EP1756256B1 - Granulation ciblee obtenue par neutralisation dans une machine de type compomix - Google Patents

Granulation ciblee obtenue par neutralisation dans une machine de type compomix Download PDF

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Publication number
EP1756256B1
EP1756256B1 EP04739932A EP04739932A EP1756256B1 EP 1756256 B1 EP1756256 B1 EP 1756256B1 EP 04739932 A EP04739932 A EP 04739932A EP 04739932 A EP04739932 A EP 04739932A EP 1756256 B1 EP1756256 B1 EP 1756256B1
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EP
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Prior art keywords
weight
acid
acids
anionic surfactant
mixer
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EP1756256A1 (fr
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Bernhard Orlich
Gerhard Blasey
Hans-Friedrich Kruse
Keiwan Ebrahimzadeh
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the present invention relates to a process for the preparation of surfactant granules. It relates in particular to a process which makes it possible to adjust the bulk density of the surfactant granules and the distribution of grain sizes in a targeted manner.
  • Surfactant granules are used for the preparation of solid detergents or cleaners which are e.g. as powder or Kompaktate, needed.
  • the preparation of surfactant granules is carried out, for example, by reaction of anionic surfactant acids with neutralizing agents. This neutralization can be carried out both with solutions of alkali metal hydroxides, as well as within a dry neutralization with solid alkaline substances, in particular sodium carbonate.
  • the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable.
  • products of this type have paste-like to cuttable properties, the flowability and pumpability of such pastes being already limited or even lost in the range of about 50% by weight of active substance, so that in the further processing of such pastes, in particular during their incorporation in Solid mixtures, for example, in solid detergents and cleaning agents, considerable problems arise. It is accordingly an old need to be able to provide anionic detergent surfactants in a dry, in particular free-flowing form.
  • the European patent application EP-A-0 438 320 discloses a batch process for the preparation of surfactant granules having bulk densities above 650 g / l.
  • a solution of an alkaline inorganic substance in water with the possible addition of other solids, is mixed with the anionic surfactant acid and granulated in a high-speed mixer / granulator with a liquid binder.
  • neutralization and granulation occur in the same apparatus, but in separate process steps, so that the process can only be operated batchwise.
  • EP-A-0 402 112 discloses a continuous neutralization / granulation process for the production of FAS and / or ABS granules from the acid in which the ABS acid is neutralized with at least 62% NaOH and then with the addition of adjuvants, for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000 is granulated.
  • adjuvants for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000 is granulated.
  • EP-A-0 508 543 (Procter & Gamble) refers to a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with direct cooling with dry ice or liquid nitrogen.
  • surfactant mixtures which are subsequently sprayed onto solid absorbents and provide detergent compositions or components therefor are also disclosed in U.S. Pat EP 265,203 (Unilever).
  • the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
  • the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
  • the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
  • a process for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in US Pat EP 507 402 (Unilever).
  • the surfactant blends disclosed herein, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
  • German patent application DE-A-42 32 874 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of anionic surfactants in their acid form.
  • a neutralizing agent solid powdery substances, in particular sodium carbonate, disclosed here, which reacts with the anionic surfactant to anionic surfactant, carbon dioxide and water.
  • the granules obtained have surfactant contents of about 30% by weight and bulk densities of less than 550 g / l.
  • EP 642 576 (Henkel KGaA) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of used Ingredients, pre-granulated solid and liquid ingredients and in a second, high-speed granulator, the pregranules are optionally mixed with the remaining ingredients and transferred into a granule.
  • German patent application DE-A-43 14 885 discloses a process for preparing washing and cleaning-active anionic surfactant granules by neutralizing the acid form of anionic surfactants with a basic compound, wherein the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant is reacted with the neutralizing agent without releasing water.
  • the neutralizing agent used is sodium carbonate, which reacts in this process to form sodium bicarbonate.
  • Further processes for the preparation of anionic surfactant granules are WO 92/06170 . DE 19858599 and US 5576285 known.
  • the bulk densities of the granules to be produced should be selectively adjustable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower process. Furthermore, it should be possible to influence the grain size distribution of the granules by varying suitable factors. Targeted process management should make it possible, in particular, for the end products to be superior to products that can be produced by prior art processes.
