EP0929653B1 - Verfahren zur herstellung von einer waschmittelzusammensetzung nach ohne-turm-verfahren - Google Patents

Verfahren zur herstellung von einer waschmittelzusammensetzung nach ohne-turm-verfahren Download PDF

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Publication number
EP0929653B1
EP0929653B1 EP97931058A EP97931058A EP0929653B1 EP 0929653 B1 EP0929653 B1 EP 0929653B1 EP 97931058 A EP97931058 A EP 97931058A EP 97931058 A EP97931058 A EP 97931058A EP 0929653 B1 EP0929653 B1 EP 0929653B1
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EP
European Patent Office
Prior art keywords
process according
detergent
surfactant
agglomerates
mixer
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EP97931058A
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English (en)
French (fr)
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EP0929653A1 (de
Inventor
Wayne Edward Beimesch
Jose Francisco Correa Romo
Steven Barrett Rogers
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • 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
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention generally relates to a non-tower process for producing a particulate detergent composition. More particularly, the invention is directed to a continuous process during which detergent agglomerates are produced by feeding a surfactant and coating materials into a series of mixers. The process produces a free flowing, detergent composition whose density can be adjusted for wide range of consumer needs, and which can be commercially sold.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules (e.g., tower process for low density detergent compositions).
  • the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (e.g., agglomeration process for high density detergent compositions).
  • the important factors which govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the various starting materials, the shape of the various starting materials, and their respective chemical composition.
  • the Laid-open No.WO93/23,523 (Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt% of the granules having a diameter over 2 mm.
  • the U.S. Patent No. 4,427,417 (Korex) describes continuous process for agglomeration which reduces caking and oversized agglomerates.
  • US5554587 discloses a process for preparing detergent compositions comprising inputting air into a mixer during the agglomeration of a surfactant paste and other detergent ingredients, so that at least a minor amount of water from said surfactant paste is absorbed by said air.
  • WO9609370 discloses a process for preparing high density detergent compositions comprising the steps of mixing a surfactant paste and dry detergent ingredients in a mixer to form first agglomerates, conditioning said first agglomerates to obtain second agglomerates having a specific particle size, recycling any agglomerates not having the desired particle size for further agglomeration to obtain second agglomerates having the desired particle size, admixing detergent ingredients to said second agglomerates to form a high density detergent composition.
  • EP663439 discloses a process for making a detergent component which comprises the steps of making a detergent paste comprising water-soluble silicate salt and surfactant or water-soluble polymer, and dispersing said paste with a builder powder under pressure.
  • WO9325378 discloses a process for preparing detergent compositions comprising the steps of dispersing a surfactant paste through a powder stream, agglomerating the paste and powder in a mixer and drying or cooling the agglomerates.
  • WO9512659 addresses the problem of preparing low relative humidity detergents in elevated process temperatures and solves this problem by employing a pre-conditioned gas in the process conditions.
  • US5489392 discloses a process for preparing high density detergents comprising the steps of mixing a surfactant paste in a mixer to form agglomerates, screening said agglomerates to form a first agglomerate mixture, separating the agglomerates according to particle size and either grinding or recycling agglomerates for further agglomeration to obtain a final agglomerate mixture having the desired particle size, admixing detergent ingredients to the final agglomerate mixture to obtain a high density detergent composition.
  • WO9201036 discloses a process for producing surfactant granules comprising the steps of mixing a water-containing surfactant with a solid to form granules, drying the granules and recycling the dried granules as a portion of the solid.
  • fluidised bed for other purposes when manufacturing particulate detergents.
  • fluidised particulate material comprising a builder
  • the process does not use the conventional spray drying towers currently which is limited in producing high surfactant loading compositions.
  • the process of the present invention is more efficient, economical and flexible with regard to the variety of detergent compositions which can be produced in the process.
  • the process is more amenable to environmental concerns in that it does not use spray drying towers which typically emit particulates and volatile organic compounds into the atmosphere.
