WO1992018603A1 - Agglomeration de pates fortement actives pour former des granules tensioactifs pouvant etre utilises dans des compositions detersives - Google Patents

Agglomeration de pates fortement actives pour former des granules tensioactifs pouvant etre utilises dans des compositions detersives Download PDF

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Publication number
WO1992018603A1
WO1992018603A1 PCT/US1992/002880 US9202880W WO9218603A1 WO 1992018603 A1 WO1992018603 A1 WO 1992018603A1 US 9202880 W US9202880 W US 9202880W WO 9218603 A1 WO9218603 A1 WO 9218603A1
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WIPO (PCT)
Prior art keywords
surfactant
paste
powder
builder
detergent
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Application number
PCT/US1992/002880
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English (en)
Inventor
Lucas Goovaerts
Jose Luis Vega
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to US08/133,063 priority Critical patent/US5494599A/en
Priority to JP4510266A priority patent/JPH06506720A/ja
Priority to SK1085-93A priority patent/SK108593A3/sk
Priority to BR9205892A priority patent/BR9205892A/pt
Publication of WO1992018603A1 publication Critical patent/WO1992018603A1/fr
Priority to NO933642A priority patent/NO933642L/no
Priority to FI934464A priority patent/FI934464A/fi

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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
    • 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

Definitions

  • the present invention relates to a process for preparing compositions comprising condensed detergent granules.
  • Granular detergent compositions have so far been principally prepared by spray drying.
  • the detergent components such as surfactants and builders, are mixed with as much as 35-50% water to form a slurry.
  • the slurry obtained is heated and spray dried, which is expensive.
  • a good agglomeration process could be less expensive.
  • Spray drying requires 30-40 wt. % of the water to be removed.
  • the equipment used to produce spray dry is expensive.
  • the granule obtained has good solubility but a low bulk density, so the packing volume is large.
  • the flow properties of the granule obtained by spray drying are adversely affected by large surface irregularities, and thus the granulate has a poor appearance.
  • EP-A-0 345 090 discloses a process for manufacturing particulate detergent compositions comprising contacting detergent acid with neutralizing agents and providing particulates by contacting the detergent acid with a particulate neutralizing agent or detergent salt with carrier in an absorption zone.
  • EP-A-0 349 201 published January 3, 1990, discloses a process for preparing condensed detergent granules by finely dispersing dry detergent builders and a high active surfactant put into a uniform dough which is subsequently chilled and granulated using fine dispersion to form uniform, free flowing granular particles.
  • EP-0 390 251 discloses a process for the continuous preparation of a granular detergent or composition comprising steps of treating, firstly, particulate starting material of detergent surfactant and builders in a high-spead mixer, secondly in a moderate-speed granulator/densifier and thirdly in a drying/cooling apparatus, with the addition of powder in the second or between the first and second step to reduce the amount of oversize particles.
  • a second route is the in-situ neutralisation of the anionic surfactant acid with caustic solutions (e.g. 50% NaOH) or caustic powders (e.g. Na 2 C0 3 ) right before or in the course of the granulation step.
  • caustic solutions e.g. 50% NaOH
  • caustic powders e.g. Na 2 C0 3
  • precautions are needed to ensure complete neutralisation of the acid to avoid undesirable effects on the rest of the surfactant matrix upon storage/or during the wash.
  • the resulting particle is a highly dense granule which can be incorporated into granular detergents.
  • the present invention brings solutions to the problems mentioned above and provides with a more flexible and versatile route to the processing of granular detergents.
  • the present invention is based on an agglomeration/ granulation step that is completely uncoupled from the sulphation/sulphonation process.
  • the basis of the invention is the introduction of the anionic surfactant in an aqueous, highly concentrated solution of its salt, most preferably of its sodium salt.
