EP0349199B1 - Procédé en deux étapes de séchage de compositions de détergent - Google Patents

Procédé en deux étapes de séchage de compositions de détergent Download PDF

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Publication number
EP0349199B1
EP0349199B1 EP89306334A EP89306334A EP0349199B1 EP 0349199 B1 EP0349199 B1 EP 0349199B1 EP 89306334 A EP89306334 A EP 89306334A EP 89306334 A EP89306334 A EP 89306334A EP 0349199 B1 EP0349199 B1 EP 0349199B1
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Prior art keywords
weight
water
slurry
granules
pyrophosphate
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German (de)
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EP0349199A1 (fr
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Larry Rudolph Genskow
George John Kaminsky
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a process for preparing granular detergent compositions by a two step drying operation that results in granules having a low level of reversion of polyphosphate builder (i.e., reversion of tripolyphosphate to pyrophosphate and orthophosphate, or reversion of pyrophosphate to orthophosphate) and/or improved solubility due to a low level of insoluble silicate formation.
  • aqueous slurry comprising the tripolyphosphate, pyrophosphate and/or silicate, other neutral or alkaline salt, water, and optional detergent surfactant
  • the slurry is spray dried in a spray drying tower in a manner such that the granule temperature does not exceed 90°C.
  • the granule temperature refers to the bulk granule temperature.
  • the partially dried granules are then placed in a secondary dryer to complete the drying operation.
  • the granule temperature does not exceed 90°C to minimize polyphosphate reversion in compositions containing tripolyphosphate and/or pyrophosphate, and to minimize formation of silicate insolubles in compositions containing silicate.
  • Granules prepared by the gentle two stage drying process herein also exhibit improved physical properties, such as better flow characteristics and lower caking grades, versus corresponding spray dried granules containing the same water content. Alternatively, granules exhibiting similar physical properties can be obtained at higher moisture levels when prepared by the present process.
  • US-A-3 629 951 and US-A-3 629 955 both published on December 28th, 1971, disclose a means for spray drying large volumes of a synthetic detergent slurry using uniformly spaced atomizing nozzles positioned at at least two different levels, the lower level being in a region having a temperature above 88°C (190°F).
  • One of the benefits claimed. is reduced phosphate reversion. No secondary drying stage is suggested.
  • GB-A-1 237 084 published on 30th June 1971, discloses a soap drying process. Soap slurries are passed through a spray-cooling or spray-drying tower and subsequently through a fluidised bed.
  • Spray-drying processes in general using aqueous crutcher mix slurries are commonly known in the state of the art. Such aqueous slurries often contain from about 25% to 50% by weight of water to allow the slurry to be pumped to the top of spray drying towers. Processes for spray drying large volumes of such slurries in spray drying towers typically utilize inlet air temperatures greater than about 200°C, and often in the range of 300°C to 375°C, in order to remove excess water in the short time (generally about 30 seconds) that the granules remain in the spray drying tower. Crisp, free flowing granules generally contain little free water.
  • the amount of free water in the granules varies depending upon the drying conditions (e.g., time, temperature, and air flow) encountered by any particular granule. Some of the granules are over-dried and not only lose all free water, but also bound water or water of hydration. It has been found that when the granule temperature exceeds about 90°C during drying, excessive amounts of tripolyphosphate and pyrophosphate in the granules revert to the lower polyphosphates. It is desirable to minimize the amount of reversion of tripolyphosphate and pyrophosphate, particularly to orthophosphates which can complex with hardness ions and form insoluble deposits on laundered fabrics. Moreover, when the granule temperature exceeds about 90°C, the formation of silicate insolubles increases.
  • This invention relates to a process for preparing a granular detergent composition comprising the steps of
  • the invention also relates to a process for preparing a granular detergent composition comprising the steps of:
  • the granular detergent compositions herein are prepared by a process that first requires the preparation of an aqueous crutcher mix slurry comprising alkali metal tripolyphosphate and/or pyrophosphate, or silicate, together with other water-soluble neutral or alkaline salt, and detergent surfactant.
  • aqueous crutcher mix slurry comprising alkali metal tripolyphosphate and/or pyrophosphate, or silicate, together with other water-soluble neutral or alkaline salt, and detergent surfactant.
  • the crutcher mix slurry contains from 5% to 50%, preferably from 5% to 40%, more preferably from 10% to 30%, by weight, of a detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof.
  • the surfactant preferably represents from 5% to 60%, more preferably from 10% to 50%, most preferably from 15% to 40%, by weight of the finished composition.
  • 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. No. 4,239,659, Murphy, issued Dec. 16, 1980.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • 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.
  • anionic synthetic surfactants are preferred herein and the amount of soap in the slurry is limited to less than 2% by weight.
  • Useful anionic synthetic surfactants include the water-soluble salts, preferably the alkali metal, ammonium and substituted ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and sulfonic acid or sulfuric acid ester group.
  • alkyl the alkyl portion of acyl groups.
  • these group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11 ⁇ 13LAS.
  • anionic surfactants suitable for use 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 ethylene oxide ether sulfates, containing from 1 to 10 units of ethylene oxide per molecule and from 8 to 12 carbon atoms in the alkyl group; and sodium or potassium salts of alkyl ethylene oxide ether sulfates, containing from 1 to 10 units of ethylene oxide per molecule and from 10 to 20 carbon atoms in the alkyl group.
  • Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 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-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • Nonionic surfactants are also useful in the compositions of the invention. However, because of their volatility, such nonionics are generally not present in amounts greater than 10% by weight of the crutcher mix slurry. Preferably, these nonionics represent less than 5% by weight of the slurry. Most preferably, these nonionics are not present in the slurry.
  • Nonionic surfactants herein 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 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionic surfactants 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 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants useful herein include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Ampholytic surfactants include aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 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 8 to 18 carbon atoms.
  • Cationic surfactants can also be included in laundry compositions of the present invention.
  • Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
  • Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
  • Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976. Such materials will normally be present in an amount from 1% to 10% by weight of the detergent composition.
  • Particularly preferred surfactants herein are anionic surfactants selected from the group consisting of the alkali metal salts of C11 ⁇ 13 alkylbenzene sulfonates, C12 ⁇ 18 alkyl sulfates, C12 ⁇ 18 alkyl linear polyethoxy sulfates containing up to 4 ethylene oxide units, and mixtures thereof.
  • the crutcher mix slurry further contain from 5% to 55%, preferably from 10% to 40%, more preferably from 15% to 30% of an alkali metal tripolyphosphate or pyrophosphate detergent builder material.
  • Tripolyphosphates herein may be Form I or Form II, anhydrous or hydrated.
  • commercially available anhydrous tripolyphosphates typically contain small amounts (e.g., 2-3% by weight) of hydrated material, which aids hydration in the crutcher slurry.
  • commercially available tripolyphosphates generally also contain 4% to 12% by weight of a mixture of pyrophosphate and orthophosphate. Of course, the amount of orthophosphate is preferably minimized, as described previously.
  • a particularly preferred material is sodium tripolyphosphate, some of which (e.g., 40-50%) preferably is present in its hexahydrate form in the crutcher mix slurry.
