EP1187904B1 - Procede de fabrication d'une composition granulaire detergente - Google Patents

Procede de fabrication d'une composition granulaire detergente Download PDF

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Publication number
EP1187904B1
EP1187904B1 EP00941566A EP00941566A EP1187904B1 EP 1187904 B1 EP1187904 B1 EP 1187904B1 EP 00941566 A EP00941566 A EP 00941566A EP 00941566 A EP00941566 A EP 00941566A EP 1187904 B1 EP1187904 B1 EP 1187904B1
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EP
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Prior art keywords
mixer
seconds
speed mixer
process according
particles
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German (de)
English (en)
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EP1187904A1 (fr
Inventor
Scott William Capeci
Girish Jagannath
Noe Ongcoy Hidalgo
Manivannan Kandasamy
Takashi Kazuta
Yuji Nakamura
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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

Definitions

  • the present invention relates to a process for making an improved granular detergent composition which has superior solubility, especially in cold temperature laundering solutions (i.e., less than about 30°C), excellent flowability, aesthetics or appearance and friability.
  • this clumping phenomenon can contribute to the incomplete dispensing of detergent in washing machines equipped with dispenser drawers or in other dispensing devices, such as a granulette.
  • the undesired result is undissolved detergent residue in the dispensing device.
  • inorganic salts In addition to the viscous surfactant "bridging" effect, inorganic salts have a tendency to hydrate which can also cause “bridging” of particles which linked together via hydration. In particular, inorganic salts hydrate with one another to form a cage structure which exhibits poor dissolution and ultimately ends up as a "clump" after the washing cycle. It would therefore be desirable to have a detergent composition which does not experience the dissolution problems identified above so as to result in improved cleaning performance.
  • 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 detergent adjunct ingredients, the shape of the various detergent adjunct ingredients, and their respective chemical composition.
  • the European patent EP-A-0 816 485 discloses a process for making particles comprising the step of mixing two non-surfactant additives to form a premix. Afterwards the premix is sprayed with nonionics to form a first intermediate particle. Then another second intermediate particle is admixed to give a final particle product of a mean particle size of between 800 and 1200 ⁇ m with a deviation of less than 100. Several mixers are mentioned.
  • US-A-5 516 448 discloses a process for making high density detergent compositions comprising the steps of charging a high-speed mixer with surfactant paste and dry starting material. After mixing in a medium-speed mixer the agglomerates have a mean size of 300-900 ⁇ m.
  • the invention meets the needs above by providing a process for making a detergent composition which has improved solubility or dissolution in laundering solutions, especially in solutions kept at cold temperatures (i.e., less than about 30°C), is aesthetically pleasing to consumers and has improved flowability.
  • a process is provided to form a granular detergent composition with improved solubility, aesthetics and flowability: mixing dry agglomerates and spray dried granules in a high-speed, low-speed, or a moderate-speed mixer, and various combinations of such mixers to form particles, wherein the granular detergent composition has at least 95% by weight of particles having a geometric mean particle diameter of from 500 microns to 1500 microns with a geometric standard deviation of from 1 to 2.
  • mixtures is meant to include a simple combination of materials and any compounds that may result from their combination.
  • cold water means water which has at a temperature of below 30°C.
  • density or “bulk density” refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of powder sample through a funnel into a smooth metal vessel (e.g., a 500 ml volume cylinder), scraping off the excess from the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
  • a smooth metal vessel e.g., a 500 ml volume cylinder
  • ambient is defined as the temperature and humidity of the environment.
  • particles means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle in an admixture of particles. For each type of particle component in an admixture, the entire size range of discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles.
  • the agglomerates themselves are considered as discrete particles and each discrete particle may be comprised of a composite of smaller primary particles and binder compositions.
  • geometric mean particle diameter means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving.