  • the end products should have a high solubility, which is precisely when used in the form of Kompakteten a condition for the rapid and complete dissolution of the detergent or cleaning agent portion.
  • the granules are expected to optimize shelf life. There should be no longer a sticking together of the individual granules, or an inhomogeneous distribution of the different granule sizes in a granulate quantity due to a broad grain size distribution with a longer storage life. Particular attention was paid to optimizing the cost of the process according to the invention in comparison to the process described in the prior art. So should process steps such as the energy-consuming evaporation of water or the use of energy-consuming high-speed mixer or high shear mixer are largely avoided.
  • the present invention is a process for the preparation of surfactant granules having a bulk density of 300 to 800 g / l by neutralization of anionic surfactant acids and optionally other acidic components with solid neutralizing agents, in which the anionic surfactant (s) and the solid (s) neutralizing agent agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 24 wt .-%.
  • anionic surfactant acids are reacted with solid neutralizing agents.
  • Suitable anionic surfactant acids for this process are in principle all anionic surfactant acids known to the person skilled in the art.
  • one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, in particular from the group is / are used as the anionic surfactant acid (s) the C 8-16 -, in particular the C 9-13 -alkylbenzenesulfonic acids used.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. For example, cleavage in an autoclave or the continuous high-pressure fission.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oct
  • Such mixtures are, for example, coconut oil fatty acid (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca.
  • % C 16 ' 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 G % by wt. C 16 , 5 wt.% C 18 , 25 wt.% C 18 ' , 45 wt.% C 18 " , 7 wt.% C 18'” ).
  • Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
  • Their alkali metal salts, in particular sodium salts the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • alkyl ether sulfuric acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • Another process for producing alkanesulfonic acids is sulfoxidation in which n- paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • petroleum fractions are separated on a large scale with molecular sieves in the n- paraffins of the desired purity and dehydrogenated to the n- olefins, resulting in both ⁇ - and i- olefins.
  • the product as a 97 Wt .-% alkylbenzenesulfonic acid (ABSS) provide, which can be used in the context of the present invention as anionic surfactant acid.
  • alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -benzenesulfonic acids used have a content of 2-phenyl-isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention.
  • the anionic surfactant in acid form before addition to the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
  • Suitable acid reactants in the context of the present invention are also the fatty acids, phosphonic acids, polymer acids or partially neutralized fatty acids mentioned Polymeric acids and "Builderklaren” and “complex builder” acids alone and in any mixtures.
  • ingredients of detergents and cleaners that can be added to the anionic surfactant especially acid detergent and cleaning agent ingredients, so for example phosphonic acids, which are in neutralized form (phosphonates) as incrustation inhibitors part of many detergents and cleansers.
  • the use of (partially neutralized) polymer acids such as polyacrylic acids, is possible.
  • acid-stable ingredients with the anionic surfactant acid.
  • offer so-called small components which would otherwise have to be added in elaborate further steps, so for example, optical brighteners, dyes, etc., in which case the acid stability is to be checked.
  • the anionic surfactant in acid form nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing Mixture, mixed.
  • This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous.
  • the different representatives from the group of nonionic surfactants are described below.
  • the anionic surfactant acids reacted in the process according to the invention have a water content between 5 and 24% by weight.
  • anionic surfactant acids containing from 5 to 24% by weight of water are used in the process described.
  • less than 5% by weight of water, based on the neutralizing agent is preferably introduced into the mixer by the neutralizing agent in this process.
  • Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-% in the neutralizing agent.
  • the neutralizing agent contains 1-2% by weight of water.
  • the anionic surfactant acid contains 5-17% by weight of water.
  • Water contents of the acid which are between 6 and 16% by weight, particularly preferably between 7 and 15% by weight and in particular between 8 and 14% by weight, are preferred for this embodiment.
  • Very particular preference is given to a form of the process in which the water content of the anionic surfactant acid is between 9 and 13% by weight and in particular between 10 and 12% by weight.
  • the bulk densities are preferably 300-600 g / l, particularly preferably 400-600 g / l, in particular 500-600 g / l.
  • the proportion of the surfactant granules which have a particle size between 100 and 800 ⁇ m before the preparation in this preferred embodiment of the method, at least 40 wt .-%, preferably at least 47 wt .-%, particularly preferably at least 55 wt .-%, very particularly preferably at least 60% by weight and in particular at least 70% by weight.