  • These high active (low moisture) surfactant pastes are of a high viscosity but remain pu pable at temperatures at which the surfactants are stable. This guarantees the ability to transport and transfer the chemical from the manufacturing location to the granulation site and to be able to have adequate storage facilities prior to the formation of a particle.
  • An important object of the present invention is to make a dense, concentrated detergent granular product by an agglomeration process as opposed to a spray-drying process. It is anoter object of the invention to provide for a granular detergent product having a good solubility and good dispersion properties, and improved dispensing from a washing machine.
  • the present invention relates to an economical process for making a dense, concentrated detergent granular product, and particularly, compositions comprising very high active condensed detergent granules.
  • Fig. 1 shows a graph of viscosity versus shear rate for a) a nil-surfactant slurry, comprising a relatively small amount of zeolite. b) a similar, typical detergent slurry containing surfactant and a relatively high proportion of zeolite. - c) a nil-surfactant slurry comprising no zeolite at all.
  • Fig. 2 shows the solubility of a spray-dried nil- surfactant powder having a relatively low level of zeolite, compared to the solubility of the powder produced from a surfactant-containing slurry.
  • the present invention comprises a process for making a free flowing granular detergent comprising : mixing an effective amount of an aqueous surfactant paste having a detergency activity of at least 40% and an effective amount of a dry detergency powder, said surfactant paste active and builder or powder having a ratio of 0.05:1 to 19:1 to form a mix; rapidly forming a uniform mixture from said mix at a temperature of from about 0"C to about 80°C; granulating said mixture into discrete detergent granules using a high speed mixing at a tip speed of about 5-50 m/sec; and wherein said surfactant paste is comprised of at least one anionic surfactant, and any other surfactants, if present, are selected from the group of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof; and wherein said mixing and granulating are conducted simultaneously, or immediately sequentially.
  • the present invention is based on an agglomeration/ granulation step that is completely uncoupled from the sulphation/sulphonation process.
  • These high active (and, preferably, low moisture) surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable.
  • anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur requires that either 1 lower viscous phases be formed or that some viscosity modifiers are used.
  • a process for making a free flowing detergent composition wherein the granulated surfactants herein are admixed with the remainder of the detergent ingredients, which are typically spray-dried into a blown powder from a slurry.
  • said slurry comprises between 15% and 55% by weight of a builder, the spray-dried slurry being mixed with the agglomerated surfactant.
  • the viscosity of the nil-surfactant slurry having low amounts of builder (detergency powder) has been found to be in the same range as the viscosity of aqueous slurries comprising surfactant, at the same moisture content and in the relevant shear-rate range. Therefore, spray-drying the nil-surfactant slurry using pressure nozzles under standard conditions is possible.
  • the advantage of lower amounts of builder powder in the nil-surfactant slurry is that viscosity-increasing components such as polymers or minors, can be included in the nil-surfactant slurry.
  • the main part of the total amount of builder powder being used for agglomeration of the active paste provides space for the use of other admixed builders such as layered silicate or citrate.
  • the spray-dried powder formed from the nil-surfactant slurry containing relatively little amounts of builder has good solubility compared to detergent compositions formed by spray-drying a slurry containing surfactant.
  • a finished product is obtained having good dispensing and dispersion properties in the wash solution.
  • Spray drying the aqueous nil-surfactant slurry comprising a part of the total amount of builder used results in a powder having improved absorption properties compared to % the builder in its raw material state.
  • larger amounts of a non-ionic surfactant can be sprayed onto the spray-dried nil-surfactant slurry.
  • One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant.
  • the anionic surfactant is preferably as concentrated as possible, (that is, with the lowest possible moisture content possible that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable. While granulation using various pure or mixed surfactants is known, for the present invention to be of practical use in industry and to result in particles of adequate physical properties to be incorporated into granular detergents, an anionic surfactant must be part of the paste in a concentration of above 10%, preferably from 10-95%, more preferably from 20- 95%, and most preferably from 40%-95%.
  • the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
  • the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5 and 20% water.
