CN1077486A - High active detergent pastes - Google Patents
High active detergent pastes Download PDFInfo
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- CN1077486A CN1077486A CN93104045.0A CN93104045A CN1077486A CN 1077486 A CN1077486 A CN 1077486A CN 93104045 A CN93104045 A CN 93104045A CN 1077486 A CN1077486 A CN 1077486A
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- ethoxy sulfate
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- 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
- C11D11/04—Special 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Abstract
A kind of detergent slurry composition, it contains the anion surfactant of 50%-94% (weight); The water of the alkyl ethoxy sulfate and 5%-35% of 1%-30% (weight) (weight).In velocity of shear is 25s
-1The time record 70 ℃ down these slurry viscosities greater than 10Pas.The rheological property of this slurry makes it be suitable for further being processed into very high-activity detergent piece material, and this piece material can be used in the free-pouring granular detergent composition.
Description
The present invention relates to pumpable high active surfactant slurry, this slurry is suitable for further being processed into detergent particles, the invention still further relates to the preparation method of this slurry.
So far, detergent granules is mainly used spray drying method for preparation.In the spraying drying operation, detergent component mixes to form a kind of slurry with water up to 35-50% as tensio-active agent and washing assistant.With the slurry heating that obtains, and spraying drying, its expense is higher.Yet a kind of good agglomeration process is comparatively cheap.
There are many non-spray-drying processes can produce detergent particles in the prior art.Great majority need direct neutralize anionic surfactant acid before the granulating step or in the granulating process.
Yet these methods all have certain limitation.Neutralization and combining closely of granulating step have been limited the scope of used processing conditions greatly.And, if instability when the anion surfactant selected for use is acid type (as alkyl-sulphate), then sulfonation and neutralization and granulating step must be closely linked.Its result will limit the logistics and/or the design of these technology equipment useds greatly, and can increase the complicacy and the difficulty of whole process control system greatly.
The object of the invention provides a kind of high reactivity anion surfactant slurry, and the rheological property that it has makes that it is suitable for that pump is taken out, the transportation between the storage, manufacturing location, and further is processed into high active detergent granules by reuniting.A key character of the present invention is that granulating/agglomeration step is separated fully with sulfonation procedure.
Have now found that and add the rheological property that a small amount of alkyl ethoxy sulfate can improve this surfactant paste greatly.
On November 28th, 1979, disclosed GB 2021141 described the surfactant paste composition in the narrow concentration range of stream layer (' G ') in mutually.
Describe among September 21 nineteen eighty-three disclosed GB 2116200 by up to about 40%(weight) contain the ethylization tensio-active agent and make the paste compound that the anion surfactant of dissolution aids is formed, reach piece material by these compositions generations.
Disclosed EP 403148 described and contained the high active surfactant composition that is less than 14% water December 19 nineteen ninety.Also mention in reducing with process auxiliaries and the viscosity of highly active slurry in the loop.Also openly make suitable process auxiliaries with polyoxyethylene glycol and ethoxylated non-ionic type tensio-active agent.
The high active surfactant composition that describe among the disclosed EP 399581 November 28 nineteen ninety contains the anion surfactant of ethoxylation and the nonionic surface active agent of ethoxylation.
The present invention relates to a kind of detergent slurry composition, it contains 50%-94%(weight) anion surfactant; 1%-30%(weight) alkyl ethoxy sulfate and 5%-35%(weight) water.In velocity of shear is 25s
-The time record the viscosity of this slurry under 70 ℃ of temperature greater than 10Pa.S.The present invention also comprises a kind of preparation method of this slurry.
The alkyl ethoxy sulfate of having found this paper can be used as rheology modifiers, makes this anion surfactant slurry have the characteristic of simple shear-thinning fluid (having a yield point).Therefore, dense slurry of the present invention also available pump is taken out, certainly can thickening in the course of processing.
Surfactant paste
Usually with have a plurality of yield points non--Newtonian, shearing weakens rheological model and describes the surfactant paste that is the strong solution form.These slurries have lower viscosity (referring to Fig. 1) usually when velocity of shear increases.
Beyond thoughtly be, have now found that under certain condition (surfactant types, concentration, inorganic content, unsulfonated material content, temperature etc.), these slurries show morphological evolutions, promptly under certain velocity of shear, viscosity increases with velocity of shear.This phenomenon is called as shear thickening.
The shear thickening that exists in these slurries makes its transportation usually, stores and be treated as a very task of difficulty.Pump take out and transport process in the slurry of issuable these shear thickenings can cause pressure obviously to descend, and may blocking pipe.For the conveying that makes these slurries (a kind of powerful operation) is suitable for industrial application, must the shear thickening situation not take place assurance, and make the rheological of this slurry become typical shearing to weaken fluid (have or do not have yield point).
This separates the neutralization of preparing washing agent finished granule and granulating step fully then.This slurry can be stored between these two steps.In addition, also can between two manufacturing locations, carry.This means that this preparation technology greatly simplifies, and become more flexible.
The physicals of slurry
This slurry has high viscosity, is 25s in velocity of shear
-1The time record its 70 ℃ viscosity greater than 10Pa.S, but it has rheological property, takes out so that it is easy to pump, and is convenient to further do to reunite handle.The viscosity of this slurry under 70 ℃ is more preferably greater than 20Pa.S.
The preparation method of this slurry is hereinafter also described.
This slurry is by two kinds of main components, and anion surfactant (" activity " component) and alkyl ethoxy sulfate (" rheology control agent ") are formed.The more detailed description of these components is as follows.