  • the proportion of coarse-grained granules with grain sizes between 800 and 1600 microns before the preparation is preferably more than 20 wt .-%, more preferably more than 25 wt .-%, in particular more than 30 wt .-%.
  • the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably less than 17 wt .-%, more preferably less than 14 wt .-%, in particular between 1 and 12 wt .-%.
  • Preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 300 to 600 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 17 wt .-%.
  • the anionic surfactant acid contains 10-24% by weight of water. Water contents are preferred for this embodiment the acid, which are between 11 and 23 wt .-%, more preferably between 12 and 22 wt .-% and in particular between 13 and 21 wt .-%. Very particular preference is given to a form of the process according to the invention in which the water content of the anionic surfactant acid is between 14 and 20% by weight and in particular between 15 and 19% by weight. If the water content of the anionic surfactant is selected from the range described in the previous section between 10 and 24 wt .-%, granules with average bulk densities are obtained after neutralization / granulation.
  • the bulk densities are preferably 500-800 g / l, particularly preferably 500-700 g / l, in particular 500-600 g / l.
  • the proportion of the surfactant granules which have a particle size between 100 and 800 ⁇ m before the preparation, in this preferred embodiment of the process at least 52 wt .-%, preferably at least 62 wt .-%, particularly preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
  • the proportion of coarse-grained granules having particle sizes between 800 and 1600 ⁇ m before preparation is less than 20% by weight, more preferably less than 15% by weight, in particular between 1 and 10% by weight.
  • the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably greater than 17 wt .-%, more preferably greater than 23 wt .-%, in particular greater than 27 wt .-%.
  • the preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 500 to 800 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 10 and 24 wt .-%.
  • the neutralized form of the anionic surfactant acids in short the anionic surfactants, may be present in varying amounts in the compositions made by the process of the present invention.
  • Preferred processes according to the invention are characterized in that the content of neutralized anionic surfactant acid in the process products is not more than 80% by weight, preferably from 8 to 72% by weight, more preferably from 10 to 65% by weight and in particular from 15 to 55% by weight. is.
  • the process according to the invention is suitable for producing surfactant-rich granules having a surfactant content of greater than 40% by weight, as well as for producing comparatively low-surfactant granules.
  • the surfactant-rich process products preferably contain neutralized anionic surfactant acids in proportions by weight of 40 to 80 wt .-%, preferably from 45 to 75 wt .-%, particularly preferably from 50 to 72 wt .-% and in particular from 60 to 70 wt .-%. These process products are preferably used in detergent concentrates.
  • surfactant-poor process products are obtained in which neutralized anionic surfactant acids in proportions by weight of not more than 50% by weight, preferably between 8 and 42% by weight, more preferably between 10 and 35% by weight and in particular between 20 and 30 wt .-% are included.
  • These process products are preferably used in the production of high-volume standard washing and cleaning agents.
  • Suitable solid neutralizing agents are in principle all neutralizing agents known to the person skilled in the art for this process.
  • one or more substances of the compounds sodium carbonate, sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate are used as neutralizing agents.
  • components which do not take part in the reaction may also be added to the neutralizing agent. These should then have sufficient stability against the added acids to avoid local decomposition and thus unwanted discoloration or other loading of the product.
  • further solids from the groups of silicates, aluminum silicates, sulfates, citrates and / or phosphates are used.
  • sodium sulfate which is still present today in some countries up to 45 wt .-% in the detergents, the / the solid neutralizing agent (s) is admixed.
  • the weight ratio of the solid neutralizing agent (s) used in the process according to the invention can vary within wide limits.
  • weight ratio of the solid neutralizing agent (s) used in the process according to the invention to the anionic surfactant acid (s) used and optionally other acidic components is between 100: 1 and 1: 5, preferably between 80: 1 and 1: 4, preferably between 60: 1 and 1: 3, very particularly preferably between 40: 1 and 1: 2 and in particular between 20: 1 and 1: 1.
  • the neutralizing agent to be used preferably contains less than 5% by weight of free water. Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-%. In a particularly preferred embodiment of the process, the neutralizing agent contains less than 2% by weight of free water. Particular preference is given to using neutralizing agents which have a content of free, i. not present in the form of water of hydration and / or water of constitution below 1 wt .-%, preferably below 0.5 wt .-% and in particular no free water.