  • high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
  • Lower water levels allow q for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.
  • Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps.
  • the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps.
  • the viscosity of the paste of this invention is measured at a temperature of 70°C.
  • the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C) .
  • High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
  • the use of in-line moisture reduction steps e.g. flash drying) , however, require the use of higher temperatures (above 100°C) .
  • the activity of the agglomerates is maintained high due to the elimination of moisture.
  • the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size.
  • the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
  • the activity of the aqueous surfactant paste is at least 30% and can go up to about 95%; preferred activities are : 50-80% and 65-75%.
  • the balance of the paste is primarily water but can include a processing aid such as a nonionic surfactant. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
  • the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
  • the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred.
  • Nonionic surfactants are used as secondary surfactants or processing aids and are not included herein as an • ⁇ active" surfactant.
  • Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al. , issued Dec. 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980.
  • cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions.
  • the following are representative examples of surfactants useful in the present compositions.
  • Water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
  • This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C Q -C_ Q carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol (A ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • alkyl glyceryl ether sulfonates especially those ethers of higher alcohols derived from tallow and coconut oil
  • sodium coconut oil fatty acid monoglyceride sulfonates and sulfates sodium or potassium salts of alky
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l- sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
  • the acid salts are typically discussed and used
  • the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
  • the salt is the surfactant paste discussed throughout this document.
  • the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
  • Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention.
  • a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 1:1, more preferably about 0.05:1.
  • Nonionics can be used up to an equal amount of the primary organic surfactant.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 4 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water- soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about l to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing ⁇ 5 from about 12 to 18 carbon atoms; condensation products of
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5RgR7N + X"", wherein 4 is alkyl having from 10 to 20, preferably from
  • R5 12-18 carbon atoms, and R5, Rs and R7 are each C- ⁇ to C7 alkyl preferably methyl;
  • X" is an anion, e.g. chloride.
  • trimethyl ammonium compounds include C ⁇ 2-
  • Specific preferred surfactants for use herein include: sodium linear C11-C13 alkylbenzene sulfonate; ⁇ -olefin sulphonates; triethanolammonium C11-C1 3 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g. C45, etc.); sodium alkyl sulfates;
  • surfactant means non- nonionic surfactants, unless otherwise specified.
  • the ratio of the surfactant active (excluding the nonionic(s) ) lb to dry detergent builder or powder ranges from 0.005:1 to 19:1, preferably from 0.05:1 to 10:1, and more preferably from 0.1:1 to 5:1. Even more preferred said surfactant active to builder ratios are 0.15:1 to 1:1; and 0.2:1 to 0.5:1) .
  • the preferred embodiment of the process of the present invention involves introduction of the anionic surfactant in via pastes as described above, it is possible to have a certain amount via the powder stream, for example in the form of blown powder. In these embodiments, it is necessary that the stickiness and moisture of the powder stream be kept at low levels, thus preventing increased "loading" of the anionic surfactant and, thus, the production of agglomerates with too high of a concentration of surfactant.
  • the liquid stream of a preferred agglomeration process can also be used to introduce other surfactants and/or polymers. This can be done by premixing the surfactant into one liquid stream or, alternatively by introducing various streams in the agglomerator.
  • fine dispersion mixing and/or granulation means mixing and/or granulation of the mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 50 m/sec. , unless otherwise specified.
  • the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
  • the more preferred mixing and granulation tip speeds are about 10-45 m/sec. and about 15-40 m/sec.
  • Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
  • any of a number of mixers/agglomerators can be used.
  • the process of the invention is continuously carried out.
  • mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
  • this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • Eirich R series RV, manufactured by Gustau Eirich Hardheim, Germany
  • L ⁇ dige R series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by L ⁇ dige Machinenbau GmbH, Paderborn Germany
  • Drais R T160 series manufactured by Drais Werke GmbH, Mannheim Germany
  • Winkworth R RT 25 series manufactured by Winkworth Machinery Ltd. , Bershire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • the temperature during the agglomeration is less than 80 ⁇ C, more preferably between 0° and 70"C, even more preferably between 10 and 60°C and most preferably between 20 and
  • Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO2, and the like; with a preferred method being solid CO2, and the most preferred method being nitrogen cooling.