  • agglomerates refers to particles formed by agglomerating raw materials with binder scuh as surfactants and or inorganic solutions / organic solvents and polymer solutions.
  • granulating refers to fluidising agglomerates thoroughly for producing free flowing, round shape granulated-agglomerates.
  • a process for preparing a granular detergent composition having a density at least about 600g/l is provided.
  • the process comprises the steps of:
  • the invention results in the production of granular detergent compositions having a high density of at least about 600g/l.
  • surfactant i.e., one or more of aqueous and/or non-aqueous surfactant(s), which is/are in the form of powder, paste and/or liquid, and fine powder having a diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns are fed into a mixer, so as to make agglomerates.
  • a mixer so as to make agglomerates.
  • an internal recycle stream of powder having a diameter of about 0.1 to about 300 microns generated from fluidising apparatus which is described hereinafter in the second step, can be fed into the mixer in addition to the fine powder.
  • the amount of such internal recycle stream of powder can be 0 to about 60 wt% of the final product from the process of the present invention.
  • the surfactant(s) can be initially fed into a mixer or premixer (e.g., a conventional screw extruder or other similar mixer) prior to the above, after which the mixed detergent materials are fed into the first step mixer as described herein for agglomeration.
  • a mixer or premixer e.g., a conventional screw extruder or other similar mixer
  • the mean residence time of the mixer is in range from about 2 to about 50 seconds and tip speed of the mixer is in range from about 4 m/s. to about 25 m/s
  • the energy per unit mass of the mixer (energy condition) is in the range from about 0.15 kj/kg to about 7 kj/kg
  • the mean residence time of the mixer is in range from about 5 to about 30 seconds and tip speed of the mixer is in range from about 6 m/s to about 18 m/s
  • the energy per unit mass of the mixer (energy condition) is in range from about 0.3 kj/kg to about 4 kj/kg
  • the mean residence time of the mixer is in range from about 5 to about 20 seconds and tip speed of the mixer is in range from about 8 m/s to about 18 m/s
  • the energy per unit mas of the mixer (energy condition) is from about 0.3 kj/kg to about 4 kj/kg.
  • mixers for the first step can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the first step.
  • An example can be Lodige CB Mixer manufacture by the Lodige company (Germany).
  • resultant product agglomerates having fine powder on the surface of the agglomerates
  • the resultant product of the first step (the agglomerates) is fed into a fluidised bed apparatus while spraying into the bed droplets of liquid detergent material in an amount of up to 20%, in order to enhance granulation for producing free flowing high density granules.
  • the resultant product from the first step is fluidised thoroughly so that the granules from the second step have a round shape.
  • about 0 to about 10%, more preferably about 2-5% of powder detergent materials of the kind used in the first step and/or other detergent ingredients can be added to the second step.
  • the liquid detergent materials sprayed into the bed may be of the kind used in the first step and/or other detergent ingredients can be added to the step, for enhancing granulation and coating on the surface of the granules.
  • condition of a fluidised apparatus is:
  • the second step can utilise more than one fluidised apparatus (e.g., combining different kinds of fluidised apparatus such as fluid bed dryer and fluid bed cooler ). If there is more than one fluidised apparatus, each may be operated under the same ranges of conditions, but the atomised liquid may be present only in one of the beds. If two different kinds of fluidised apparatus would be used, mean residence time of the second step in total can be from about 2 to about 20 minutes, more preferably, from about 2 to 12 minutes.
  • a coating agent to improve flowability and/or minimise over agglomeation of the detergent composition can be added in one or more of the following locations of the instant process: (1) the coating agent can be added directly after the fluid bed cooler or fluid bed dryer and/or (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler.
  • the coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
  • the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping for detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
  • the total amount of the surfactants in products made by the present invention, which are included in the following detergent materials, finely atomized liquid and adjunct detergent ingredients is generally from about 5% to about 60%, more preferably from about 12% to about 40%, more preferably, from about 15 to about 35%, in percentage ranges.