  • the neutralizing agent described in the above section is mixed in the free-fall mixer with anionic surfactant acid containing 5 to 24 wt .-% of water.
  • the choice of the weight ratio between neutralizing agent and water influences the storability and the dissolution behavior as well as the bulk density of the granules and the distribution of the particle sizes.
  • the weight ratio of the solid neutralizing agent used to the water introduced with the anionic surfactant acid is between 800: 1 and 2: 3.
  • the ratio of the proportionate weights of neutralizing agent and water is between 19: 1 and 19: 6.
  • the water content of the process end products is preferably less than 26% by weight, preferably 1-15% by weight, more preferably 1-10% by weight and in particular 4-5% by weight.
  • the neutralization reaction naturally produces water.
  • a process procedure should be chosen in which, instead of water and CO 2, mainly sodium bicarbonate is formed. This procedure will be described below.
  • Characteristic of the process according to the invention is the use of free-fall mixers for carrying out the neutralization of anionic surfactant acids with solid neutralizing agents.
  • the free-fall mixers can be operated continuously or discontinuously.
  • such a mixer is referred to as a free-fall mixer in which the mix is taken up by wall friction and subsequently falls freely through the mixing space due to its own gravity.
  • Such free-fall mixers have a movable or rotating reactor housing or a moving mixing vessel.
  • Suitable containers are those with simple geometric shapes (cylinder, single or double cone, cube, etc.).
  • preferred mixing containers have as far as possible obtuse-angled inner corners, since this facilitates both the free movement of the mixed material and the emptying and cleaning of the container after the end of the process. The movement of the container must be transferred to the mix in the interior, so that the most irregular possible confusion and loosening of the reaction mixture takes place.
  • the solid neutralizing agent moving in the tumbling mixer forms a falling powder curtain onto which the anionic surfactant acids are sprayed.
  • the types of movement for the free-fall mixer are, in particular, rotation about a container axis (drum or rotary tube mixer) or about axes that do not coincide with geometric axes of the container or perpendicular to its symmetry planes (tumble mixer), or vibrate, preferably with high amplitude and low frequency and changing directions of the rashes, so that irregular shaking or tumbling movements occur.
  • a directed component of motion must occur to ensure the continuous mass transfer and thus to allow a continuous process.
  • a discontinuous process wherein a directional component of motion is not desired.
  • Particularly suitable for continuous operation are those free-fall mixers which rotate about their horizontal, preferably about their little inclined axis. Due to the inclination of the axis of rotation, the mixture due to its own gravity on a directed movement, which allows a continuous discharge of the mix from the mixer. Such a directed movement can except by the inclination of the axis of rotation of course also be generated by a continuous input of anionic surfactant acids and solid neutralizing agent.
  • the angle of inclination of the axis of rotation of a preferably used rotatable container with a certain number of revolutions correlates.
  • the rotatable container of the tumbler mixer has an inclination angle ⁇ of 0 to 20 °, in particular from 0 to 15 °, most preferably from 1 to 15 ° and the movement of the rotatable container of the tumbler over the drive is set simultaneously to 20 to 70 revolutions per minute and in particular to 30 to 60 revolutions per minute.
  • Free-fall mixers preferred in the context of the present invention are drum mixers, tumble mixers, cone mixers, double-cone mixers or V mixers.
  • the free-fall mixers used in accordance with the invention provide, in the case of rotating or tumbling movements, walls alternately upraised and falling back inside, and thus diversion, widening or narrowing of the space, displacement and division of the material flow.
  • Such reactors may further comprise static and / or mobile mixing and / or cutting tools.
  • double-cone mixers with rotatable containers without mixing tools are used as free-fall mixers, wherein the continuously operated double-cone mixers are subdivided into a mixing zone and a post-mixing zone and have a knock-off strip which is fastened to an end plate and from there the entire mixing zone passes through and if necessary extends into the post-mixing zone.
  • the ratio of the length of the mixing zone to the length of the post-mixing zone is preferably at least 1: 1.
  • the tee bar may have a width of 50 to 150 mm, preferably from 75 to 130 mm.