  • a highly attractive opinion in a preferred embodiment of the present invention to further increase the concentration of surfactant in the final particle is accomplished by the addition to a liquid stream containing the anionic surfactant and/or other surfactant, of other elements that result in increases in viscosity and/or melting point and/or decrease the stickiness of the paste.
  • the addition of these elements can be done in line as the paste is pumped into the agglomerator.
  • Example of these elements can be various powders, described in more detail later herein.
  • the present invention produces granules of high density for use in detergent compositions.
  • a preferred composition of the final agglomerate for incorporation into granular detergents has a high surfactant concentration.
  • the particles/agglomerates made by the present invention are more suitable for a variety of different formulations.
  • These high surfactants containing particle agglomerates require fewer finishing techniques to reach the final agglomerates, thus freeing up large amounts of processing aids (inorganic powders, etc.) that can be used in other processing steps of the overall detergent manufacturing process (spray drying, dusting off, etc) .
  • the granules made according to the present invention are large, low dust and free flowing, and preferably have a bulk density of from about 0.5 to about 1.0 g/cc, more preferably from about 0.6 to about 0.8 g/cc.
  • the weight average particle size of the particles of this invention are from about 200 to about 1000 microns.
  • the preferred granules so formed have a particle size range of from 200 to 2000 microns.
  • the more preferred granulation temperatures range from about 10°C to about 60°C, and most preferably from about 20°C to about 50°C.
  • the desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers. If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.
  • the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk.
  • the exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 2-4%.
  • Any compatible detergency builder or combination of builders or powder can be used in the process and compositions of the present invention.
  • the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zA10 2 -ySi0 2 ) dl wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is l, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC ⁇ 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous.
  • Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns.
  • Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • the term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaC ⁇ 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains
  • Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis) , and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least about 50 mg eq. CaC0 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units) .
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula Na 12 [(A10 2 )12(Si02) 12 ] • XH 2 0 wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. The alkali metal, and especially sodium, salts of the above are preferred. Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • 0 her useful water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhyroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si0 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • the compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.l, 1980, and is preferably free of the latter.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch, can be used in preferred embodiments of the present invention.
  • organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate) , polyacrylamides, polyacrylates and various copolymers, such as those of aleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range Of 2,000 to 100,000.
  • Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • compositions of the 35 present invention can be included in the compositions of the 35 present invention. These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.
  • flow aids include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.
  • Optically brighteners may be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by way of the spray-dried slurry, or via both of these routes.
  • Particulate suds suppressors may also be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by dry adding.
  • the suds suppressing activity of these particles is based on fatty acids or silicones.
  • LAS and AS as used herein mean, respectively, “sodium lauryl benzene sulfonate” and “alkyl sulfate.”
  • MES sodium methyl ester sulphonate.
  • C45 mean C14 and C15 alkyl, unless otherwise specified.
  • TAS means Tallow alkyl sulphate.
  • Dobanol 45E7 is a C 4/C15 alcohol ethoxylate with 7 units of ethylene oxide and is manufactured by Shell Co.
  • Example 1 An aqueous surfactant LAS paste having a detergent activity of 78% and a water content of 21% is pumped via a positive displacement pump into a L ⁇ dige CB 55 at a rate of 20 T/hr. The viscosity of the paste is 25,000 cps at a temperture of 70 ⁇ C. At the same time, a powder stream containing a mixture of 1:1 ratio by weight of Zeolite A to citrate dihydrate finely divide, is also fed to the L ⁇ dige CB 55 mixer at a rate of 4 T/hr. Also flowing into the same mixer are two streams containing the recycle of the classification of the agglomerates, one containing wet coarse particles and the other dry fine particles.