Anion surfactant
Aqueous surfactant paste contains a kind of organic surface active agent that is selected from anion surfactant and composition thereof.Be used for tensio-active agent of the present invention as described in the people's such as Laughlin of the US 3664961 of the Norris of on May 23rd, 1972 approval and approval on December 30th, 1975 the US 3919678.
This slurry contains the anion surfactant of high density, and it accounts for the 50%-94% of this slurry weight, is preferably 60%-85%.
The anion surfactant that is used for the present composition is the water-soluble salt of higher fatty acid, i.e. " soap ".This comprises alkali metal soap, as contains 8-24 carbon atom, the sodium of the higher fatty acid of preferably about 12-18 carbon atom, potassium, ammonium and alkylammonium salt.Can make these soaps by the direct saponification of fat and oil or by the free fatty acids neutralization.Useful especially is the sodium and the sylvite of the fatty acid mixt that obtained by Oleum Cocois and tallow, i.e. sodium or potassium tallow and coconut soap.
Useful anion surfactant also comprises the water-soluble salt of the organosulfur reaction product of the alkyl group that contains 10-20 the carbon atom of having an appointment in the molecular structure and sulfonic acid or sulfate group (moieties that comprises carboxyl groups in the term " alkyl "), is preferably its basic metal, ammonium and alkylammonium salt.The example of this class synthetic surfactant is sodium and potassium alkyl-sulphate, particularly by higher alcohols (C
8-C
18Carbon atom) alkyl-sulphate that obtains of (those alcohol that reduction makes as the glyceryl ester by tallow or Oleum Cocois) sulfation; And the alkylbenzene sulfonate of sodium and potassium, wherein alkyl group contains 9-15 carbon atom approximately, is the straight or branched structure, as US 2220099 and US 2477383 described those types.Useful especially is the linear straight chain alkylbenzene sulfonate, and wherein average carbon atom number is about 11-13 in the alkyl group, is abbreviated as C
11-C
13LAS.
Other anion surfactant that is suitable for comprises the water-soluble salt of α-alpha-sulfonated fatty acid methyl ester among the present invention, contains 6-20 carbon atom in its fatty acid group approximately, then contains 1-10 the carbon atom of having an appointment in ester group; The water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid contains 2-9 carbon atom approximately in its carboxyl groups, and its alkyl group part contains 9-23 carbon atom approximately; The water-soluble salt that contains the alkene sulfonate of 12-24 carbon atom approximately; β-oxyalkyl chain alkyl sulfonate contains 1-3 carbon atom approximately in its alkyl group, and its alkyl group part contains 8-20 carbon atom approximately.
The preferred anionic surfactants surfactant paste is the mixture of linearity or branch-alkylbenzene sulfonate (alkyl with 10-16 carbon atom) and alkyl-sulphate (alkyl with a 10-18 carbon atom).Normally by a kind of fluid organic material and sulphur trioxide are reacted to generate sulfonic acid or sulfuric acid, this acid that neutralizes then makes to generate this sour salt these slurries.This salt is the described in the whole text surfactant paste of this paper.Sodium salt preferably, this is because with respect to other neutralization reagent, it helps final enforcement, and the cost of NaOH is low, but is not must usefulness, because other reagent such as KOH also can use.
Being used for particularly preferred tensio-active agent of the present invention comprises: the linear C of sodium
11-C
13Alkylbenzene sulfonate; Alhpa olefin sulfonate, C
11-C
13The alkyl benzene sulphonate (ABS) triethanol ammonium; Alkyl-sulphate (tallow, coconut, palm, synthetic source such as C
14-C
15Deng) the water-soluble sodium salt and the sylvite of methyl ester sulfonate and coconut and tallow fatty acids.
Most preferably be linear C
11-C
13Sodium alkyl benzene sulfonate, tallow alkyl sulfonate and composition thereof.
Alkyl ethoxy sulfate
Rheology control agent in this slurry is selected from the alkyl oxidation of ethylene ether sulfate (being commonly referred to alkyl ethoxy sulfate) of the ammonium salt of basic metal, alkaline-earth metal, ammonium or replacement, its each molecule contains the ethylene oxide of 1-7 the unit that have an appointment, and wherein alkyl group contains 10-18 the carbon atom of having an appointment.The content of alkyl ethoxy sulfate is the 1%-30% of slurry weight, is preferably 1%-15%.
The sodium or the sylvite that preferably contain the alkyl ethoxy sulfate of 2-4 unit ethylene oxide approximately.
Most preferably synthetic, side chain C
13-C
15, C
14-C
15Or C
12-C
15The sulfating product of ethoxylated alcohol, its each molecule on average contains the ethylene oxide of 3 units that have an appointment.
Anion surfactant will change with the rheological property of selected anion surfactant with the ratio of alkyl ethoxy sulfate.This ratio variation range is 2: 1(is as being under the tallow alkyl sulfate situation at anion surfactant) to 50: 1(is as being under the mixture situation of 75%LAS and 25% tallow alkyl sulfate at this anion surfactant).Preferred ratio is applicable to that anion surfactant is C at 9: 1
14-C
15The situation of alkyl-sulphate.
The water-content of this slurry
The water-content of this slurry is a 5%-35%(weight).For can make high active detergent granules in granulating/agglomeration step, low water-content is preferred.