  • the top edge of the stripper has a distance from the internal mixer wall which is preferably at most 10% of the drum diameter of the narrowest point of the rotatable container, preferably at most 5% of the narrowest point of the rotatable container and more preferably less than 2.5% of the narrowest point of the rotatable container container accounts.
  • the distance to the nearest inner mixer wall may well be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
  • the residence time of the reaction mixture in the free-fall mixer in preferred embodiments of the present inventive method is preferably less than 20 minutes, preferably between 1 and 600 seconds, more preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
  • the temperature of the mixture to be applied as low as possible is.
  • liquid, acidic component refers to the anionic surfactant acid, which comprises water and optionally further acidic components.
  • the reaction between anionic surfactant (s) and sodium carbonate is conducted so that the reaction Na 2 CO 3 + 2 anionic surfactant H ⁇ 2 anionic surfactant Na + CO 2 + H 2 O is largely suppressed and in their place the reaction Na 2 CO 3 + anionic surfactant H ⁇ anionic surfactant Na + NaHCO 3 entry,
  • the sodium carbonate is in this case used in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate in the reaction arises.
  • the amount of sodium carbonate on average (based on the agent, without consideration of any water of hydration present) is related to the amount of sodium bicarbonate on average (based on the agent, without consideration of any water of hydration present).
  • the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, and in preferred processes according to the invention the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 50: 1 to 5: 1, preferably 40: 1 to 5.1: 1, particularly preferably 35: 1 to 5.2: 1 and in particular 30: 1 to 5.25: 1.
  • Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants.
  • the content of the process end products can vary with respect to sodium bicarbonate.
  • the content of the process end products of sodium hydrogencarbonate is from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight and in particular from 1 to 10% by weight. -%, in each case based on the total weight of the process end products.
  • the content of the process end products of sodium bicarbonate is between 2 and 10% by weight, preferably between 2.5 and 10% by weight, more preferably between 3 and 10% by weight and in particular between 4 and 10% by weight.
  • the granules can be aftertreated if necessary.
  • the surfactant granules after passing through the post-mixing zone, are either discharged directly via the discharge or transported on via a conveying device.
  • the aftertreatment of the surfactant granules continuously or discontinuously perform. It is particularly preferred to connect to a batchwise operated mixing a likewise batchwise aftertreatment, which allows the whereabouts of the surfactant granules in the original reactor.
  • aftertreatment in the context of the present application, in particular the spray granulation, that is, the further addition of liquid binder, the encapsulation, the powdering with surface modifiers, the application of nonionic surfactants, drying or spray drying, cooling, and the separation of coarse and / or fines is summarized.
  • a powdering agent or surface modifier As a powdering agent or surface modifier, all known, finely divided representatives of this group can be added via a solids feed.
  • Amorphous and / or crystalline aluminosilicates such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example of amorphous silicates and carbonates, are preferred here.
  • nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, alkyl glycosides of the general formula RO (G) x , alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, amine oxides and polyhydroxy fatty acid amides used.
  • For drying hot air is preferably used.
  • the cooling is preferably carried out by cold air or dry ice. Separated coarse and / or fines are preferably recycled to the process, preferably the coarse fraction being ground before being returned to the tumble mixer.
  • the aftertreatment comprises a spray granulation and / or an encapsulation and / or a powdering with heatmodiflzierern and / or an exposure to nonionic surfactants and / or drying and / or spray drying on inert bodies and / or cooling and / or a separation of coarse and / or fines.
  • the aftertreatment of the process products after discharge from the free-fall mixer on a reaction section is a characteristic of particularly preferred embodiments of the present inventive method, again such method variants are particularly preferred in which it is in the reaction section to a pneumatic fluidized bed and / or a conveyor belt and / or is a mixer. If this conveying and metering screw leads into the post-mixing zone (a direct connection of the conveying device to the discharge unit is also possible), then it is preferred that the screw only projects maximally into the second length half of the post-mixing zone and thus not into the part of the post-mixing zone that still includes the tee bar.
  • the residence time in the post-mixing zone is preferably between 1 and 19 minutes, preferably between 2 and 17 minutes, very particularly preferably between 3 and 14 minutes, in particular between 3 and 10 minutes.
