone horizontal aligument arrangement substantially, to help efficient drying, cooling and drying and cooling zone conveying material on the cardinal principle horizontal direction.
Correspondingly, drying zone and preferred cooling zone have stirring tool that the tensio-active agent mashed prod by aforementioned region and shaped particles are stirred and carry.Stirring tool is one group of blade and/or scraper that axially is installed in the circumferentially extending in the rotating shaft preferably.Blade and/or scraper preferably tilt with effective conveying material, and preferably the gap with inwall is not more than 10mm, for example 5mm.
We find that the present invention is specially adapted to produce the high-quality detergent granules that contains LAS, and this is that the previously known technology can not obtain.But anionic group also can be PAS, LES or any other anion surfactant, and the mixture of these components and LAS or do not contain the mixture of LAS.
The most common form with free acid of LAS is commercially available.Different with very unsettled PAS acid, LAS acid is very stable and the market sale of many manufacturers arranged, Petralab 550 (Petresa) for example, Deter (Deter), Marliean (Huls), Nalkylene 540L (Vista) and Isorchem L83 (Enichem).As a kind of viscous liquid, it is easy to handle, stores and processing.Under any circumstance, the liquid anion precursor substance of anion surfactant and neutralizing agent are sent into the inlet region of drying zone or drying zone and formed anion surfactant on the spot, just can in drying zone, form mashed prod.
The LAS acid that is neutralized is with Powdered commercially available.
The LAS powder mainly is a roller drying or spray-dired, has reasonable powder property during newborn output.But seldom preferably adopt, because they can absorb moisture and the intractable that becomes sticky from air, their flowability degenerates and becomes and lumps easily.The typical powder that can obtain (available from Huls) from market is Marlan ARL (80%LAS), Marlan A390 (90%LAS), Marlan A396 (96%LAS), or (available from Unger) Ufaryl DL90 (90%LAS), Ufaryl DL85 (85%LAS) and Ufaryl DL80 (80%LAS).
The PAS that buys on market at present is finely powdered or noodles shape.Fine powder generally is a dust-like, contains in a large number the particle less than 150 microns.Generally with the dry PAS of soap flakes shape through the extrusion production strip PAS that appears, it has very big particle size and very low porosity generally speaking, causes solubility property very poor.Be to increase the content of detergent active material in the detergent composition, the detergent particles that feeds intake after the what is called is arranged as everyone knows, can provide activity substance content high composition.
But, after being not suitable in general, finely powdered PAS and noodles shape PAS be dosed in the washing combination, particle size is different in general because composition grain is with the rearmounted particle that drops into, and it is very poor therefore to tend to segregation and outward appearance.The obtainable washing granule of the method according to this invention has high-load detergent active material, suitable porosity and particle size characteristic.
So, a third aspect of the present invention provides the anionic surfactant granules that contains particle weight 60% at least, preferably contain LAS or form by LAS, and containing the detergent particles that is no more than 5% water, this particle is coated with according to the present invention first or the stratification agent that obtains of the method for second aspect by bag.
According to a forth aspect of the invention, the detergent particles that contains anion surfactant is provided, preferably contain LAS or form by LAS, and preferably its amount is at least 60% of particle weight, and wherein, this particle is coated with the stratification agent by bag, and containing porosity is 0% to 25% of particle volume, size-grade distribution is as follows: at least 80% particle size is at 180 to 1500 microns, preferred 250 to 1200 microns, and less than 10% and preferably less than 5% particle diameter less than 180 μ m.
In this detergent particles, the amount of suitable anion surfactant is at least 70% of a particle weight, preferably at least 80%, preferably at least 85%.Preferably this particle also contains water, and its amount is 0% to 8%, preferred 0 to 4% of particle weight.Water in the particle can improve particle integrity, thereby reduces fine grain amount.
Preferably the long-width ratio of detergent particles is no more than 2, more preferably totally is that spheric is emanated out to reduce from other particle of preparation said composition, and improves the profile directly perceived of powder.