  • the agglomerates leaving the L ⁇ dige CB 55 mixer are dried in a controlled temperature fluid bed with air exit temperatures of 50-55 ⁇ C. After drying for an average residence time of approximately 15 minutes, the agglomerates are cooled in a second fluid bed to powder exit temperatures below 45 P C. The cool dry product leaving the cooler is classified through mesh sieves and the desired particle sizes stored in a silo.
  • the agglomerates made during this Example have a detergent activity of 25% and a density of 780 g/L.
  • Example 2 is similar to Example 1. In this case, an aqueous surfactant C45AS paste with a detergent activity of
  • the viscosity of the paste is 35,000 cps at a temperature of 70°C.
  • the powder stream consists of a mixture of a 2:1 ratio by weight of Zeolite A and sodium carbonate finely divided and is fed at a rate of 2.0 T/hr.
  • the agglomerates made during this Example have a detergent activity of 39% and a density of 675 g/L.
  • This Example describes the process in batch mode in a pilot plant scale high shear mixer, an Eirich RV02.
  • the mixer is filled first with a mixture of the powders to be used, in this particular case a 2:1 ratio of Zeolite A and finely divided sodium carbonate (3 kg) .
  • An aqueous surfactant MES paste with a detergent activity of 65% and a water content of 33% is then added on top of the powder mixture while the mixer is being operated at 1600 rpm. Enough paste is added until granulation is achieved (in this case, 1.6 kg of the MES paste) .
  • the agglomerates are discharged onto a fluid bed drier and then classified through adequate sieves.
  • the resulting agglomerates are made with a detergent activity of 22% and a density of 750 g/L.
  • This Example is similar to Example 3.
  • the powder mixture is again a 2:1 ratio of Zeolite A to finely divided carbonate.
  • the surfactant is an ao :eous paste of C45AS with a detergent activity of 78% ana a water content of 13%.
  • both the powders (1.05 kg) and the paste (3 kg) are added to the mixer (the Eirich RV02) before starting the granulation.
  • a certain amount (2 kg) of dry ice is also added to the mixer to lower the temperature below -15°C.
  • the mixer is then started at a speed of 1600 rpm. At first, at the low temperature achieved, the mixture is in the form of a fine powder.
  • the mixer is operated until the temperature raises to the point (12°C) where granulation occurs.
  • the process is then stopped and the agglomerates are dried in a fluid bed and classified through mesh sieves.
  • the agglomerates made have a detergent activity of 60% and a density of 625 g/L. They show excellent
  • An aqueous surfactant C 45 AS paste with a detergent activity of 71% and a water content of 28% is pumped via a positive displacement pump into a L ⁇ dige CB 30.
  • a powder stream containing a mixture of 2:1 ratio by weight of Zeolite A finely divided sodium carbonate is also fed AS to the l ⁇ dige CB 30.
  • the rate of the powder stream is maintained constant at 400 Kg/hr.
  • the rate of the paste stream is varied until agglomerates of an adequate particle size distribution (a maximum yield between 200 ⁇ m and 1800 ⁇ m) are obtained. Operation at ambient conditions required a rate of 245 kg/hr.
  • a Braun Multipractic food processor is used to manufacture agglomerates containing a full detergent formula for use in laundry cleaning.
  • All the powder components of the formula are weighed and added to the food processor. This mixture contains :
  • All the powders are in a finely divided form prior to addition to the mixer.
  • the mixer is then operated at a low speed for a period of about 1 minute to ensure good mixing of the powders.
  • a mixture of surfactant pastes is prepared in a separate food processor. This mixture contains :
  • the pastes are well mixed by operating the food processor at high speed for a period of about 1 minute. After this, the powder premix is added on top of the paste premix and the food processor is operated at medium speed until granulation occurs (about 1 minute) .
