EP0349199A1 - Procédé en deux étapes de séchage de compositions de détergent - Google Patents

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

Info

Publication number
EP0349199A1
EP0349199A1 EP89306334A EP89306334A EP0349199A1 EP 0349199 A1 EP0349199 A1 EP 0349199A1 EP 89306334 A EP89306334 A EP 89306334A EP 89306334 A EP89306334 A EP 89306334A EP 0349199 A1 EP0349199 A1 EP 0349199A1
Authority
EP
European Patent Office
Prior art keywords
water
weight
granules
slurry
sodium
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP89306334A
Other languages
German (de)
English (en)
Other versions
EP0349199B1 (fr
Inventor
Larry Rudolph Genskow
George John Kaminsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0349199A1 publication Critical patent/EP0349199A1/fr
Application granted granted Critical
Publication of EP0349199B1 publication Critical patent/EP0349199B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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 granular detergent compositions prepared 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 about 90 o 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 about 90 o 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.
  • Aqueous crutcher mix slurries often contain from about 25% to about 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 o C, and often in the range of 300 o C to 375 o 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. However, 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 o 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 o C, the formation of silicate insolubles increases.
  • This invention relates to granular detergent compositions prepared by:
  • the invention also relates to granular detergent compositions prepared by:
  • the invention further relates to the two stage drying process used to prepare the above granular detergent compositions.
  • 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, pyrophos­phate, and/or silicate, together with other water-soluble neutral or alkaline salt, and preferably detergent surfactant.
  • aqueous crutcher mix slurry comprising alkali metal tripolyphosphate, pyrophos­phate, and/or silicate, together with other water-soluble neutral or alkaline salt, and preferably detergent surfactant.
  • the crutcher mix slurry can contain from 0% to about 50%, preferably from about 5% to about 40%, more preferably from about 10% to about 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 about 5% to about 60%, more preferably from about 10% to about 50%, most preferably from about 15% to about 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.
  • 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, both incorporated herein by reference.
  • 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 generally limited to less than about 5%, preferably less than about 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 about 10 to about 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 about 9 to about 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, both of which are incorporated herein by reference.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 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 about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; 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 from about 10 to about 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 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-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to 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; water-soluble 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 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 about 10% by weight of the crutcher mix slurry. Preferably, these nonionics represent less than about 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 about 6 to 15 carbon atoms, in either a straight chain or branched chain con­figuration, with from about 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 about 9 to 15 carbon atoms with from about 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 about 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 about 10 to 18 carbon atoms and two 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 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 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 about 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 about 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, incorporated herein by reference.
  • 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, which is incorporated herein by reference. Such materials will normally be present in an amount from about 1% to about 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 about 4 ethylene oxide units, and mixtures thereof.
  • the crutcher mix slurry further contain from about 5% to about 55%, preferably from about 10% to about 40%, more preferably from about 15% to about 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 about 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 Na4P2O7.10H20 tetrapotassium pyrophosphate K4P2O7, sodium acid pyrophosphate or "acid pyro" Na2H2P2O7 and its hexahydrate Na2H2P2O7.6H20, 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 about 1% to about 50%, preferably from about 3% to about 30%, more preferably from about 5% to about 20%, by weight of an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from about 1.6 to about 3.2, preferably from about 1.6 to about 2.4.
  • an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from about 1.6 to about 3.2, preferably from about 1.6 to about 2.4.
  • Sodium silicate particularly having a molar ratio of from about 1.6 to about 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 about 50%, preferably from about 5% to about 40%, more preferably from about 10% to about 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 about 6, the molar ratio of z to y is from about 1.0 to about 0.5 and x is from about 10 to about 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 about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 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 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.
  • 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 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 with 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 capacity of at least about 50 mg eq. CaCO2/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. Patent 3,985,669, Krummel, et al, issued October 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 Na12[(AlO2)12.(SiO2)12].xH2O wherein x is from about 20 to about 30, especially about 27.
  • the crutcher mix slurry herein also contains from about 5% to about 65%, preferably from about 10% to about 50%, more preferably from about 15% to about 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.
  • Other neutral or alkaline salts herein are described in U.S. Patent 4,379,080, Murphy, issued April 5, 1987, incorporated herein by reference. 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
  • 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 about 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, incorporated herein by reference.
  • 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, incorporated herein by reference. 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.
  • 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, both incorporated herein by reference.
  • 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, incorporated herein by reference.
  • 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 abut 25% to about 50%, preferably from about 30% to about 45%, more preferably from abut 30% to about 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 about 200 o C in a manner so that the bulk granule temperature does not exceed about 90 o C to obtain base granules containing from about 5% to about 25% water. If there is more than about 5% alkali metal tripolyphosphate in the slurry, the base granules preferably contain from about 8% to about 20% by weight of water. Otherwise, the base granules preferably contain from about 7% to about 15% by weight of water.
  • the air inlet temperature is preferably at least about 230 o C, more preferably at least about 260 o C. It is also preferred that the granule temperature not be allowed to exceed about 85 o C, and more preferably not exceed about 80 o 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 about 90 o C to obtain granules containing from about 2% to about 20%, preferably from about 2% to about 8%, water.
  • the granule temperature does not exceed about 85 o C. More preferably, it does not exceed about 80 o C.
  • the granules should contain at least about 4% water, and preferably contain from about 8% to about 16% water, after drying in the secondary dryer.
  • the drying should be accomplished so that no more than about 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 about 0.1% to about 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 about 7.0 to about 11.0, preferably from about 8.0 to about 11.0, and most preferably from about 9.0 to about 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 o C.
  • a slip stream sample of partially dried granules having a temperature of less than about 55 o 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 o 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 o 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 o C.
  • This demonstrates the lower tripoly­phosphate reversion that can be obtained using the two stage drying operation of the present invention versus a conventional spray drying process and the importance of maintaining the granule temperature under 90 o C during the two stage drying operation.
  • 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 o C.
  • a sample of partially dried granules having a temperature of less than about 55 o 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 o 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 o 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 o C.
  • a 13.6 kg sample of partially dried granules having a temperature of less than about 55 o 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 o 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 o 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 o C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP89306334A 1988-06-29 1989-06-23 Procédé en deux étapes de séchage de compositions de détergent Expired - Lifetime EP0349199B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US21280588A 1988-06-29 1988-06-29
US212805 1988-06-29