Preferred LAS anion surfactant chain length is C 8To C 16, more preferably from C 9To C 15, most preferably from C 10To C 14Close limit.
If add PAS, this tensio-active agent chain length is C 10To C 22, preferred C 12To C 18, more preferably C 12To C 14Close limit, Coco PAS is especially desirable.
Detergent particles can contain PAS and other tensio-active agent and/or nonsurfactant mixture of ingredients on demand.
Other suitable tensio-active agent can comprise the straight chained alkyl ether sulfate, the oxo process alcohol sulfate.C for example 11To C 15And C 13To C 15Alcohol sulfate, secondary alcohol sulfate and sulfonate, unsaturated tensio-active agent is sodium oleate, oleyl sulfate, alkene sulfonate for example, or its mixture.
Especially preferably be rich in the detergent particles of LAS, promptly wherein the amount of LAS more preferably surpasses the total amount of all other tensio-active agents and nonsurfactant above the amount of any other tensio-active agent or nonsurfactant.
To adopt the sodium salt of tensio-active agent in general, but also may have the salt of K, Ca or Mg.Yet the inlet region before preferably the anion surfactant of sour form and neutralizing agent being sent into drying zone or be right after drying zone forms anion surfactant on the spot, to form this anionic group.
If generate anionic agent on the spot in drying zone, the neutralization heat of then emitting in drying zone can reduce the required of indirect heating drying zone, thereby is very beneficial for the method that adopts the tensio-active agent mashed prod to make raw material.
And, if precursor acids can liquid state rather than aqueous solution mode send into drying zone, and neutralizing agent can concentrate, that also is good.The total amount that enters the water of drying zone is compared and can be significantly reduced with the method that adopts the tensio-active agent mashed prod.Described mashed prod may need the water of at least 30% weight can be pumped fortune.
Also can before adding the stratification agent, directly form detergent particles from the precursor acid starting material, rather than two step method: generate tensio-active agent, then form mashed prod and dry, to form detergent particles.Its advantage is to avoid forming the tensio-active agent mashed prod, because it need carry and store this mashed prod, and gives the technical difficulty that causes.
Precursor acids, for example LAS or PAS acid are suitable for sending into drying zone with liquid phase.Because precursor acids may be heat-labile,, make to reduce to minimum, and preferably can avoid fully because caused this acid heat of the temperature that raises decomposes so preferred N-process should be enough fast, and react completely basically.
Precursor acids is suitable for being 40 to 60 ℃ in temperature carries down, is that liquid state is unlikely thermolysis again to guarantee it.Neutralizing agent can be at any temperature required drying zone of input down.
The neutralizing agent of introducing is suitable to the aqueous solution or slurries or solid material introducing.
The conventional neutralizing agent that can adopt comprises alkali-metal oxyhydroxide, for example sodium hydroxide and alkali-metal carbonate, and for example yellow soda ash preferably adds with solid material.
The amount of neutralizing agent is advisable with 25 to 55% of the aqueous solution or slurry weight, and preferred 30 to 50%.Neutralizing agent concentration height may cause undesirable crystallization effect, and concentration is low because the ratio of water is undesirable too greatly also.
For water-content in the control drying zone can change the concentration of neutralizing agent solution or slurries.So just can reach best viscosity characteristics, thus make material in the drying zone keep carrying/can be pumped the state of fortune.
Can adopt neutralizing agent with respect to precursor acids excessive amount on stoichiometric ratio.As the thermolysis of fruit part precursor acids, issuable acid, for example sulfuric acid can combine with excessive neutralizing agent.
Contain in advance the method for the mashed prod of neutral tensio-active agent with employing and compare, adopt neutralization on the spot can export product fast.