  • the pyrophosphate salts useful herein can be obtained commercially or can be formed by neutralization of the corresponding pyrophosphoric acids or acid salts.
  • the preferred material herein is sodium or potassium pyrophosphate.
  • tetrasodium pyrophosphate Na4P2O7 and its decahydrate Na4P2O7.10H2O tetrapotassium pyrophosphate K4P2O7, sodium acid pyrophosphate or "acid pyro" Na2H2P2O7 and its hexahydrate Na2H2P2O7.6H2O, and pyrophosphoric acid H4P2O7.
  • Monosodium pyrophosphate and trisodium pyrophosphate also exist, the latter as the anhydrous form or the mono- or nona-hydrate.
  • the generic formula for the anhydrous forms of these compounds can be expressed as M x H y P2O7, where M is alkali metal and x and y are integers having the sum of 4.
  • the crutcher mix slurry contains from 1% to 50%, preferably from 3% to 30%, more preferably from 5% to 20%, by weight of an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from 1.6 to 3.2, preferably from 1.6 to 2.4.
  • an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from 1.6 to 3.2, preferably from 1.6 to 2.4.
  • Sodium silicate particularly having a molar ratio of from 1.6 to 2.2, is preferred.
  • the alkali metal silicates can be purchased in either liquid or granular form. Silicate solutions or slurries can conveniently be used to avoid having to dissolve the dried form in the aqueous crutcher mix slurry of the components herein.
  • the slurry also contains up to 50%, preferably from 5% to 40%, more preferably from 10% to 30%, by weight of a finely divided water-insoluble aluminosilicate ion exchange material of the formula Na z [(AlO2) z .(SiO2) y ].xH2O wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5 and x is from 10 to 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO2.ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 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 18% to 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 microns to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 microns.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 microns to 4 microns.
  • particle size diameter herein represents the average particle size diameter 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 CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least 3.26 mmolCa++/litre/minute/gram/litre (2 grains Ca++/gallon/minute/gram/gallon) of aluminosilicate (anhydrous basis), and generally lies with the range of from 3.26 mmolCa++/litre/minute/gram/litre (2 grains/gallon/minute/gram/gallon) to 9.78 mmolCa++/litre/minute/gram/litre (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 6.52 mmolCa++/litre/minute/gram/litre (4 grains/gallon/minute/gram/gallon).
  • the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg eq. CaCO 2/g (12 mg Mg++/g) and a Mg++ exchange rate of at least 2.72 mmol/litre/minute/gram/litre (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. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • 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 Na12[(AlO2)12.(SiO2)12].xH2O wherein x is from 20 to 30, especially about 27.
  • the crutcher mix slurry herein also contains from 5% to 65%, preferably from 10% to 50%, more preferably from 15% to 40%, by weight, of a water-soluble neutral or alkaline salt other than the tripolyphosphate, and pyrophosphate described above in compositions containing these ingredients, or other than the alkali metal silicate and aluminosilicate materials described above in compositions containing these ingredients.
  • a water-soluble neutral or alkaline salt other than the tripolyphosphate, and pyrophosphate described above in compositions containing these ingredients, or other than the alkali metal silicate and aluminosilicate materials described above in compositions containing these ingredients.
  • Other neutral or alkaline salts herein are described in U.S. Patent 4,379,080, Murphy, issued April 5, 1987.
  • Such neutral or alkaline salts have a pH in solution of about seven or greater, and can be either organic or inorganic in nature. While some of the salts are inert, many of them also function
  • neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides and sulfates.
  • the alkali metal, and especially sodium, salts of the above are preferred.
  • Sodium sulfate and sodium carbonate are typically found in detergent granules and are preferred salts herein.
  • the water-soluble salts herein preferably include the compounds commonly known as detergent builder materials.
  • Such builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • Preferred are the alkali metal, especially sodium, salts of the above.