  • the surfactants which are included in the above can be from any part of the process of the present invention., e.g., from either one of the first step and/or the second step of the present invention.
  • the amount of the surfactant of the present process can be from about 5% to about 60%, more preferably from about 12% to about 40%, more preferably, from about 15 to about 35%, in total amount of the final product obtained by the process of the present invention.
  • the surfactant of the present process which is used as the above mentioned starting detergent materials in the first step, is in the form of powdered, pasted or liquid raw materials.
  • the surfactant itself is preferably selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.
  • anionics and nonionics are preferred and anionics are most preferred.
  • Nonlimiting examples of the preferred anionic surfactants useful in the present invention include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C 10 -C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C 10 -C 18 alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates).
  • LAS C 11 -C 18 alkyl benzene
  • Useful anionic surfactants also include 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 about 23 carbon atoms in the alkane moiety; 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.
  • exemplary surfactants useful in the paste of the invention include C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10 -C 18 alkyl polyglycosides and the corresponding sulfated polyglycosides, and C 12 -C 18 alpha-sulfonated fatty acid esters.
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R 1 ) 2 N + R 2 COO - , wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group or C 10 -C 16 acylamido alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl and R 2 is a C 1 -C 5 hydrocarbyl
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14 acylamidopropylbetaine; C 8-14 acylamidohexyldiethyl betaine; 4[C 14-16 acylmethylamidodiethylammonio]-1-carboxybutane; C 16-18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethylbetaine; and [C 12-16 acylmethylamidodimethylbetaine.
  • Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R 1 ) 2 N + R 2 SO 3 - wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably a C 12 -C 13 alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl, and R 2 is a C 1 -C 6 hydrocarbyl group, preferably a C 1 -C 3 alkylene or, preferably, hydroxyalkylene group.
  • Suitable sultaines include C 12 -C 14 dimethylammonio-2-hydroxypropyl sulfonate, C 12 -C 14 amido propyl ammonio-2-hydroxypropyl sultaine, C 12 -C 14 dihydroxyethylammonio propane sulfonate, and C 16-18 dimethylammonio hexane sulfonate, with C 12-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
  • the amount of the fine powder of the present process, which is used in the first step, can be from about 94% to 30%, preferably from 86% to 54%, in total amount of starting material for the first step .
  • the starting fine powder of the present process preferably selected from the group consisting of ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulphates, aluminosilicates, crystalline layered silicates, nitrilotriacetates (NTA), phosphates, precipitated silicates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkane sulfonic acids) and internal recycle stream of powder occurring from the process of the present invention, wherein the average diameter of the powder is from 0.1 to 500 microns, preferably from 1 to 300 microns, more preferably from 5 to 100 microns.
  • the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble).
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from about 20 to about 30, preferably about 27.
  • These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
  • aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram.
  • the amount of the finely atomized liquid sprayed into the fluidised bed of the present process can be from about 1% to about 10% (active basis), preferably from 2% to about 6% (active basis) in total amount of the final product obtained by the process of the present invention.
  • the finely atomized liquid of the present process can be selected from the group consisting of liquid silicate, anionic or cationic surfactants which are in liquid form, aqueous or non-aqueous polymer solutions, and mixtures thereof.
  • Other optional examples for the finely atomized liquid of the present invention can be sodium carboxy methyl cellulose solution, polyethylene glycol (PEG), and solutions of dimethylene triamine pentamethyl phosphonic acid (DETMP),
  • anionic surfactant solutions which can be used as the finely atomized liquid in the present inventions are about 88 - 97% active HLAS, about 30 - 50% active NaLAS, about 28% active AE3S solution, about 40-50% active liquid silicate, and so on.