  • the agglomerates made are dried in a fluid bed, and classified using mesh sieves. These agglomerates have excellent physical properties and very good solubility, showing excellent performance in laundry cleaning.
  • STPP fast hydrating sodium tripolyphosphate
  • a l ⁇ dige FM mixer fitted with internal ploughs and high speed choppers with cutter blades.
  • an aqueous surfactant LAS paste with a detergent activity of 78% and a water content of 21% is added on top and the mixer is closed.
  • the mixer is then started and at the same time, water is poured through a hole at the lid of the mixer until granulation occurs.
  • the agglomerates are then discharged, dried • in a fluid bed drier and classified through mesh sieves.
  • the resulting agglomerates have a detergent activity of 25% and show excellent physical and solubility properties to be apt to be incorporated into granular detergents.
  • a nil-surfactant slurry of the composition as given under A and C herebelow and a slurry comprising surfactant of the 2,0 compositions as given under B herebelow were spray-dried using a pressure nozzle under standard conditions, the inlet temperature of the drying air being between 250"C and 320'C, the outlet temperature of the drying air being between 80°C and 120°C and the pressure of the nozzle being between 50 and 100 bar.
  • the ingredients of the slurries, by weight % are :
  • Fig. 1 shows that in the range of shear rates of 1000 to 10.000 ⁇ " ⁇ , the nil-surfactant slurry of composition A of the example has a viscosity that is comparable to the viscosity of the slurry of composition B, that contains surfactant and a larger amount of builder.
  • Spray-drying of compositions having relatively low levels of zeolite using known pressure nozzles therefor presents no problems.
  • Fig. 2 shows the solubility of the nil-surfactant spray-dried powder produced from the slurry of composition A, compared to the spray-dried active powder produced from the slurry of composition B.
  • the spray-dried nil- surfactant powder has a slightly slower rate of dissolution and as a result gel formation is reduced and less residues remain after dispensing.
  • Zanussi (R) laundry machine at a water feed rate of 2 lmin" ⁇ at 20°C, conventional detergents with spray-dried surfactants showed 30-90% residue, whereas the granular detergent comprising the nil-surfactant spray-dried powder and the agglomerated surfactant paste showed less than 5% residues.
  • the particle size distribution of the nil-surfactant spray-dried powder is good for use in a detergent powder, the mass remaining on standard sieves being :
  • the frangibility of the nil-surfactant spray-dried powder was tested by placing the nil-surfactant spray-dried powder remaining on standard sieves no 22 and 36 in a ball mill for 5 minutes and determining the percentage falling through standard sieve 36 after the ball-mill treatment. The percentage passing through the sieve 36 after ball-mill treatment was 66.15% for the nil-active spray-dried powder, which is comparable with the frangibility of the conventional powder formed of the slurry of composition B of this example.
  • This example demonstrates that a high-density granular detergent is obtained by spray-drying a nil-surfactant slurry, subsequently spraying a non-ionic surfactant onto the nil-surfactant spray-dried slurry and mixing the resultant powder with the granulated surfactant and dry additives such as bleach and enzyme.
  • a nil-surfactant slurry was spray-dried using pressure nozzles at 50-100 bar pressure, the drying air having a inlet temperature of 250°C-320°C and an outlet temperature of 80°C-120°C, the composition of the slurry being by weight % :
  • the spray-dried powder had a bulk density of 610 g/1.
  • an alkyl alcohol ethylene oxide condensate (AE3) is sprayed onto the spray-dried powder.
  • the resulting powder is mixed with the agglomerated aninonic surfactant which is produced according to one of the examples 1 to 7, and further ingredients such as builder, bleach and enzyme are added.
  • the finished detergent composition having the following components by weight %, has a density of 800 g/1.
  • Nonionic surfactant 6% Surfactant powder made by agglomeration 19%
  • a powder having the following components by weight % was made by spray-drying :
  • the powders of the composition given under D and E were sprayed with an alcohol containing 25 carbon atoms 3H ethoxylated with 3 moles of ethylene oxide per mole of alcohol (C 2 5AE 3 ) as a nonionic surfactant.