  • inorganic phosphate builders are polymeric metaphosphate having a degree of polymerization of from 6 to 21.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176; and 3,400,148.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, and tetraborate decahydrate.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Salts of nitrilotriacetic acid, such as sodium nitrilotriacetate, are particularly preferred.
  • Polymeric polycarboxylate 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.
  • Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al.
  • These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution and converted to the corresponding salt.
  • Preferred polycarboxylate builders herein are described in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987.
  • the neutral or alkaline salt of the present invention is preferably selected from the alkali metal polycarboxylates, carbonates, sulfates, and silicates (in compositions containing tripolyphosphates and/or pyrophosphates), and mixtures thereof.
  • the crutcher mix slurry herein also contains from 25% to 50%, preferably from 30% to 45%, more preferably from 30% to 40%, by weight, of water.
  • the aqueous crutcher mix slurry is spray dried in a spray drying tower at an inlet air temperature of at least 200 o C in a manner so that the bulk granule temperature does not exceed 90°C to obtain base granules containing from 5% to 25% water. If there is more than 5% alkali metal tripolyphosphate in the slurry, the base granules preferably contain from 8% to about 20% by weight of water. Otherwise, the base granules preferably contain from 7% to 15% by weight of water.
  • the air inlet temperature is preferably at least 230 o C, more preferably at least 260°C. It is also preferred that the granule temperature not be allowed to exceed 85°C, and more preferably not exceed 80°C, to minimize reversion of polyphosphates when present in the granules and also to minimize formation of silicate insolubles when silicate is present.
  • the resulting base granules which are generally free flowing agglomerates, are then further dried in a secondary dryer in a manner so that the granule temperature again does not exceed 90 o C to obtain granules containing from 2% to 20%, preferably from 2% to 8%, water.
  • the granule temperature does not exceed 85°C. More preferably, it does not exceed 80°C.
  • the granules should contain at least 4% water, and preferably contain from 8% to 16% water, after drying in the secondary dryer.
  • the drying should be accomplished so that no more than 5% by weight of each of the tripolyphosphate and pyrophosphate is reverted to lower phosphates during the drying in the spray tower and in the secondary dryer.
  • Any secondary dryer capable of drying the granules at the required temperature and moisture levels can be used in the practice of this invention.
  • Suitable secondary dryers include rotary drum dryers, pneumatic conveying dryers, air lift dryers, conveyor and tray-type dryers, and the like.
  • a fluid bed dryer is particularly preferred.
  • the resulting granular detergent compositions can be used as is as finished detergent compositions or as detergent additive compositions.
  • the granules are preferably admixed with or agglomerated with other optional ingredients to provide finished detergent compositions.
  • compositions of the present invention can be included in the compositions of the present invention.
  • auxiliary detergent surfactant and builder materials bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
  • bleaching agents and bleach activators suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes.
  • Bleaching agents and activators are also described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,
  • typical laundry wash water solutions comprise from 0.1% to 2% by weight of the composition. Fabrics to be laundered are agitated in these solutions to effect cleaning, stain removal, and optional fabric care benefits.
  • the pH of a 0.1% by weight aqueous solution of this composition will be in the range of from 7.0 to 11.0, preferably from 8.0 to 11.0, and most preferably from 9.0 to 10.5.
  • a crutcher slurry is prepared containing the following components.
  • Component Wt. % Sodium C13 linear alkylbenzene sulfonate 7.5 Sodium C14 ⁇ 15 alkyl sulfate 7.5 Sodium tripolyphosphate (anhydrous) 32.8 Sodium silicate (1.6 ratio) 4.6 Sodium polyacrylate (MW 4500) 0.9 Polyethylene glycol (MW 8000) 0.4 Sodium sulfate and minors 9.8 Water 36.5