Precursor substance in the stirring heating district and neutralizing agent (hereinafter being referred to as raw material) can provide effective heat transfer in general and help removing moisture.Stir the duration of contact that reduces between raw material and the drying zone wall, add net heat and shift, just can reduce the possibility that causes pyrolysated " hot spot " to form.And, drying improve can shorten in the drying zone the residence time/raising output.
Other nonsurfactant component that can exist in the detergent particles comprises dispersion aids, preferred polymers dispersion aids, more preferably urea, sugar, polyalkylene oxide and hereinafter described washing assistant.
If necessary, this detergent particles can contain organic and/or inorganic salt, but as the salt of hydration.Suitable material in the salt, tri-polyphosphate, Citrate trianion, carbonate, vitriol, the muriate of preferred sodium.Also can comprise silico-aluminate, clay, silica and other inorganic materials.
This particle can contain one or more nonionogenic tensides, for example below about being mentioned with the matrix powder of this particle fusion those.
Also can comprise inorganic materials in same this particle, for example PEG and other polymkeric substance washing assistant or soap class, those as hereinafter mentioning.
When the anion surfactant component contains LAS, there is salt in preferred especially this particle.
The amount of salt can be up to 50% of this particle weight, and is preferably the highest by 30%.
This detergent particles is dosed in the resulting matrix powder of conventional washing composition production method after can be directly, ordinary method comprises the non-tower production method, wherein all components of detergent composition are pressed method mixing and the granulating of describing among the EP-A-367 339, and comprise spray-drying process (then can select rearmounted tower multiviscosisty).Because the detergent particles that the present invention produces can be dosed into later in this powder, so formulation flexibility is very big, and the amount of active substance can strengthen on demand in whole compositions formulated.Further advantage is to produce the matrix powder that is substantially free of the washing composition active material, and the washing composition property controlled compound go up substantially can be fully as after the particle that feeds intake add.
Therefore another aspect of the present invention provides the cleaning composition that contains described detergent particles in the present invention third and fourth aspect and matrix powder.
When the matrix powder was produced with spray-drying process, detergent active material content was particularly advantageous in the selection reduction matrix powder, thereby because the low high yield that can guarantee of detergent active compound content improves integral production efficient in spray-drying process.
Composition of the present invention also can contain detergent builder compound except detergent active compound, and appoints and to contain bleach and other activeconstituents to strengthen scourability.
Except after the detergent particles that feeds intake, detergent composition of the present invention can also contain one or more detergent active compounds (tensio-active agent), these compounds can be selected from: the negatively charged ion of soap class and non-soap, positively charged ion, nonionic, both sexes and zwitterionic detergent active compound, and their mixture.Many suitable detergent active compounds all can be buied from market, and have a detailed description in the literature, for example, and in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch work) book.Preferred available detergent active compound is soap class and synthetic non-soap anionic and non-ionic compound.
Anion surfactant is that this area professional is known.Example comprises alkylbenzene sulfonate, and particularly alkyl chain length is C 8-C 15Linear alkylbenzene sulfonate; The second month in a season and primary alkyl sulphates, particularly C 12-C 15Primary alkyl sulphates; Sulfated alkyl ether; Alkene sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinate amber salt; And fatty sulfonate.General preferred its sodium salt.
Operable ionic surfactant pack is drawn together the second month in a season and primary alcohol ethoxylate, the C that particularly every mol of alcohol and average 1 to 20 moles of ethylene oxide form 8-C 20Fatty alcohol ethoxylate, and the C of particularly every mol of alcohol and the formation of average 1 to 10 moles of ethylene oxide 10-C 15Primary aliphatic alcohols and secondary alcohol ethoxyl compound.The ionic surfactant pack of non-ethoxylated thing is drawn together alkylpolyglycosides, glycerol monoethers and poly-hydroxyl acid amides (glucamide).
The total amount of tensio-active agent is advisable to 40wt% with 5 in this detergent composition, though also can adopt the amount that exceeds this scope.