The selectivity composition
In slurry of the present invention, can contain detergent composition other component commonly used.These components comprise additional surfactant, hydrotropic agent, short infusion or suds suppressor, anti-dark dose and sanitas, dirty sticking suspension agent, soil releasing agent, sterilant, PH conditioning agent, enzyme stabilizers, spices, polymkeric substance (comprising polyacrylic ester) and multipolymer (comprising toxilic acid and acrylic acid multipolymer).
Additional surfactant is selected from negatively charged ion, zwitter-ion, both sexes, positively charged ion and nonionic surface active agent.
Suitable anion surfactant comprises alkyl polyglucoside, alkyl glycerol base oxethyl sulfonate and alkyl glucose amide.
Suitable nonionic surface active agent comprises the polyethylene oxide condensate of alkylphenol and contains the water-soluble condensation product of 8-22 fat of carbon atom alcohol, and this Fatty Alcohol(C12-C14 and C12-C18) can be the straight or branched structure, and every mol of alcohol contains 4-25 molar ethylene oxide compound.
The semi-polarity nonionic surface active agent comprises amine oxide, phosphine oxide, and sulfoxide also is applicable to this slurry.
Amphoterics comprises by those of secondary amine and tertiary amines derived, zwitterionics comprise by fatty quaternary ammonium deutero-those, phosphorus and sulfonium compound are also available.
Technology
Be preferably in a kind of continuous neutralized system, as from Seattle, WA USA chemical company bought continuously in and produce this surfactant paste in the loop.In continuously and in the loop, organosulfur/sulfonic acid and metal hydroxides strong solution (oxyhydroxide weight is approximately greater than 45%) be added to carry out in the neutral loop.For the present invention, the most handy alkali hydroxide soln, hydroxide concentration are 50%-75%, and this is because higher concentration can make the water in the final slurry less.
This loop also will add other water vapor, or mixes so that reach the desired water yield in the final slurry with this metal hydroxides.
Be used for preparing the organosulfur/sulfonic acid of surfactant paste preferably at sedimentation membrane reactor SO
3Make by method of sulfonating, referring to " synthetic detergent " the 7th edition, A.S.Davidson and B.Milwidsky, John Wiley and Sons, Inc., 1987, the 151-168 pages or leaves.
During the content of alkali metal hydroxide cans be compared to most and the required stoichiometry of organosulfur/sulfonic acid excessive slightly.But remaining (free) alkalescence should be no more than about 1.5%M
2O(wherein M is a metal), otherwise this slurry can be difficult to circulation because of viscosity is high.If it is about below 0.1% that residue alkalescence drops to, then owing to hydrolytic action, this surfactant paste can be steady in a long-term.Therefore, the residue alkalescence of this slurry in neutralized system (usable acid titration and measure) preferably is about 0.1%-1.5%, is preferably 0.2%-1.0%, is most preferably 0.3%-1.0%.
Organosulfur/sulfonic acid and alkali metal hydroxide are put into continuously and the loop, preferably put into the high-shear mixer in this and loop, so that their fast as far as possible mixing.
Can add alkyl ethoxy sulfate in any appropriate steps of this technology, be added in this slurry after being included in the neutralization circulation, or even in hold tank, add, as long as enough mechanical energy is provided, so that the salt final blending of alkyl ethoxy sulfate and anion surfactant is together.
A preferred embodiment of the present invention be during alkyl ethoxy sulfate directly is added to and the loop in.Like this, rheological characteristics of the present invention in and embody in the slurry in the loop.And need not other mixing step later on.
Another kind method is to make the ethoxylated alcohol sulfation simultaneously in the anion surfactant sulfonation.Then these two kinds of components can in and the loop in be neutralized the slurry of being wanted component to obtain together.
The further processing of slurry
Slurry of the present invention can be processed into high-activity detergent piece material with any common granulating/agglomeration step.This slurry is mixed with the dry detergent powder and make its caking.
Can make other composition that this slurry viscosity increases and/or fusing point improves and/or viscosity reduces by in the liquid stream that contains this anion surfactant and/or other tensio-active agent, adding, can realize extremely attractive selection scheme in the preferred embodiment of the present invention, with surfactant concentrations in the final particle of further increase.In the preferred embodiment of the inventive method, these compositions can join in the pipeline when mashing pump being extracted in the caking machine.The example of these compositions is various powder, comprises zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate or the like, and process auxiliaries such as starch.
Flow of powder
Though the preferred embodiment of the inventive method comprises the above-mentioned slurry that passes through and introduce anion surfactant, but still have a certain amount ofly, for example be the form of voluminous powder by flow of powder.In these embodiments, the viscosity of this flow of powder and humidity must remain on low-level, thereby prevent that this anion surfactant " load " from increasing and the contained surfactant concentration of piece material of generation is too high.The liquid stream of preferred reunion operation also can be used for introducing other tensio-active agent and/or polymkeric substance.By this tensio-active agent being premixed in a kind of liquid stream, or another kind of method, can accomplish this point by will various liquid streams introducing in these caking machines.These two kinds of process implementing schemes can make the performance (distribution, gelling, dissolution rate etc.) of finished particle produce difference, especially, and when before particle forms, generating the blended tensio-active agent.For various selection process, these differences all can find suitable utilization then.
Also find, utilize methods described herein, can in final chemical formula, introduce high-load some compound (as non-ionic type by any other known processing approach, and some key property (caking, compression etc.) of this matrix is not had disadvantageous effect citric acid).