  • Cationic surfactants can also be used as finely atomized liquid herein and suitable quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • aqueous or non-aqueous polymer solutions which can be used as the finely atomized liquid in the present inventions are modified polyamines which comprise a polyamine backbone corresponding to the formula: having a modified polyamine formula V (n+1) W m Y n Z or a polyamine backbone corresponding to the formula: having a modified polyamine formula V (n-k+1) W m Y n Y' k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
  • homopolymeric polycarboxylates which have molecular weights above 4000, such as described next are preferred.
  • Particularly suitable homopolymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from above 4,000 to 10,000, preferably from above 4,000 to 7,000, and most preferably from above 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Co-polymeric polycarboxylates such as a Acrylic/maleic-based copolymers may also be used.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. It is preferable for the above polymer solution to be pre-complexed with anionic surfactant such as LAS.
  • the starting detergent material in the present process can include additional detergent ingredients and/or, any number of additional ingredients can be incorporated in the detergent composition during subsequent steps of the present process.
  • adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
  • Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, C 10-18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below).
  • crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity.
  • the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water.
  • These crystalline layered sodium silicates are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously. Such crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509, previously incorporated herein by reference.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
  • 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, all of which are incorporated herein by reference.
  • nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • 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 ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric add.
  • Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is 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 methylene malonic acid.
  • Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
  • polyacetal carboxylates 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 of which are 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, converted to the corresponding salt, and added to a detergent composition.
  • Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
  • Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.
  • Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
  • Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
  • Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
  • Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
  • the process can comprise the step of spraying an additional binder in the mixer for the present invention.
  • a binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components.
  • the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, liquid silicates, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof.
  • suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the disclosure of which is incorporated herein by reference.
  • optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
  • Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying by way of apparatus discussed previously.
  • Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
  • the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
  • Such techniques and ingredients are well known in the art.
  • surfactant paste structuring process e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder, prior to the process of the present invention.
  • Step 1 250 - 270 kg/hr of aqueous coconut fatty alcohol sulfate surfactant paste (C 12 -C 18 , 71.5% active) is dispersed by the pin tools of a CB-30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15 microns). 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder.
  • the surfactant paste is fed at about 40 to 52°C, and the powders are fed at room temperature.
  • the condition of the CB-30 mixer is as follows:
  • Step 2 The agglomerates from the CB mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 120 kg/hr of liquid silicate (43% solids, 2.0R) is added in the fluid bed drying apparatus at 35°C.
  • the condition of the fluid bed drying apparatus is as follows:
  • Step 1 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C 11 -C 18 alkyl benzene sulfonate; 95% active) at about 50 °C, and 20 kg/hr of AE 3 S liquid (C 10 -C 18 alkyl alkoxy sulfates, EO-3; 28% active) is dispersed by the pin tools of a CB-30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15 microns), 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder.
  • the surfactant paste is fed at about 40 to 52°C, and the powders are fed at room temperature.
  • the condition of the CB-30 mixer is as follows:
  • Step 2 The agglomerates from the CB-30 mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 80 kg/hr of liquid silicate (43% solids, 2.0 R) is added in the fluid bed drying apparatus at 35°C.
  • the condition of the fluid bed drying apparatus is as follows:
  • Step 1 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C 11 -C 18 alkyl benzene sulfonate; 95% active) at about 50 °C, and 250 - 270 kg/hr of aqueous coconut fatty alcohol sulfate surfactant paste (C 12 -C 18 , 71.5% active) is dispersed by the pin tools of a CB-30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15 microns), 80-120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder.
  • the surfactant paste is fed at about 40 to 52°C, and the powders are fed at room temperature.
  • the condition of the CB-30 mixer is as follows:
  • Step 2 The agglomerates from the CB-30 mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 80 kg/hr of liquid silicate (43% solids, 2.0 R) is added in the fluid bed drying apparatus at 35°C.
  • the condition of the fluid bed drying apparatus is as follows:
  • the resultant from the fluid bed drying apparatus is fed to a fluid bed cooling apparatus.