Detergent composition of the present invention also contains washing assistant in general.Its total amount suitable in composition is 10 to 80wt%, preferred 15 to 60%.Washing assistant can be the auxiliary that contains other component, perhaps if necessary, also can adopt the isolating separately lotion-aid particle that contains one or more washing assistants.
The inorganic builders that can provide comprises yellow soda ash, if necessary, can combine use with the lime carbonate crystal seed, as pointed among the GB-A-1 437 950; Crystalline state or amorphous silico-aluminate such as zeolite (open in GB-A-1 473 201); Amorphous silico-aluminate (open in GB-A-1 473 202); And crystalline state/non-crystalline state blended silico-aluminate (open in GB 1 470 250); And layered silicate (open in EP-B-164514) all can.Also can add inorganic phosphate builders, for example, the orthophosphoric acid salt of sodium, pyrophosphate salt and tri-polyphosphate, but be based on the environmental protection reason, no longer preferred these materials.
Silico-aluminate is regardless of being as the stratification agent and/or joining in the detergent particles body that its suitable total amount is 10 to 60wt%, preferred 15 to 50wt%.The zeolite that uses in most of commercialization granular detergent compositions is zeolite A.But advantageously, the high aluminium zeolite P (zeolite MAP) of description and patent protection also can use in EP-A-384070.Zeolite MAP is a kind of alkali metal aluminosilicate of P type, and the ratio of its sial is no more than 1.33, preferably is no more than 1.15 and more preferably no more than 1.07.
The organic washing-assisting detergent that can add comprises polycarboxylate polymer such as polyacrylate, vinylformic acid/maleic acid and propylene phosphinate; Monomer multi-carboxylate such as Citrate trianion, gluconate, oxygen connection succinate, glycerine list, two, three succinates, carboxyl methoxy succinate, carboxymethyloxymalo,ates, dinicotinic acid salt, hydroxyethyliminodia,etates, alkyl and thiazolinyl malonate and succinate; And sulfonated soap.The multipolymer of toxilic acid, vinylformic acid and vinyl acetate ester is particularly preferred, because it is biodegradable, thus compliance with environmental protection requirements.Herein not with above-named as limit.
Particularly preferred organic washing-assisting detergent is a Citrate trianion, and suitable consumption is from 5 to 30wt%, preferred 10 to 25wt%; And the polymerizing acrylic acid thing, the more preferably multipolymer of vinylformic acid/toxilic acid, suitable consumption be from 0.5 to 15wt%, and preferred 1 to 10wt%.Preferred washing assistant is an alkali metal salt, particularly sodium-salt form.
Suitable builder system contains the crystalline state layered silicate, and for example, available from the SKS-6 of Hoechst, zeolite is as zeolite A and optional alkali metal citrate.
Also can contain bleach system according to detergent composition of the present invention, peroxide bleaching compound preferably, for example, and inorganic persalt or organic peroxide acid, they can produce hydrogen peroxide in the aqueous solution.The peroxide bleaching compound can and bleach-activating agent (bleaching precursor substance) use together, to improve the bleaching action under the low wash temperature.Particularly preferred bleach system contains peroxide bleaching compound (preferred SPC-D, can use with bleach-activating agent arbitrarily), and transition metal bleach catalyzer (in EP 458 397A and EP-A-509 787 open and require patent protection).
Composition of the present invention can contain basic metal, and the carbonate of preferred sodium is to increase cleansing power and processing easily.The suitable amounts of yellow soda ash can be from 1 to 60wt%, and preferred 2 to 40wt%.But, contain on a small quantity or do not contain yellow soda ash composition also within the scope of the invention.
Add the small quantities of powder structural agent, for example, lipid acid (or fatty acid soaps class), sugar, acrylate or acrylate/maleate polymkeric substance, or water glass (its suitable amounts from 1 to 5wt%) can improve the flowability of powder.