Agglomeration step
Term used herein " reunion ", the meaning be meant in a finely divided mixing tank, is about the speed (except as otherwise noted) of second 5m/ second-50m/ with insert tip speed, and said mixture is mixed and/or granulating.The total holdup time of mixing and granulating operation is preferably 0.1-10 minute, more preferably 0.1-5 minute, is preferably 0.2-4 minute.Preferred mixing and granulating tip speed are about 10-45m/ second and are about 15-40m/ second.
Any unit of treat surface promoting agent or subassembly of being applicable to all can be used for carrying out the inventive method.Suitable device comprises, for example, and sedimentation film sulphonation reactor, digestive shelf, esterifier etc.For mixing/reunion, many mixing tanks/reunion device is all available.In a preferred embodiment, the inventive method is carried out continuously.Particularly preferably be Co., the Fukae that Japan makes by Fukae Powtech Kogyo
RThe mixing tank of FS-G series; This equipment is the shape of bowl shaped container basically, the charging by the top, and agitator is equipped with in its bottom, has Z-axis in fact, and a cutting unit is arranged on its sidewall, and this agitator and cutting unit are operated independently of one another, its speed independent variable.This container can be installed a cooling jacket, or if need, adorns a cryogenic unit.
Find that also other similar mixing tank also is applicable to the inventive method, it comprises Dierks and Sohne, the Diosna of Germany
RV series and TK Fielder Ltd., the Pharma Matrix of England
RCan believe that other mixing tank that is applicable to the inventive method is Fuji Sangyo Co., the Fuji of Japan
RThe Roto of VG-C series and Zanchetta and Cosrl Italy
R
Other preferred suitable device can comprise the Hardheim by Gustau Eirich, the Eirich that Germany makes
RRV series, by Lodige Mashinenbau GmbH, the Lodige that Paderborn Germany makes
RFM series (being used for batch mixes), Baud KM series (is used for continuous mixing/reunion; By Drais Werke GmbH, the Drais that Mannheim Germany makes
RT160 series; And by Winkworth Machinery Ltd., Bershire, the Winkworth that England makes
RRT25 series.
Two examples of the mixing tank that is suitable for are the Littleford mixing tanks of chopping blade in having, and model is #FM-130-D-12, and has the Cuisinart Food Processor of 7.75 inches (19.7cm) blades, Model #DCX-Plus.Any have finely divided mixing and a granulating ability, and residence time other mixing tank between 0.1-10 minute all can use.Preferably " turbine type " rotating plasma mixing tank has several blades on its turning axle.The present invention's method in batches or continuously carries out.
Service temperature
Preferred service temperature also should be low as much as possible, because can make in the finished particle surfactant concentration higher like this.The temperature of aggregation procedure is preferably and is lower than 100 ℃, more preferably 10-90 ℃, most preferably is 20-80 ℃.Adopt many known methods in the prior art, the cold water jacket as nitrogen cooling, equipment adds solid CO
2And similar approach all can reach the low operating temperature that is applicable to technology of the present invention, and the best way is the nitrogen cooling.
Final piece material is formed
The present invention produces the high-density block material that is used for detergent composition.The preferred final piece material component that adds in the granulated detergent has high surfactant concentration.By increasing surfactant concentrations, the particle/piece material that is prepared by the present invention more is applicable to various prescription.These particle agglomerates that contain high surfactant only need carry out precision work slightly can become final piece material, thereby a large amount of processing aids (inorganic powder etc.) that other procedure of processing (spraying drying, dedusting etc.) of being used for whole production of detergents technology will be used have been saved.
The piece material that makes by the present invention is big, low dirt and energy unrestricted flow, and its bulk density preferably is about 0.4-1.2g/cm
3, and preferably be about 0.6-0.8g/cm
3The median size of particle weight of the present invention is about the 200-1000 micron.So its particle diameter of particle that generates is preferably the 200-2000 micron.Preferred granulating temperature is about 10-60 ℃, preferably is about 20-50 ℃.
Dry
By at common powder drying equipment,, the water content of wanting in the free-flow motion block material of the present invention can be adjusted to the level that is applicable to required purposes as dry in the fluidized bed dryer.If with warm air fluidisation bed dryer, must be careful during use, in order to avoid this particulate temperature-sensitive decomposition of components.It also is favourable adopting cooling step before extensive the storage.This step also can be carried out in common fluidized-bed with the freezing air operation.Drying/the cooling of this piece material also can be carried out in any miscellaneous equipment (as rotatory drier etc.) that is applicable to powder for drying.
Washing composition is used, and the final moisture content of this piece material need remain on lower level, so that the piece material is stored and transported with bulk.Accurate humidity depends on the composition of this piece material, but free-water (promptly not expecting crystal seed bonded water with any) concentration is 1-8% usually, is preferably 2-4%.
The granular detergent composition that contains this piece material
The present invention also comprises unrestricted flow granular detergent composition that contains above-mentioned block of material and preparation method thereof;
Described detergent composition can contain additional decontamination auxiliary agent and be added in this piece material to obtain the powder of unrestricted flow granular detergent composition.This additional decontamination auxiliary agent and powder can be mixed into aqueous slurry, and spraying drying to be generating a kind of powder, and/or simply are added in the piece material that is dry powder.
In the preferred embodiment of the present invention, be added in the slurry of surfactant-free to major general's part washing assistant, the physicals of this slurry is applicable to traditional method it to carry out spraying drying.Then by thereby these spray-dired particles and of the present invention block material and any other decontamination auxiliary agent and powder mixes are made free-pouring granular detergent composition together.