  • the crutcher slurry is held approximately 5-10 minutes so that 30-80% of the tripolyphosphate hydrates to the hexahydrate form.
  • the slurry is spray dried by atomizing with swirl nozzles at 35-84 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 332°C.
  • a slip stream sample of partially dried granules having a temperature of less than about 55°C and containing about 18.8% water is captured from within the spray tower and continuously fed to a fluidized bed, having a cross-sectional area of 0.14 m2. Fluid bed air is heated to about 165°C and pumped through a perforated distribution plate at sufficient rate to fluidize the bed of granules.
  • Dried granules are continuously withdrawn from the bed at about 72.7 kg/hr. and contain 10.4% water.
  • the temperature of the sample is about 88°C.
  • Less than about 3% of the tripolyphosphate has reverted to pyrophosphate and orthophosphate during the drying process. This compares to about 15% reversion in a sample taken from the bottom of the spray tower at the same time and having a temperature of about 104°C.
  • the black-fabric solubility grade for the above fluid bed sample is 9.5 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 7.5 for the totally spray dried sample taken from the bottom of the spray drying tower. Further, the cake grade for the fluid bed sample is 1.5 (kg force to break a 6.35 cm diameter x 6.35 cm long cylindrical plug formed under a 9.1 kg weight for one minute) versus a grade of 3.3 for the totally spray dried sample.
  • a crutcher slurry is prepared containing the following components.
  • Component Wt. % Sodium C12 linear alkylbenzene sulfonate 3.3 Sodium tallowalkyl sulfate 5.3 Sodium C14 ⁇ 15 alkyl sulfate 5.3 Sodium toluene sulfonate 0.8 Sodium tripolyphosphate 4.5 Tetrasodium pyrophosphate 18.2 Sodium silicate (1.6 ratio) 4.5 Sodium polyacrylate (MW 4500) 1.0 Sodium sulfate and minors 24.6 Water 32.5
  • the slurry is dried in two stages as described in Example I to provide a composition of the present invention.
  • a crutcher slurry is prepared containing the following components.
  • Component Wt. % Sodium C13 linear alkylbenzene sulfonate 7.3 Sodium C14 ⁇ 15 alkyl sulfate 7.3 Tallow fatty acid 0.7 Sodium Zeolite A (hydrated, avg. dia. 3 microns) 17.9 Sodium silicate (1.6 ratio) 1.4 Sodium carbonate 3.7 Sodium polyacrylate (MW 4500) 1.1 Polyethene glycol (MW 8000) 1.1 Sodium sulfate and minors 26.1 Water 33.4
  • the slurry is spray dried by atomizing with swirl nozzles at 77 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 254°C.
  • a sample of partially dried granules having a temperature of less than about 55°C and containing about 18.8% water is captured from within the spray tower and charged to a batch fluidized bed having a cross-sectional area of 0.14 m2. Fluid bed air is heated to about 163°C and pumped through a perforated distribution plate at sufficient rate to fluidize the bed of partially dried granules.
  • a sample of dried granules is withdrawn from the bed and contains 8.8% water.
  • the temperature of the sample is about 47°C.
  • the black-fabric solubility grade for the fluid bed sample is 9.0 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 7.5 for a sample taken at the exit of the spray tower during the same time period.
  • a crutcher slurry is prepared containing the following components.
  • Component Wt. % Sodium C13 linear alkylbenzene sulfonate 9.5 Sodium C14 ⁇ 15 alkyl polyethoxy (2.25) sulfate 4.1 Tallow fatty acid 0.1 Sodium silicate (2.4 ratio) 13.2 Sodium carbonate 13.8 Sodium sulfate 23.7 Minors 0.6 Water 35.0
  • the slurry is spray dried by atomizing with swirl nozzles at 28-84 kg/cm2 pressure into a counter-current spray drying tower having an inlet air temperature of about 343°C.
  • a 13.6 kg sample of partially dried granules having a temperature of less than about 55°C and containing about 9.2% water is captured from within the spray tower and charged to a batch fluidized bed having a cross-sectional area of 0.14 m2.
  • the fluid bed inlet air is heated to about 152°C and pumped through a perforated distribution plate at sufficient rate to thoroughly fluidize the bed of partially dried granules.
  • a sample of dried granules is withdrawn from the bed and contains 5.6% water.
  • the temperature of the sample is about 84°C.
  • the black-fabric solubility grade for the fluid bed sample is 7.0 (on a 0-10 scale, where 10 equals no insolubles) versus a grade of 3.5 for a sample taken at the exit of the spray tower during the same time period and having a temperature of 123°C.