  • Nonionic surfactant (kg) (C 25 AE 3 )
  • composition given at E requires less Zeolite-A, so that the remaining Zeolite-A can be used for agglomeration of the surfactant paste or for dry-mixing.

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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention se rapporte à un procédé de préparation d'un détergent granulaire fluide, ce procédé consistant à: mélanger une quantité efficace d'une pâte tensioactive aqueuse présentant une activité détersive de 40 % au moins, et une quantité efficace d'une poudre détersive sèche, afin de produire un mélange, ladite pâte active tensioactive et l'adjuvant ou la poudre présentant un rapport compris entre 0,05:1 et 19:1; former rapidement un mélange uniforme à partir dudit mélange à une température comprise entre 0 °C et 80 °C environ; granuler ledit mélange en granules détersifs séparés au moyen d'un malaxage à grande vitesse, atteignant une vitesse de pointe de 5-50 m/sec environ; ladite pâte tensioactive étant composée d'au moins un agent tensioactif anionique; et ledit mélange et la granulation s'effectuant simultanément ou de façon séquentielle. Les constituants sans agent tensioactif du détergent granulaire fini, autres que la pâte active granulée, comprennent une partie (relativement petite) de la quantité totale d'adjuvant, une autre partie de l'adjuvant ayant été utilisée pour la granulation. Les constituants sans agent actif peuvent être séchés par pulvérisation afin de former une poudre présentant une couleur agréable, de bonnes caractéristiques de dissolution et de fragilité et des caractéristiques granulométriques et de densité appropriées, destinée à être directement mélangée à sec avec les autres ingrédients du détergent granulaire fini.
PCT/US1992/002880 1991-04-12 1992-04-09 Agglomeration de pates fortement actives pour former des granules tensioactifs pouvant etre utilises dans des compositions detersives WO1992018603A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US08/133,063 US5494599A (en) 1991-04-12 1992-04-09 Agglomeration of high active pastes to form surfactant granules useful in detergent compositions
JP4510266A JPH06506720A (ja) 1991-04-12 1992-04-09 洗剤組成物で有用な界面活性剤粒状物を調整するための高活性ペーストの凝集法
SK1085-93A SK108593A3 (en) 1991-04-12 1992-04-09 Agglomeration of high active pastes to form surfactant granules useful in detergent compositions
BR9205892A BR9205892A (pt) 1991-04-12 1992-04-09 Aglomeraçao de pastas altamente ativas para formargranulos de tensoativos uteis em composiçoes detergentes.
NO933642A NO933642L (no) 1991-04-12 1993-10-11 Aglomerering av hoeyaktive pastaformige materialer for aa danne overflateaktive granuler som kan anvendes i detergentblandinger
FI934464A FI934464A (fi) 1991-04-12 1993-10-11 Agglomeration av ytterst aktiva pastor foer att bilda ytaktiva granuler, vilka aer anvaendbara i tvaettmedelskompositioner

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EP91870061 1991-04-12

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AU (1) AU1878592A (fr)
BR (1) BR9205892A (fr)
CA (1) CA2108167A1 (fr)
CZ (1) CZ213493A3 (fr)
FI (1) FI934464A (fr)
HU (1) HUT67135A (fr)
MX (1) MX9201722A (fr)
NO (1) NO933642L (fr)
SK (1) SK108593A3 (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014529A1 (fr) * 1992-12-23 1994-07-07 Ici Australia Operations Proprietary Limited Procede de granulation
AU666249B2 (en) * 1992-12-23 1996-02-01 Huntsman Surfactants Technology Corporation Granulation process
US5723433A (en) * 1993-09-24 1998-03-03 The Chemithon Corporation Sovent removal process