  • the agents prepared by the process according to the invention may have different bulk densities depending on the content of the individual ingredients, in particular of the water, and other Aidsparametem. Preference is given to embodiments of the process according to the invention in which the bulk density of the process end products is from 300 to 800 g / l, preferably from 350 to 700 g / l, more preferably from 400 to 650 g / l and in particular from 500 to 600 g / l.
  • the granules obtained have an increased solubility in water / aqueous solutions and an increased shelf life compared to the granules described in the prior art. Both the sticking of individual granules and the segregation of a quantity of granules after movement (tilting / shaking) of the storage container were not observed.
  • These process products furthermore have a particle size distribution with an average particle size d 50 below 5000 ⁇ m, preferably between 20 and 3000 ⁇ m, more preferably between 40 and 2000 ⁇ m and in particular between 50 and 1600 ⁇ m.
  • the surfactant granules having a particle size between 100 and 1600 ⁇ m preferably have a weight fraction of at least 80% by weight, preferably at least 82% by weight, particularly preferably at least 85% by weight, very particularly preferably at least 90% by weight. % and in particular at least 95 wt .-% on. It will be Surfactant granules which have a particle size between 100 and 800 microns prior to the preparation, in the inventive method in proportions by weight of at least 52 wt .-%, preferably at least 62 wt .-%, more preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
  • the surfactant granules prepared by the process according to the invention are particularly suitable for the production of detergents or cleaners, in particular solid detergents or cleaners, for example by further agglomeration, by extrusion or compaction.
  • Such washing or cleaning agents contain in addition to the previously mentioned ingredients such as the anionic surfactants other ingredients, especially from the group of builders, co-builders, bleach, bleach activators, dyes and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
  • Builders are used in detergents or cleaners especially for binding calcium and magnesium.
  • Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • a substance class with cobuilder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the Aminoalkanphosphonate also have a pronounced Schwerrnetallbindeabmögen. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is an integer from 1.9 to 4 and y is a number from 0 to 20 and preferred Values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • acidifying agents especially acidifying agents, chelating agents or coating-inhibiting polymers are further preferred ingredients of detergents or cleaners.
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Bleach activators aid the action of the bleaching agents.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • bleach catalysts can also be present in the secondary products of the process according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • Detergents or cleaning agents may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Preferred agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • biuret method biuret method.
  • Detergents or detergents may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms.
  • Dyes and fragrances can be added to detergents or cleaners to improve the aesthetic appearance of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • the fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and by a slower release of fragrance for long-lasting fragrance of the textiles to care.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • dyes In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • Detergents or cleaning agents may contain as optical brighteners derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • the process end products of the process according to the invention can not only be mixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention.
  • Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.

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Claims (13)

  1. Procédé pour la préparation de produits de granulation contenant un ou plusieurs tensioactifs, possédant une densité apparente de 300 à 800 g/l, par neutralisation d'acides de tensioactifs anioniques, et de manière facultative d'autres composants acides comprenant des agents de neutralisation solides, dans lequel on agglomère l'acide ou les acides de tensioactifs anioniques et le/les agents de neutralisation solides dans un mélangeur à chute libre, et on les soumet de manière facultative à un traitement ultérieur, caractérisé en ce que l'acide de tensioactif anionique présente une teneur en eau entre 5 et 24 % en poids.