Claims (11)

  1. Procédé de préparation d'une composition détergente granulaire comprenant les étapes consistant à :
    (a) former une suspension aqueuse comprenant, en poids ,
    (1) un agent tensio-actif détergent ;
    (2) de 5% à 55%, de préférence de 15% à 30%, d'un tripolyphosphate ou pyrophosphate d'un métal alcalin, ou leurs mélanges ;
    (3) de 5% à 65% d'un sel neutre ou alcalin hydrosoluble autre que le tripolyphosphate et le pyrophosphate de (2) ; et
    (4) de 25% à 50%, de préférence 30% à 45% d'eau ;
    (b) sécher par pulvérisation la suspension aqueuse dans une tour de pulvérisation à une température d'entrée d'air d'au moins 200°C pour obtenir des granules de base comprenant de 5% à 25% en poids d'eau ; et
    (c) sécher les granules de base dans un dessicateur secondaire pour obtenir des granules contenant de 2% à 20% en poids d'eau, mais au moins 4% en poids d'eau lorsque la suspension comprend plus de 5% en poids de tripolyphosphate, avec pas plus de 5% en poids de chacun des éventuels tripolyphosphate et pyrophosphate présents dans la suspension retournant au pyrophosphate, à l'orthophosphate, et à leurs mélanges, au cours des étapes (b) et (c),
       caractérisé en ce que la suspension aqueuse comprend de 5% à 50% en poids d'un agent tensio-actif détergent, de préférence de 10% à 30% d'un agent tensio-actif anionique, et en ce que la quantité de savon dans la suspension est limitée à moins de 2% en poids, et en ce que la température des granules n'excède pas 90øC à un moment quelconque au cours des étapes (b) et (c).
  2. Procédé selon la revendication 1 dans lequel l'agent tensio-actif anionique est choisi dans le groupe constitué par les sulfonates d'alkyle en C₁₁-C₁₃-benzène, les sulfates d'alkyle en C₁₂-C₁₈, les sulfates d'alkyle en C₁₂-C₁₆ éthoxylés avec une moyenne allant jusqu'à quatre motifs d'oxyde d'éthylène, et leurs mélanges.
  3. Procédé selon les revendications 1 ou 2 dans lequel la température d'entrée d'air de la tour est d'au moins 230°C, de préférence d'au moins 260°C, la température des granules de base n'excède pas 85°C, et les granules de base comprennent de 8% à 20% en poids d'eau.
  4. Procédé selon l'une quelconque des revendications précédentes dans lequel on sèche les granules de base dans un dessicateur secondaire, de préférence un dessicateur à lit fluidisé, tout en ne dépassant pas une température des granules de 85°C pour obtenir des granules contenant de 8% à 16% en poids d'eau.
  5. Procédé selon les revendications 1, 2 ou 3, dans lequel on sèche les granules de base dans un dessicateur secondaire, de préférence un dessicateur à lit fluidisé, tout en ne dépassant pas une température de granule de base de 85°C pour obtenir des granules comprenant de 2% à 8% en poids d'eau avec pas plus de 2% en poids de chacun des éventuels tripolyphosphate et pyrophosphate présents dans la suspension retournant au pyrophosphate, à l'orthophosphate, et à leurs mélanges au cours des étapes (b) et (c).
  6. Procédé de préparation d'une composition détergente granulaire comprenant les étapes consistant à
    (a) former une suspension aqueuse comprenant, en poids :
    (1) un agent tensio-actif détergent ;
    (2) de 1% à 50%, de préférence de 3% à 30%, d'un silicate de métal alcalin ayant un rapport molaire de SiO₂ à l'oxyde de métal alcalin compris entre 1,6 et 3,2, de préférence un silicate de sodium ayant un rapport molaire de SiO₂ à l'oxyde de sodium compris entre 1,6 et 2,4 ;
    (3) de 5% à 65% d'un sel neutre ou alcalin hydrosoluble autre que le silicate de (2) et l'aluminosilicate ; et
    (4) de 25% à 50%, de préférence de 30% à 45% d'eau ; et
    (b) sécher par pulvérisation la suspension aqueuse dans une tour de pulvérisation à une température d'entrée d'air d'au moins 200°C pour obtenir des granules de base comprenant de 5% à 25% en poids d'eau ; et
    (c) sécher les granules de base dans un dessicateur secondaire pour obtenir des granules comprenant de 2% à 20% en poids d'eau,
       caractérisé en ce que la suspension aqueuse comprend de 5% à 50% en poids d'un agent tensio-actif détergent, de préférence de 10% à 30% d'un agent tensio-actif anionique ; et en ce que la quantité de savon dans la suspension est limitée à moins de 2% en poids, et en ce que la température des granules ne dépasse pas 90°C à un moment quelconque au cours des étapes (b) et (c).
  7. Procédé selon la revendication 6, caractérisé en ce que la suspension comprend de 5% à 50% d'une matière échangeuse d'ions à base d'aluminosilicate finement divisé choisie dans le groupe constitué par :
    (i) une matière de type aluminosilicate cristallin de formule :