US6058623A (en) * 1993-09-24 2000-05-09 The Chemithon Corporation Apparatus and process for removing volatile components from a composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5486303A (en) * 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
AU3796497A (en) * 1996-07-26 1998-02-20 Procter & Gamble Company, The Preparation of low ldensity detergent agglomerates containing silica
JP6407682B2 (ja) * 2014-11-27 2018-10-17 花王株式会社 衣料用粉末洗剤組成物の製造方法

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US4092261A (en) * 1974-10-10 1978-05-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing and cleansing agent compositions
US4136051A (en) * 1974-02-25 1979-01-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
US4399048A (en) * 1977-10-06 1983-08-16 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
JPS6072999A (ja) * 1983-09-30 1985-04-25 花王株式会社 超濃縮粉末洗剤の製法
US4515707A (en) * 1983-06-27 1985-05-07 The Chemithon Corporation Intermediate product for use in producing a detergent bar and method for producing same
JPS61118500A (ja) * 1984-11-14 1986-06-05 ライオン株式会社 濃縮型洗剤組成物の製造方法
US4869843A (en) * 1986-01-17 1989-09-26 Kao Corporation High-density granular detergent composition
US4919847A (en) * 1988-06-03 1990-04-24 Colgate Palmolive Co. Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt
US4925585A (en) * 1988-06-29 1990-05-15 The Procter & Gamble Company Detergent granules from cold dough using fine dispersion granulation
EP0390251A2 (fr) * 1989-03-30 1990-10-03 Unilever N.V. Compositions détergentes et procédé pour leur préparation

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Publication number Priority date Publication date Assignee Title
US3920586A (en) * 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4136051A (en) * 1974-02-25 1979-01-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
US4092261A (en) * 1974-10-10 1978-05-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing and cleansing agent compositions
US4399048A (en) * 1977-10-06 1983-08-16 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
US4515707A (en) * 1983-06-27 1985-05-07 The Chemithon Corporation Intermediate product for use in producing a detergent bar and method for producing same
JPS6072999A (ja) * 1983-09-30 1985-04-25 花王株式会社 超濃縮粉末洗剤の製法
JPS61118500A (ja) * 1984-11-14 1986-06-05 ライオン株式会社 濃縮型洗剤組成物の製造方法
US4869843A (en) * 1986-01-17 1989-09-26 Kao Corporation High-density granular detergent composition
US4919847A (en) * 1988-06-03 1990-04-24 Colgate Palmolive Co. Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt
US4925585A (en) * 1988-06-29 1990-05-15 The Procter & Gamble Company Detergent granules from cold dough using fine dispersion granulation
EP0390251A2 (fr) * 1989-03-30 1990-10-03 Unilever N.V. Compositions détergentes et procédé pour leur préparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014529A1 (fr) * 1992-12-23 1994-07-07 Ici Australia Operations Proprietary Limited Procede de granulation
AU666249B2 (en) * 1992-12-23 1996-02-01 Huntsman Surfactants Technology Corporation Granulation process
US5723433A (en) * 1993-09-24 1998-03-03 The Chemithon Corporation Sovent removal process
US6058623A (en) * 1993-09-24 2000-05-09 The Chemithon Corporation Apparatus and process for removing volatile components from a composition

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FI934464A0 (fi) 1993-10-11
SK108593A3 (en) 1994-04-06
MX9201722A (es) 1992-10-01
FI934464A (fi) 1993-10-11
CZ213493A3 (en) 1994-10-19
BR9205892A (pt) 1994-09-27
HU9302873D0 (en) 1994-01-28
NO933642D0 (no) 1993-10-11
CA2108167A1 (fr) 1992-10-13
AU1878592A (en) 1992-11-17
JPH06506720A (ja) 1994-07-28
CN1067674A (zh) 1993-01-06
TW218890B (fr) 1994-01-11
NO933642L (no) 1993-12-13
HUT67135A (en) 1995-02-28

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