Publications (2)

Publication Number Publication Date
EP0349199A1 true EP0349199A1 (fr) 1990-01-03
EP0349199B1 EP0349199B1 (fr) 1995-03-08

Family

ID=22792491

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89306334A Expired - Lifetime EP0349199B1 (fr) 1988-06-29 1989-06-23 Procédé en deux étapes de séchage de compositions de détergent

Country Status (3)

Country Link
EP (1) EP0349199B1 (fr)
DE (1) DE68921512T2 (fr)
ES (1) ES2068894T3 (fr)

Cited By (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
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
US7910533B2 (en) 2005-08-19 2011-03-22 The Procter & Gamble Company Solid laundry detergent composition comprising anionic detersive surfactant and calcium-augmented technology
US7910534B2 (en) 2005-08-19 2011-03-22 The Procter & Gamble Company Solid laundry detergent composition comprising alkyl benzene sulphonate and a hydratable material
US8129323B2 (en) 2005-08-19 2012-03-06 The Procter & Gamble Company Solid laundry detergent composition comprising alkyl benzene sulphonate, carbonate salt and carboxylate polymer

Citations (4)

* Cited by examiner, † Cited by third party
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
EP0110592A1 (fr) * 1982-11-08 1984-06-13 The Procter & Gamble Company Détergents granulaires contenant du pyrophosphate et tripolyphosphate comme moyens du procédé

Family Cites Families (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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
EP0110592A1 (fr) * 1982-11-08 1984-06-13 The Procter & Gamble Company Détergents granulaires contenant du pyrophosphate et tripolyphosphate comme moyens du procédé

Cited By (8)

* 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
EP0934395A1 (fr) * 1996-10-25 1999-08-11 The Procter & Gamble Company Compositions detergentes
EP0934395A4 (fr) * 1996-10-25 2000-02-23 Procter & Gamble Compositions detergentes
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
WO2007020608A1 (fr) * 2005-08-19 2007-02-22 The Procter & Gamble Company Procede de preparation d'une composition de detergeant de lessive solide comprenant au moins deux etapes de sechage
US7910533B2 (en) 2005-08-19 2011-03-22 The Procter & Gamble Company Solid laundry detergent composition comprising anionic detersive surfactant and calcium-augmented technology
US7910534B2 (en) 2005-08-19 2011-03-22 The Procter & Gamble Company Solid laundry detergent composition comprising alkyl benzene sulphonate and a hydratable material
US8129323B2 (en) 2005-08-19 2012-03-06 The Procter & Gamble Company Solid laundry detergent composition comprising alkyl benzene sulphonate, carbonate salt and carboxylate polymer

Also Published As

Publication number Publication date
EP0349199B1 (fr) 1995-03-08
ES2068894T3 (es) 1995-05-01
DE68921512T2 (de) 1995-11-09
DE68921512D1 (de) 1995-04-13

Similar Documents

Publication Publication Date Title
US5565422A (en) Process for preparing a free-flowing particulate detergent composition having improved solubility
US4487710A (en) Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
US4605509A (en) Detergent compositions containing sodium aluminosilicate builders
US4274975A (en) Detergent composition
EP0581857B1 (fr) Compositions detersives granulaires pour lessive, presentant une solubilite amelioree
US4303556A (en) Spray-dried detergent compositions
EP0451894B2 (fr) Compositions détergentes granulaires à haute densité apparente et leur procédé de préparation
US4695284A (en) Cool water fabric washing process using a particulate detergent containing a nonionic and a fatty acid builder salt
US4180485A (en) Spray-dried detergent compositions
EP0061226B1 (fr) Compositions détergentes séchées par atomisation
EP0260971B1 (fr) Composition détergente et son procédé de production
US5300250A (en) Granular laundry compositions having improved solubility
US5538671A (en) Detergent compositions with builder system comprising aluminosilicates and polyaspartate
US4215007A (en) Process for the manufacture of low-phosphorus or phosphorus-free detergents containing aluminosilicates
US5736502A (en) Process for preparing detergent compositions
EP0349199B1 (fr) Procédé en deux étapes de séchage de compositions de détergent
US4704221A (en) Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant
CA1229021A (fr) Detersif granulaire contenant de l'aluminosilicate de sodium ou d'autres adjuvants pour detergent exempts de phosphore
US5536432A (en) Process for the production of a detergent composition
US5998356A (en) Process for making granular detergents
CA2231577C (fr) Procede de fabrication de detergents granulaires
EP0063399B2 (fr) Compositions détergentes granulaires contenant des polymères pelliculaires
EP0837123A2 (fr) Composition détergente à stabilité améliorée contenant un agent de blanchiment halogéné, et procédé pour sa fabrication
USH1604H (en) Process for continuous production of high density detergent agglomerates in a single mixer/densifier
EP0723581A1 (fr) Procede continu pour produire un detergent granulaire a haute densite

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19900608

17Q First examination report despatched

Effective date: 19930310

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR GB IT

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 68921512

Country of ref document: DE

Date of ref document: 19950413

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2068894

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990504

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990602

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19990611

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990624

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000623

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000624

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000623

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010403

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20020204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050623