  2. Procédé selon la revendication 1, caractérisé en ce que l'acide de tensioactif anionique présente une teneur en eau entre 6 et 22, de préférence entre 7 et 20 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on met en oeuvre, à titre d'acide(s) de tensioactif(s) anionique(s), une ou plusieurs substances du groupe des acides carboxyliques, des demi-esters de l'acide sulfurique et des acides sulfoniques, de préférence du groupe des acides gras, des acides alkylsulfuriques gras et des acides alkylarylsulfoniques, en particulier du groupe des acides alkyl(en C8-C16), en particulier alkyl(en C9-C13)benzènesulfoniques.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la teneur des produits issus du procédé en acides neutralisés de tensioactifs anioniques s'élève au maximum à 50 % en poids, de préférence de 8 à 42 % en poids, de manière particulièrement préférée de 10 à 35 % en poids et en particulier de 15 à 25 % en poids.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le composant acide liquide présente, lors de son entrée dans le mélangeur à chute libre, une température de 20 à 60 °C, de préférence de 30 à 55 °C et en particulier de 40 à 50 °C.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la densité apparente des produits de granulation contenant un ou plusieurs tensioactifs, s'élève de 350 à 700 g/l, de manière particulièrement préférée de 400 à 650 g/l et en particulier de 500 à 600 g/l.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les produits de granulation contenant un ou plusieurs tensioactifs présente une distribution granulométrique dont la granulométrie moyenne d50 est inférieure à 5000 µm, de préférence s'élève entre 20 et 3000 µm, de manière particulièrement préférée entre 40 et 2000 µm et en particulier entre 50 et 1600 µm.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la fraction pondérale des produits de granulation contenant un ou plusieurs tensioactifs dont la granulométrie se situe entre 100 et 1600 µm s'élève, avant le traitement, à au moins 80 % en poids, de préférence à au moins 82 % en poids, de manière particulièrement préférée à au moins 85 % en poids, de manière tout particulièrement préférée à au moins 90 % en poids et en particulier à au moins 95 % en poids.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la fraction pondérale des produits de granulation contenant un ou plusieurs tensioactifs dont la granulométrie se situe entre 100 et 800 µm s'élève, avant le traitement, à au moins 52 % en poids, de préférence à au moins 62 % en poids, de manière particulièrement préférée à au moins 70 % en poids, de manière tout particulièrement préférée à au moins 76 % en poids et en particulier à au moins 80 % en poids.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que, en ce qui concerne le mélangeur à chute libre, il s'agit d'un mélangeur à tambour, d'un mélangeur à culbutage, d'un mélangeur à cône, d'un mélangeur à double cône ou d'un mélangeur en V.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le temps de séjour du mélange réactionnel dans le récipient rotatif est inférieur à 20 minutes, de préférence s'élève entre 1 et 600 secondes, de manière particulièrement préférée entre 1 et 300 secondes et en particulier entre 1 et 120 secondes.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que les produits issus du procédé sont soumis à un traitement ultérieur sur un tronçon de réaction, après leur sortie du mélangeur à chute libre.
  13. Procédé selon la revendication 12, caractérisé en ce que, en ce qui concerne le tronçon de réaction, il s'agit d'un lit fluidisé pneumatique et/ou d'une bande transporteuse et/ou d'un mélangeur.
EP04739932A 2004-06-16 2004-06-16 Granulation ciblee obtenue par neutralisation dans une machine de type compomix Revoked EP1756256B1 (fr)

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DE102005038070A1 (de) * 2005-08-10 2007-03-15 Henkel Kgaa Wasch- und Reinigungsmittel mit gut löslichen Kapseln
DE102012217877A1 (de) * 2012-10-01 2013-08-14 Henkel Ag & Co. Kgaa Nontower-Verfahren
CA3086996A1 (fr) * 2017-12-27 2019-07-04 Toray Industries, Inc. Methode de recuperation d'acide nucleique

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US4587029A (en) * 1983-06-27 1986-05-06 The Chemithon Corporation Intermediate product for use in producing a detergent bar
CA2027518A1 (fr) * 1990-10-03 1992-04-04 Richard L. Tadsen Methode de preparation de compositions detergentes a haute densite, contenant des particules tensio-actives sensibles au ph
DE4216774A1 (de) * 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
US5576285A (en) * 1995-10-04 1996-11-19 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
EP0862611B1 (fr) * 1995-11-06 2001-09-12 Kao Corporation Procede de production de granules de silicate de metal alcalin cristallin et detergent granulaire d'une densite elevee
GB9526097D0 (en) * 1995-12-20 1996-02-21 Unilever Plc Process
JPH09241698A (ja) * 1996-03-13 1997-09-16 Lion Corp 高嵩密度粒状洗剤組成物の製造方法
GB9712583D0 (en) * 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
DE19858859A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
GB0119708D0 (en) * 2001-08-13 2001-10-03 Unilever Plc Process for the production of detergent granules
DE10258011A1 (de) * 2002-12-12 2004-07-08 Henkel Kgaa Trockenneutralisationsverfahren

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WO2005123893A1 (fr) 2005-12-29
US20080261857A1 (en) 2008-10-23
EP1756256A1 (fr) 2007-02-28
DE502004010375D1 (de) 2009-12-24
JP2008502746A (ja) 2008-01-31

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