Decontamination auxiliary agent and powder
Any suitable decontamination auxiliary agent or the mixture or the powder of washing assistant all can be used for the inventive method and composition.
Detergent composition of the present invention can contain the following crystal aluminosilicate ion-exchange material of chemical formula,
Wherein Z and Y are at least about 6, and the mol ratio of Z and Y is about 1.0-0.4, and Z is about 10-264.Be applicable to that amorphous hydrated alumino-silicate materials of the present invention has following empirical formula
Wherein M is the ammonium of sodium, potassium, ammonium or replacement, and Z is about 0.5-2, and Y is 1, and it is 50 milligramequivalent CaCO that the magnesium ion exchange capacity that described material has is at least about the anhydrous silico-aluminate of every gram
3Hardness.Preferably particle diameter is about the hydration natrolite A of 1-10 micron.
Silico-aluminate ion-exchange promoter material among the present invention is hydrated form, and contains about 10%-28%(weight) water (if crystalloid), also can contain the more water of volume (if amorphous).Preferred crystalloid aluminosilicate ion exchange material contains the water of 18%-22% approximately in its crystal substrate.Another feature of this crystalloid aluminosilicate ion exchange material is that particle diameter is about the 0.1-10 micron.Amorphous material is less usually, as less than 0.01 micron.Preferred its particle diameter of ion-exchange material is about the 0.2-4 micron.Term used herein " particle diameter " expression conventional method of analysis is as the average particulate diameter with the ion-exchange material of the given weight of scanning electronic microscope microscopic inspection.Another feature that the crystal aluminosilicate ion-exchange material of this paper has usually is its calcium ion-exchanged capacity, is at least about 200mg equivalent CaCO
3The water hardness/g silico-aluminate (in moisture-free basis), this scope is about 300-352mg eq/g usually.It is that its calcium ion exchange rate is at least about 2 grain Ca that the aluminosilicate ion exchange material of this paper also has another feature
2+/ gallon per minute/gram/gallon silico-aluminate (moisture-free basis), its scope is about 2-6 grain/gallon per minute/gram/gallon usually, based on calcium ion hardness.Its calcium ion exchange rate of best silico-aluminate as washing assistant is at least about 4 grains/gallon per minute/gram/gallon.
The Mg that the amorphous aluminosilicate ion-exchange material has usually
+ 2Exchange capacity is at least about 50mg equivalent CaCO
3/ g(12mg Mg
+ 2/ g), and Mg
+ 2Exchange velocity is at least about 1 grain/gallon per minute/gram/gallon.When using Cu radiation (1.54
When unit) testing, amorphous material does not show the visible diffractogram.
Being used to implement aluminosilicate ion exchange material of the present invention can buy from the market.Be applicable to that its structure of silico-aluminate of the present invention can be crystal type or amorphous, and can be naturally occurring silico-aluminate or synthetic obtaining.People such as the production method of aluminosilicate ion exchange material such as US 3985669(Krummel, on October 12nd, 1976, approval was listed in this paper reference) described.It is commercially available being used for preferred synthetic crystallization aluminosilicate ion exchange material of the present invention, is called zeolite A, zeolite B and X zeolite.In a particularly preferred embodiment, this crystal aluminosilicate ion-exchange material has following chemical formula:
Wherein x is about 20-30, particularly is about 27, and its particle diameter is usually less than about 5 microns.
Granulated detergent of the present invention can contain neutrality or basic salt, and PH is 7 or bigger in this salts solution, and its character is organic or inorganic.This auxiliary salt helps detergent particles of the present invention to have desired density and shatter value.Although some is an inert in this salt, manyly in them also can in washings, play the decontamination promoter effect.
The example of neutral water-soluble salt comprises basic metal, ammonium or replaces muriate, fluorochemical and the vitriol of ammonium.In the above-mentioned salt, the salt of basic metal, especially sodium is preferred.Usually sodium sulfate is used for detergent particles, it is a kind of particularly preferred salt.Citric acid and general, any other organic or inorganic acid all can add in the granulated detergent of the present invention, as long as they are chemically compatible with other composition in this piece material composition.
Other useful water-soluble salt comprises known compound as detergent builders.Washing assistant is selected from various water miscible basic metal, ammonium usually or replaces phosphoric acid salt, polyphosphate, phosphonate, polyphosphonic acid salt, carbonate, silicate, borate and the poly-hydroxy sulfonate of ammonium.Preferably above-mentioned basic metal, particularly sodium salt.
The specific examples of inorganic phosphate builders is polymer metaphosphate and the orthophosphoric acid salt that three polyphosphate, pyrophosphate salt, the polymerization degree of sodium and potassium is about 6-21.The example of polyphosphate auxiliary agent is the sodium and the sylvite of ethene di 2 ethylhexyl phosphonic acid, 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 phosphate builder compound such as US 3159581,3213030,3422021,3422137,3400176 and 3400148(have listed this paper reference in) described in.
The example of the inorganic assistant agent of non-phosphorus is carbonate, supercarbonate, sesquicarbonate, tetraboric acid decahydrate and silicate, the wherein SiO of sodium and potassium
2Be about 0.5-4.0 with the mol ratio of alkalimetal oxide, preferably be about 1.0-2.4.The composition that is made by the inventive method need not excessive carbonate to handle, and does not preferably contain the finely powdered lime carbonate (as people such as Clarke, on April 1st, 1980, the US 4196093 of approval was described) more than 2%, and does not preferably contain this lime carbonate.
The above-mentioned powder that is generally used in the washing composition all can be used in the preferred embodiments of the present invention as zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate etc. and process auxiliaries such as starch.