  • the condition of the fluid bed cooling apparatus is as follows:

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Claims (10)

  1. Agglomerationsverfahren zur Herstellung einer granulären Detergenszusammensetzung mit einer Dichte von mindestens etwa 600 g/l, umfassend die Schritte:
    (a) Dispergieren eines Tensids, und Beschichten des Tensids mit feinem Pulver mit einem Durchmesser von 0.1 bis 500 µm in einem Mischer, wobei Bedingungen des Mischers beinhalten (i) 2 bis 50 Sekunden mittlere Verweilzeit, (ii) 4 bis 25 m/s Spitzengeschwindigkeit und (iii) 0,15 bis 7 kj/kg Energiezustand, wobei Agglomerate gebildet werden; und
    (b) Granulieren der Agglomerate in einer Wirbelbett-Trocknungsvorrichtung, während Tropfen flüssigen Detergensmaterials in einer Menge von bis zu 20% in das Bett gesprüht werden, wobei Bedingungen der Wirbelvorrichtung umfassen (i) 1 bis 10 Minuten mittlere Verweilzeit, (ii) 100 bis 300 mm Tiefe an nichtfluidisiertem Bett, (iii) nicht mehr als 50 µm Tropfensprühgröße, (iv) 175 bis 250 mm Sprühhöhe, (v) 0,2 bis 1,4 m/s Wirbelgeschwindigkeit und (vi) 12 bis 100°C Betttemperatur.
  2. Verfahren nach Anspruch 1, wobei 2 bis 10% (Wirkstoffbasis) flüssiges Detergensmaterial in das Bett gesprüht werden.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei das gesprühte flüssige Detergensmaterial gewählt ist aus Lösungen von Silicat, anionisches Tensid, kationisches Tensid und Polymer.
  4. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei ein Beschichtungsmittel direkt nach der Wirbelbett-Trocknungsvorrichtung zugegeben wird, um die Fließfähigkeit zu verbessern oder Übergranulation zu minimieren.
  5. Verfahren nach mindestens einem der Ansprüche 1 bis 3, wobei die Wirbelbett-Trocknungsvorrichtung gefolgt wird von einem Wirbelbett-Kühler.
  6. Verfahren nach Anspruch 5, wobei ein Beschichtungsmittel zwischen der Wirbelbett-Trocknungsvorrichtung und dem Wirbelbett-Kühler oder direkt nach dem Wirbelbett-Kühler zugesetzt wird, um Fließfähigkeit zu verbessern, oder Übergranulation zu minimieren.
  7. Verfahren nach Anspruch 1, wobei eine wässrige oder nichtwässrige Polymerlösung mit dem Tensid in Schritt (a) dispergiert wird.
  8. Verfahren nach Anspruch 1, wobei ein interner Kreislaufstrom aus Pulver aus der Wirbelbett-Vorrichtung weiterhin Schritt (a) zugesetzt wird.
  9. Verfahren nach Anspruch 1, wobei das feine Pulver aus der Gruppe gewählt wird, bestehend aus Sodaasche, pulverförmiges Natriumtripolyphosphat, hydratisiertes Tripolyphosphat, Natriumsulfaten, Aluminosilicaten, kristallinen Schichtsilicaten, Phosphaten, ausgefällten Silicaten, Polymeren, Carbonaten, Citraten, Nitrilotriacetaten, pulverförmigen Tensiden und Mischungen hiervon.
  10. Verfahren nach Anspruch 1, wobei die Gesamtmenge an Tensiden für das Verfahren nach Anspruch 1 etwa 5% bis etwa 60% der Gesamtmenge einer Zusammensetzung, wie durch das Verfahren nach Anspruch 1 erhalten, beträgt.