            Naz [ (AlO₂)z (SiO₂)y ].xH₂O



    dans laquelle z et y valent au moins 6, le rapport molaire de z à y est de 1,0 à 0,5 et x vaut de 10 à 264, ladite matière ayant un diamètre particulaire compris entre 0,1 micromètre et 10 micromètres, une capacité d'échange d'ions calcium d'au moins 200 mg d'éq. CaCO₃ /g. et une vitesse d'échange d'ions calcium d'au moins 3,26 mmol de Ca⁺⁺ /litre/minute/gramme/litre ; (2 grains de Ca⁺⁺/gallon/minute/gramme/gallon)
    (ii) une matière de type aluminosilicate hydraté amorphe de formule brute :



            Mz (zAlO₂.ySiO₂)



    dans laquelle M représente le sodium, le potassium, l'ammonium ou l'ammonium substitué, z vaut de 0,5 à 2 et y vaut 1, ladite matière ayant une capacité d'échange de magnésium d'au moins 50 milligrammes d'équivalents de dureté CaCO₃ par gramme d'aluminosilicate anhydre et une vitesse d'échange de Mg⁺⁺ d'au moins 2,72 mmol/litre/minute/gramme/litre ; (1 grain/gallon/minute/gramme/gallon) et
    (iii) leurs mélanges.
  8. Procédé selon les revendications 6 ou 7, dans lequel l'agent tensio-actif de synthèse anionique est choisi dans le groupe constitué par les sulfonates d'alkyle en C₁₁-C₁₃-benzène, les sulfates d'alkyle en C₁₂-C₁₈, les sulfates d'alkyle en C₁₂-C₁₆ éthoxylés avec une moyenne allant jusqu'à quatre motifs d'oxyde d'éthylène, et leurs mélanges .
  9. Procédé selon les revendications 6, 7 ou 8, dans lequel la suspension comprend de 5% à 40%, de préférence de 10% à 30%, en poids d'une matière échangeuse d'ions de type aluminosilicate de formule



            Na₁₂[(AlO₂)₁₂.(SiO₂)₁₂].xH₂O



    dans laquelle x vaut de 20 à 30.
  10. Procédé selon les revendications 6, 7; 8, ou 9 dans lequel on sèche par pulvérisation la suspension à une température d'entrée d'air dans la tour d'au moins 260 °C tout en ne dépassant pas une température des granules de 85°C pour obtenir des granules de base comprenant de 7% à 15% en poids d'eau.
  11. Procédé selon les revendications 6, 7, 8, 9 ou 10 dans lequel on sèche les granules de base dans un dessicateur secondaire, de préférence un dessicateur à lit fluidisé, tout en ne dépassant pas une température des granules de 85°C pour obtenir des granules contenant de 2% à 8% en poids d'eau.
EP89306334A 1988-06-29 1989-06-23 Procédé en deux étapes de séchage de compositions de détergent Expired - Lifetime EP0349199B1 (fr)

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US21280588A 1988-06-29 1988-06-29
US212805 1988-06-29

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EP0349199B1 true EP0349199B1 (fr) 1995-03-08

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318584A (en) * 1996-10-25 1998-04-29 Procter & Gamble Process for preparing detergent compositions by spray drying
ES2354819T3 (es) 2005-08-19 2011-03-18 The Procter And Gamble Company Composición detergente para lavar ropa, sólida, que comprende alquil benceno sulfonato, sal carbonato y polímero de carboxilato.
ATE465235T1 (de) 2005-08-19 2010-05-15 Procter & Gamble Festförmige waschmittelzusammensetzung enthaltend alkylbenzolsulphonat und ein hydratbarer stoff
EP1754776A1 (fr) * 2005-08-19 2007-02-21 The Procter and Gamble Company Procédé pour la préparation d'une composition détergente solide pour le lavage, comprenant au moins deux pas séchant
PL1754781T3 (pl) 2005-08-19 2013-09-30 Procter & Gamble Stała kompozycja detergentowa do prania zawierająca anionowy środek powierzchniowo czynny i technologię wspomagania wapniem

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629951A (en) * 1970-07-31 1971-12-28 Procter & Gamble Multilevel spray-drying method
US3629955A (en) * 1970-07-31 1971-12-28 Procter & Gamble Multilevel spray-drying apparatus
US4019998A (en) * 1974-09-27 1977-04-26 The Procter & Gamble Company Process for preparing a pyrophosphate-silicate detergent product

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Publication number Priority date Publication date Assignee Title
FR1481514A (fr) * 1965-05-28 1967-05-19 Knapsack Ag Procédé de préparation de détersifs contenant du tripolyphosphate de sodium
GB1237084A (en) * 1967-10-02 1971-06-30 Unilever Ltd Soap drying process
US4116852A (en) * 1975-02-14 1978-09-26 The Procter & Gamble Company Builders and built detergent compositions
GR79391B (fr) * 1982-11-08 1984-10-22 Procter & Gamble

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629951A (en) * 1970-07-31 1971-12-28 Procter & Gamble Multilevel spray-drying method
US3629955A (en) * 1970-07-31 1971-12-28 Procter & Gamble Multilevel spray-drying apparatus
US4019998A (en) * 1974-09-27 1977-04-26 The Procter & Gamble Company Process for preparing a pyrophosphate-silicate detergent product

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DE68921512D1 (de) 1995-04-13
EP0349199A1 (fr) 1990-01-03
ES2068894T3 (es) 1995-05-01
DE68921512T2 (de) 1995-11-09

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