The material that can add in the detergent composition of the present invention comprises water glass; Comprise the silicate corrosion inhibitor; Anti-redeposition agent is as cellulose polymer compound; Fluorescent agent; Inorganic salt are as sodium sulfate; Foaming control agent or short foaming agent (when suitable); Proteolytic ferment and lipolytic enzyme; Dyestuff; Color dot is sewed agent; Spices; Froth suppressor; With the fiber softening compound.Be not limited to above cited.
Substrate composition is fit to use spray drying method for preparation: compatible insensitive component slurries spraying drying hot in nature, be sprayed to then, be admixed to and/or after be dosed on the component that is not suitable for by the slurries processing.The detergent particles of producing according to the inventive method is dosed in the substrate composition after with ordinary method.
The preferred tap density of detergent composition of the present invention is at least 500g/l, more preferably 550g/l at least.
This powder can be used the rearmounted tower multiviscosisty method of spray-drying process, spray-dried powders, or all non-tower process such as dry mixed granulation prepare.For mixing herein, it is favourable adopting super mixer/Fitz chilsonator.Adopt the method for super mixer/Fitz chilsonator for example to exist, EP-A-340013, EP-A-367339 have disclosure among EP-A-390251 and the EP-A-420317.
Now explain the present invention in more detail with following non-limiting instance.Technological process
Use 1.2m 2VRV equipment, three equal chuck sections are arranged.Liquid and powder charging opening are positioned at tight the place ahead of the first hot-zone section, in the end in two sections middle chuck layer charging opening are arranged.Adding the grain mouth by this is added to the mouth that boils in the last section.Electronic oil heater is given the first two chuck section heating, and the oil temperature of use is between 120 ℃ and 190 ℃.With chuck treated, that circulating waters 15 ℃ cool off last section.In the steam pumping extraction fan, open a bypass, the make-up gas current control by reactor 10 and 50m 3Between/the hr.All experiments are all made of the full speed electric motor, and its top speed is about 30m/sec.
One-way pump is calibrated the LAS acid with the room temperature that feeds intake, and a peristaltic pump is calibrated with 47% sodium hydroxide that feeds intake.Screw feeder is calibrated the zeolite A24 that uses with feed intake yellow soda ash and stratification.Yellow soda ash and liquid add in the tight the place ahead of the first hot pressing section, and the agent of zeolite stratification adds in the 3rd section that is cooled.Zeolite adds with minimum, leaves moisture eliminator to obtain free flowing powder.
In these examples, used following dummy suffix notation:
D (4,3)=weighted mean particle diameter;
DFR=kinetics flow velocity;
The uncompacted compression testing of UCT=.Embodiment 1
LAS acid and sodium hydroxide
Experiment is carried out under different output and jacket temperature.Some device parameter and powder are listed in table 1.In following all examples, all need the agent of zeolite stratification.
Table 1 specimen holder sleeving temperature estimated output tap density DFR %COMP UCT D (4,3)<180>1400
178 ℃ 41.9 599 128 12.4 0.25 869 2.96 14.44 of 178 ℃ of 91.9 463 101 17.6 0.0 1,522 0.0 78.81 E of 178 ℃ of 76.0 576 129 5.3 0.0 1,351 1.11 49.82 D of 178 ℃ of 65.2 617 130 4.7 0.0 1,116 3.32 33.2 C of 170 ℃ of 37.9 621 142 4.1 0.0 845 1.58 8.2 B of KG/HOUR micron micron micron A
Sample A has fabulous powder property and rational average particle size particle size.Consider that these powder all contain the 90%LAS that has an appointment, its flowability is unusual.When output increased, all some reduced sample B to the flowability of D, and particle size increases simultaneously.The increase of particle size is because the interior residual moisture of particle is higher.When output reduced, mobile improvement and particle size reduced in E.
Just can not produce any of above-mentioned powder without the agent of zeolite stratification.Embodiment 2
LAS acid and solid phase yellow soda ash
Experiment is to carry out under the different degree of neutralization of yellow soda ash.Some device parameter and powder property are listed in table 2.The agent of zeolite stratification all must be arranged in following all examples.