The summary of accompanying drawing
Fig. 1 represents shear-stress and the viscosity figure to velocity of shear.Testing size is a 77%(weight) C
11-C
13The LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium solution, measuring temperature is 70 ℃.
Fig. 2 represents the figure that shear-stress and viscosity are done velocity of shear.The slurry of test is a 76%(weight) C
14-C
15Sodium alkyl sulfate solution, measuring temperature is 70 ℃.
Fig. 3 represents the figure that 5 kinds of its shear-stresses of different paste compounds are done velocity of shear.C
14-C
15Sodium alkyl sulfate solution: C
13-C
15The weight percentage of alkyl ethoxy sodium sulfate (average 3 ethoxy groups) is (a) 70: 0, (b) 68: 2, and (c) 66.5: 3.5, (d) 63: 7, (e) 56: 14.
Each test, the aqueous slurry temperature is 70 ℃.
Fig. 4 represents the figure that shear-stress and viscosity are done velocity of shear.The slurry of being tested is a 78%(weight) C
11-C
13The mixture of LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium and tallow alkyl sodium sulfate.These two kinds of tensio-active agents exist with equivalent.The probe temperature of this aqueous slurry is 70 ℃.
Fig. 5 represents the figure that shear-stress and viscosity are done velocity of shear.The slurry of being tested is a 74.8%(weight) C
11-C
13The mixture of linear alkyl sodium sulfonate and tallow alkyl sodium sulfate.Two kinds of tensio-active agents exist with equivalent.This slurry also contains 3.2%(weight) C
13-C
15Alkyl ethoxy sodium sulfate (3 ethoxy groups are on average arranged).The probe temperature of this aqueous slurry is 70 ℃.
Embodiment
1. in each following embodiment, by fatty alcohol sulphuric acidization, then in continuously and in the loop, neutralize making the anion surfactant slurry with the aqueous sodium hydroxide solution of 48-50%, production rate be the 1-2 ton/hour.
C
14-C
1576% active slurry of sodium alkyl sulfate has rheological diagram as shown in Figure 2.Be about 20-40S in velocity of shear
-1Shi Youyi tangible shear thickening district.
Following example a-e explanation is by adding C
13-C
15Alkyl ethoxy sodium sulfate (3 ethoxy groups are on average arranged) and improve the situation of rheological diagram.In example b-e, alkyl ethoxy sulfate is injected and the loop.
a b c d e
Alkyl-sulphate 70 68 66.5 63 56
Alkyl ethoxy sulfate 02 3.5 7 14
Water (and impurity)
*30 30 30 30 30
From the shear thickening performance of the visible composition a-c of Fig. 3, on the contrary, example d and e do not show the shear thickening performance, but they present the performance (having a yield point) that shearing weakens liquid.
2. in following example, make C by neutralizing with the 48-50% aqueous sodium hydroxide solution
11-C
13The mixture of linear alkyl benzene sulfonate and tallow alkyl sulfate (each composition weight equate), production rate be the 1-2 ton/hour.
F (Fig. 4) G (Fig. 5)
C
11-C
13LAS 39 37.1
TAS 39 37.4
Alkyl ethoxy sulfate 0 3.2
Water (and impurity)
*22 22
F(sees Fig. 4 at example) in said composition in and present instability in the loop because the rheological characteristics of said composition makes the big fluctuation of pressure generation.This makes us stably not produce this paste compound with the loop in continuously.
G(sees Fig. 5 at example) in said composition contain 3.2%(weight) C13-C
15Alkyl ethoxy sulfate (average 3 ethoxy groups), this has resulting paste compound and shears the performance that weakens liquid.
Attention: in example 1 and 2, also comprising a spot of impurity in the percent of total of described water, mainly is the material of unsulfonated, as alcohol, and lipid acid.
Claims (14)
1, a kind of washing composition paste composition, it contains:
(a) anion surfactant of 50%-94% (weight), this tensio-active agent is selected from following salt:
C
12-C
20Alkyl-sulphate, side chain or linear C
10-C16 alkylbenzene sulfonate, C
14-C
16Alkene or alkane sulfonate, senior (C
12-C
18) salt of lipid acid, C
12-C
20Alkyl methyl sulfonated ester and composition thereof;
(b) 1%-30% (weight) chemical formula is R (OC
2H
4)
nOSO
3The alkyl ethoxy sulfate of M
Wherein R is a kind of aliphatic hydrocarbon group, and side chain or linearity contain 10-18 carbon atom, and ethoxylation group mean number n is 1-7, and M is the ammonium of a kind of basic metal, alkaline-earth metal ammonium or replacement,
(c) water of 5%-35% (weight);
This slurry is 25S in velocity of shear
-1The time viscosity under 70 ℃ of temperature recording greater than 10Pa.S.
2, by a kind of detergent paste of claim 1, the content that it is characterized by anion surfactant (a) is the 60%-85% of said composition weight.
3, by a kind of detergent paste of claim 1 or 2, it is characterized by alkyl ethoxy sulfate (b) content is the 1%-15% of said composition weight.
4, by each a kind of detergent paste of claim 1-3, it is characterized by in velocity of shear is 25S
-1The time record this slurry viscosity under 70 ℃ of temperature greater than 20Pa.S.
5, by each a kind of detergent paste of claim 1-4, the mean value n that it is characterized by the ethoxylation group in alkyl ethoxy sulfate (b) is 2-4.