EP97931058A 1996-10-04 1997-06-05 Verfahren zur herstellung von einer waschmittelzusammensetzung nach ohne-turm-verfahren Expired - Lifetime EP0929653B1 (de)

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US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
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CN1239508A (zh) 1999-12-22
JP3299986B2 (ja) 2002-07-08
JP3299987B2 (ja) 2002-07-08
JP3299984B2 (ja) 2002-07-08
AU3303097A (en) 1998-04-24
AU3378597A (en) 1998-04-24
CA2268060C (en) 2003-04-22
JP2000503716A (ja) 2000-03-28
CA2268067A1 (en) 1998-04-09
EP0929645A1 (de) 1999-07-21
JP3299985B2 (ja) 2002-07-08
AR010509A1 (es) 2000-06-28
MX9903193A (en) 2000-01-31
EP0929653A1 (de) 1999-07-21
EP0929648B1 (de) 2002-09-04
CA2267424C (en) 2004-01-06
CA2268055C (en) 2004-02-03
AU3478297A (en) 1998-04-24
DE69726439D1 (de) 2004-01-08
JP3299982B2 (ja) 2002-07-08
WO1998014549A1 (en) 1998-04-09
JP2000507632A (ja) 2000-06-20
CN1239506A (zh) 1999-12-22
CN1239991A (zh) 1999-12-29
CA2268060A1 (en) 1998-04-09
WO1998014555A1 (en) 1998-04-09
AU3568397A (en) 1998-04-24
JP2000503718A (ja) 2000-03-28
EP0929652A1 (de) 1999-07-21
WO1998014557A1 (en) 1998-04-09
CN1133738C (zh) 2004-01-07
CA2267291C (en) 2002-12-10
JP2000503715A (ja) 2000-03-28
CA2268063C (en) 2002-10-29
DE69721287D1 (de) 2003-05-28
CA2268063A1 (en) 1998-04-09
JP2000503720A (ja) 2000-03-28
EP0929650A1 (de) 1999-07-21
MX9903195A (en) 1999-09-30
ATE255159T1 (de) 2003-12-15
JP2000503721A (ja) 2000-03-28
WO1998014553A1 (en) 1998-04-09
BR9612732A (pt) 1999-08-24
CN1156560C (zh) 2004-07-07
AR010507A1 (es) 2000-06-28
EP0929651B1 (de) 2003-11-26
EP0929654A1 (de) 1999-07-21
BR9713246A (pt) 1999-11-03
EP0929650B1 (de) 2003-08-06
CA2268062A1 (en) 1998-04-09
ES2193386T3 (es) 2003-11-01
ES2178778T3 (es) 2003-01-01
JP2000503719A (ja) 2000-03-28
CN1239995A (zh) 1999-12-29
ATE246726T1 (de) 2003-08-15
CA2267291A1 (en) 1998-04-09
DE69723986D1 (de) 2003-09-11
ATE223476T1 (de) 2002-09-15
AR010508A1 (es) 2000-06-28
CN1239507A (zh) 1999-12-22
CA2268052A1 (en) 1998-04-09
CN1156563C (zh) 2004-07-07
JP3299981B2 (ja) 2002-07-08
BR9711861A (pt) 1999-08-24
AR010511A1 (es) 2000-06-28
CN1239993A (zh) 1999-12-29
CA2268055A1 (en) 1998-04-09
ES2201305T3 (es) 2004-03-16
EP0929651A1 (de) 1999-07-21
CN1156561C (zh) 2004-07-07
JP2000504062A (ja) 2000-04-04
EP0929649A1 (de) 1999-07-21
DE69726440D1 (de) 2004-01-08
BR9712490A (pt) 1999-10-19
JP3299983B2 (ja) 2002-07-08
EP0929655A1 (de) 1999-07-21
MX219076B (en) 2004-02-10
CN1133739C (zh) 2004-01-07
WO1998014554A1 (en) 1998-04-09
AR010510A1 (es) 2000-06-28
CN1156562C (zh) 2004-07-07
AU3478597A (en) 1998-04-24
ES2212109T3 (es) 2004-07-16
CA2268068C (en) 2003-06-03
ES2210544T3 (es) 2004-07-01
CA2268052C (en) 2003-12-30
DE69715224D1 (de) 2002-10-10
WO1998014551A1 (en) 1998-04-09
WO1998014558A1 (en) 1998-04-09

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