Table 2 specimen holder sleeving temperature estimated output %NA2CO3 piles up DFR %COMP UCT D (4,3)<180>1400
KG/HOUR transforms 145 ℃ 72.2 83 601 141 7.1 0.0 of 145 ℃ of 64.9 73 597 131 11.2 0.0 849 0.29 4.64 D of density micron micron 145 ℃ of 57.6 63 594 140 7.6 0.0 946 0.3 6.57 C of 145 ℃ of 42.7 42 624 131 5.9 0.0 812 1.47 6.25 B of micron A
Because do not add water, the moisture evaporation degree is very low in these experiments.Water is mainly from the Zhong Heshui of LAS acid.Like this, adopt 145 ℃ of lower chuck layer temperature.Adopt fixed powdered sodium carbonate flow, increase the LAS acid content simultaneously, so that consistent, as shown in table 3 with the degree of neutralization of 42% to 83% LAS acid.
The all powder of being produced all has excellent flowing performance and rational average particle size particle size.When in and degree when increasing, output also increases, powder property does not degenerate.
Just can not produce any of above-mentioned powder without the agent of zeolite stratification.
According to of the present invention open, together with the four corner of the present invention that claims limited, improving described embodiment and other embodiment is conspicuous to this area professional.

Claims (14)

1. a production contains the method for the detergent particles of anion surfactant, this method comprises the following steps: the pasty substance that contains water and anion surfactant is sent into drying zone, pasty substance in the heat drying district is to reduce its water-content, then in the cooling zone, cool off pasty substance to form detergent particles, it is characterized in that, in cooling stages, the stratification agent is introduced in the cooling zone.
2. a production contains the method for the detergent particles of anion surfactant, this method comprises the following steps: the pasty substance that contains water and anion surfactant is sent into drying zone, pasty substance in the heat drying district is to reduce its water-content, then the cooling pasty substance is characterized in that with the pasty substance in the cold air stream processing cooling zone to form detergent particles in the cooling zone.
3. method according to claim 1 and 2, wherein anion surfactant contains linear alkylbenzene sulfonate.
4. method according to claim 3, wherein linear alkylbenzene sulfonate accounts for 10% to 100% of anion surfactant gross weight.
5. according to the described method of above-mentioned arbitrary claim, wherein pasty substance contains the water that is no more than 50wt%.
6. according to the described method of above-mentioned arbitrary claim, wherein the stratification agent comprises silico-aluminate, silica or its mixture.
7. method according to claim 1, wherein the stratification agent is by being to join the cooling zone in 1: 5 to 1: 20 with respect to final particle weight ratio.
8. according to the described method of above-mentioned arbitrary claim, wherein anion surfactant is that anion surfactant with free acid form mixes generation mutually with neutralizing agent.
9. according to the described method of above-mentioned arbitrary claim, wherein the gained particle contains at least 75% (weight) anion surfactant and the water that is no more than 10% (weight).
10. according to the described method of above-mentioned arbitrary claim, wherein gained particle tool D (4,3) average particulate diameter is 180 to 1500 microns.
11. contain the anion surfactant that accounts for particle weight at least 60% and be no more than the detergent particles of the water of particle weight 5%, this particle is wrapped by the stratification agent and is coated with, and can obtain according to the method for aforementioned any claim.
12. contain anion surfactant, its amount is at least 60% detergent particles of particle weight, wherein this particle is wrapped by the stratification agent and is coated with, and porosity is 0% to 25% of a particle volume, and particle size distribution has 180 to 1500 micron-scales at least 80% particle.
13. according to claim 11 or 12 described detergent particles, wherein anion surfactant contains linear alkylbenzene sulfonate.
14. a detergent composition contains each described detergent particles and matrix powder among the with good grounds claim 11-13.
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AU733689B2 (en) 2001-05-24
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WO1997032002A1 (en) 1997-09-04

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