6, by each a kind of detergent paste of claim 1-5, the ratio that it is characterized by anion surfactant (a) and alkyl ethoxy sulfate (b) is 9: 1-50: 1.
7, by each a kind of detergent paste of claim 1-3, it is characterized by anion surfactant (a) and comprise tallow alkyl sulfate, C
11-C
13Linear alkyl benzene sulfonate, or its mixture; And alkyl ethoxy sulfate (b) comprises the side chain C that on average has 3 ethoxylation groups
12-C
15Alkyl ethoxy sulfate.
8, a kind of high-activity detergent piece material, it contains 30%-80%(weight) as each the slurry of claim 1-7.
9, a kind of high-activity detergent piece material by claim 8 contains a kind of washing composition dry powder, and this powder is selected from zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate, starch and composition thereof.
10, by a kind of preparation method of the paste compound of claim 1-7, comprise and use a kind of basic metal, the oxyhydroxide that is preferably sodium in and this anion surfactant (a) that neutralizes continuously in the loop.
11,, it is characterized by adding alkyl ethoxy sulfate (b) after neutralize anionic surfactant (a) by a kind of method of claim 10.
12, by a kind of method of claim 10, it is characterized by in neutralize anionic surfactant (a) process, in during alkyl ethoxy sulfate (b) is added to salt form and the loop.
13,, make anion surfactant (a) and alkyl ethoxy sulfate (b) cosulfonate before it is characterized by neutralization by a kind of method of claim 10.
14, a kind of preparation method of unrestricted flow granulated detergent; comprise with significant quantity as each the described a kind of detergent paste of claim 1-7 and the washing composition dry powder blend of significant quantity; generate a kind of uniform mixture fast by this mixture; make this mixture be granulated into dispersive detergent bar material, and this this detergent composition of detergent bar material and remaining is mixed mutually.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870040A EP0560001B1 (en) | 1992-03-10 | 1992-03-10 | High active detergent pastes |
| EP92870040.0 | 1992-03-10 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122640A Division CN1098351C (en) | 1992-03-10 | 1997-11-27 | Process for making detergent paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077486A true CN1077486A (en) | 1993-10-20 |
| CN1054630C CN1054630C (en) | 2000-07-19 |
Family
ID=8212244
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93104045A Expired - Fee Related CN1054630C (en) | 1992-03-10 | 1993-03-10 | High active detergent pastes |
| CN97122640A Expired - Fee Related CN1098351C (en) | 1992-03-10 | 1997-11-27 | Process for making detergent paste |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122640A Expired - Fee Related CN1098351C (en) | 1992-03-10 | 1997-11-27 | Process for making detergent paste |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0560001B1 (en) |
| JP (2) | JP3514758B2 (en) |
| CN (2) | CN1054630C (en) |
| AT (1) | ATE180273T1 (en) |
| AU (1) | AU3781393A (en) |
| CA (1) | CA2131172C (en) |
| DE (1) | DE69229218T2 (en) |
| DK (1) | DK0560001T3 (en) |
| EG (1) | EG19954A (en) |
| ES (1) | ES2131524T3 (en) |
| IE (1) | IE930175A1 (en) |
| MA (1) | MA22817A1 (en) |
| MX (1) | MX9301337A (en) |
| PH (1) | PH30683A (en) |
| TR (1) | TR27088A (en) |
| WO (1) | WO1993018123A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105849085A (en) * | 2013-12-27 | 2016-08-10 | 花王株式会社 | Method for producing internal olefin sulfonate |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9226003D0 (en) † | 1992-12-14 | 1993-02-10 | Unilever Plc | Detergent production |
| DZ1837A1 (en) * | 1993-12-15 | 2002-02-17 | Albright & Wilson | Structured surfactants. |
| US6166095A (en) * | 1993-12-15 | 2000-12-26 | Albright & Wilson Uk Limited | Method of preparing a drilling fluid comprising structured surfactants |
| DK0663439T3 (en) * | 1994-01-17 | 2000-09-18 | Procter & Gamble | Process for the preparation of detergent granules |
| WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
| US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
| US5554587A (en) * | 1995-08-15 | 1996-09-10 | The Procter & Gamble Company | Process for making high density detergent composition using conditioned air |
| ATE264384T1 (en) * | 1996-07-04 | 2004-04-15 | Procter & Gamble | METHOD FOR CONDITIONING SURFACTANT PASTES FOR THE PURPOSE OF FORMING HIGHLY ACTIVE SURFACTANT GRANULATES |
| DE19648014C2 (en) * | 1996-11-20 | 2002-09-19 | Cognis Deutschland Gmbh | Anhydrous surfactant mixtures |
| CA2280898C (en) * | 1997-02-27 | 2003-04-01 | Manivannan Kandasamy | Process for making a detergent composition by adding co-surfactants |
| JP6243036B2 (en) * | 2013-09-09 | 2017-12-06 | ザ プロクター アンド ギャンブル カンパニー | Method for making liquid cleaning composition |
| WO2019106982A1 (en) * | 2017-11-29 | 2019-06-06 | 花王株式会社 | Internal olefin sulfonate composition and method for preserving internal olefin sulfonate |
| US20190292490A1 (en) * | 2018-03-22 | 2019-09-26 | The Procter & Gamble Company | Process of making liquid household care compositions |
| MX2020011976A (en) * | 2018-05-10 | 2021-01-15 | Procter & Gamble | Detergent granule. |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US469227A (en) * | 1892-02-23 | William g | ||
| DE1692009B2 (en) * | 1968-02-17 | 1973-02-15 | Farbwerke Hoechst AG, vormals Mei ster Lucius & Bruning, 6000 Frankfurt | PROCESS FOR MANUFACTURING PUMPABLE, FLOWABLE DETERGENT PASTE |
| JPS5116036B2 (en) * | 1972-05-23 | 1976-05-21 | ||
| JPS5116045B2 (en) * | 1972-08-08 | 1976-05-21 | ||
| GB1546127A (en) * | 1976-11-18 | 1979-05-16 | Shell Int Research | Detergent compositions |
| US4692271B1 (en) * | 1977-12-09 | 1997-07-22 | Albright & Wilson | Concentrated aqueous surfactant compositions |
| US4440665A (en) * | 1978-05-26 | 1984-04-03 | Albright & Wilson Limited | Concentrated aqueous surfactant compositions |
| EP0024711B2 (en) * | 1979-09-01 | 1989-02-08 | Henkel Kommanditgesellschaft auf Aktien | Watery tenside concentrates and process for the improvement of the flowing property of difficultly movable watery tenside concentrates |
| EP0039110B1 (en) * | 1980-04-24 | 1985-01-02 | THE PROCTER & GAMBLE COMPANY | Liquid detergent compositions |
| US4487710A (en) | 1982-03-01 | 1984-12-11 | The Procter & Gamble Company | Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid |
| GB8412045D0 (en) * | 1984-05-11 | 1984-06-20 | Unilever Plc | Detergent compositions |
| ES8607378A1 (en) * | 1984-08-06 | 1986-05-16 | Kao Corp | Powder detergent of high density |
| GB8420945D0 (en) * | 1984-08-17 | 1984-09-19 | Unilever Plc | Detergents compositions |
| JP2662221B2 (en) * | 1987-07-15 | 1997-10-08 | 花王株式会社 | High density granular concentrated detergent composition |
| DE68924373T2 (en) * | 1988-06-29 | 1996-05-15 | Procter & Gamble | Process for the preparation of concentrated granules of surfactants. |
| US5080848A (en) * | 1988-12-22 | 1992-01-14 | The Proctor & Gamble Company | Process for making concentrated surfactant granules |
| CA2017922C (en) * | 1989-06-09 | 1995-07-11 | Frank Joseph Mueller | Formation of discrete, high active detergent granules using a continuous neutralization system |
-
1992
- 1992-03-10 AT AT92870040T patent/ATE180273T1/en not_active IP Right Cessation
- 1992-03-10 DE DE69229218T patent/DE69229218T2/en not_active Expired - Fee Related
- 1992-03-10 ES ES92870040T patent/ES2131524T3/en not_active Expired - Lifetime
- 1992-03-10 EP EP92870040A patent/EP0560001B1/en not_active Expired - Lifetime
- 1992-03-10 DK DK92870040T patent/DK0560001T3/en active
-
1993
- 1993-03-01 WO PCT/US1993/001790 patent/WO1993018123A1/en active Application Filing
- 1993-03-01 CA CA002131172A patent/CA2131172C/en not_active Expired - Fee Related
- 1993-03-01 JP JP51579793A patent/JP3514758B2/en not_active Expired - Fee Related
- 1993-03-01 AU AU37813/93A patent/AU3781393A/en not_active Abandoned
- 1993-03-03 TR TR00164/93A patent/TR27088A/en unknown
- 1993-03-08 MA MA23111A patent/MA22817A1/en unknown
- 1993-03-08 EG EG13793A patent/EG19954A/en active
- 1993-03-08 PH PH45832A patent/PH30683A/en unknown
- 1993-03-09 IE IE017593A patent/IE930175A1/en not_active IP Right Cessation
- 1993-03-10 CN CN93104045A patent/CN1054630C/en not_active Expired - Fee Related
- 1993-03-10 MX MX9301337A patent/MX9301337A/en not_active IP Right Cessation
-
1997
- 1997-11-27 CN CN97122640A patent/CN1098351C/en not_active Expired - Fee Related
-
2002
- 2002-09-18 JP JP2002271900A patent/JP2003147390A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105849085A (en) * | 2013-12-27 | 2016-08-10 | 花王株式会社 | Method for producing internal olefin sulfonate |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9301337A (en) | 1994-01-31 |
| AU3781393A (en) | 1993-10-05 |
| CA2131172A1 (en) | 1993-09-16 |
| CN1054630C (en) | 2000-07-19 |
| CN1098351C (en) | 2003-01-08 |
| DE69229218T2 (en) | 1999-12-16 |
| IE930175A1 (en) | 1993-09-22 |
| ES2131524T3 (en) | 1999-08-01 |
| EG19954A (en) | 1999-05-31 |
| DE69229218D1 (en) | 1999-06-24 |
| DK0560001T3 (en) | 1999-11-08 |
| PH30683A (en) | 1997-09-16 |
| ATE180273T1 (en) | 1999-06-15 |
| CN1190670A (en) | 1998-08-19 |
| MA22817A1 (en) | 1993-10-01 |
| JPH07507818A (en) | 1995-08-31 |
| CA2131172C (en) | 1998-08-18 |
| JP3514758B2 (en) | 2004-03-31 |
| EP0560001A1 (en) | 1993-09-15 |
| TR27088A (en) | 1994-10-18 |
| WO1993018123A1 (en) | 1993-09-16 |
| EP0560001B1 (en) | 1999-05-19 |
| JP2003147390A (en) | 2003-05-21 |
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