  • the phrase "geometric standard deviation" or “span” of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50 th percentile of the cumulative distribution (D 84.13 /D 50 ); See Gotoh et al, Powder Technology Handbook, pp. 6-11, Meral Dekker 1997.
  • builder means any inorganic material having “builder” performance in the detergency context, and specifically, organic or inorganic material capable of removing water hardness from washing solutions.
  • the present invention is directed to a process which produces a granular detergent composition having at least 95% by weight of particles having a geometric mean particle diameter of from 500 microns to 1500 microns with a geometric standard deviation of from 1 to 2.
  • the present invention is directed towards a process for making a granular detergent composition
  • a process for making a granular detergent composition comprising the step of mixing dry agglomerates and spray dried granules to form particles, wherein the granular detergent composition comprises at least 95% by weight of particles having a geometric mean particle diameter of from 500 microns to 1500 microns with a geometric standard deviation of from 1 to 2.
  • any recycled fines generated could also be added to the mixer.
  • Wet agglomerates are optional and include those particles that are manufactured via a granulation type process wherein detergent adjunct ingredients such as described below are admixed with a liquid binder material such as surfactant or a precursor thereof in at least one mixer to form granules of detergent materials. These particles are known as “wet agglomerates” until dried and as “dry agglomerates” upon exiting a drying stage, and optionally other conditioning stages such as sizing, grinding and cooling.
  • Binders include but are not limited to water, anionic surfactants and their precursors, nonionic surfactants, cationic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid, and mixtures thereof.
  • Spray dried granules include those particles which are manufactured via a conventional spray-drying technique wherein a slurry of detergent materials is prepared and sprayed downward into an upwardly flowing stream of gas to dry the particles.
  • a dry, free flowing material is produced from the process.
  • the slurry is passed to a tower where the slurry is sprayed into a stream of air at temperatures ranging from 175°C to 450°C to dry the detergent slurry and form detergent particles.
  • resultant densities of these particles range from 200 to 650 g/l.
  • Detergent adjunct ingredients are optional and include but are not limited to, carbonates, phosphates, sulfates, zeolites, or the like.
  • a list of detergent components which can be used as a detergent adjunct ingredient is described in detail below. Of course other conventionally known ingredients may be included as well.
  • the mixer contains dry agglomerates and spray dried granules at a weight ratio ranging from 5:95 to 95:5, more preferably at a ratio ranging from 10:90 to 90:10, and even more preferably from 30:70 to 70:30.
  • Two types of materials are fed into at least one mixer for agglomeration.
  • the two types of materials can be fed into at least one pre-mixer (e.g. a conventional screw extruder, including a twin-screw extruder or other similar mixer) prior to agglomeration in at least one mixer, after which the mixed materials are fed into the initial mixer as described herein.
  • at least one pre-mixer e.g. a conventional screw extruder, including a twin-screw extruder or other similar mixer
  • the agglomeration step can be carried initially in at least one high-speed mixer, a moderate-speed mixer, a low-speed mixer, and combinations of mixers thereof.
  • the same type of mixer can be used in a series, or in any combination with the other types of mixers, which may also be in a series.
  • the process can be batch or continuous.
  • two or more mixers can be used in series and/or in parallel, for example to accommodate thoroughput.
  • one embodiment of the process of the present invention may include mixing at least two materials from the group in at least one high-speed mixer, followed by at least one moderate-speed mixer, with optionally a conditioning step in a fluid bed granulator.
  • mixing may take place in at least one high-speed mixer, followed by at least one moderate-speed mixer, followed by at least one high-speed mixer, followed by a conditioning step in at least one conditioning apparatus, such as a fluid bed granulator.
  • the same mixture is mixed in a high-speed mixer after the initial mixing in a moderate-speed mixer, before being conditioned.
  • mixers, pre-mixers, and/or conditioning apparatus of the process of the present invention are only a few of the possible variations of mixers, pre-mixers, and/or conditioning apparatus of the process of the present invention. Detailed examples are also disclosed below.
  • Residence times of the mixtures will vary depending on the type of mixer and the operating parameters.
  • the mean residence time is from 0.1 to 60 seconds, more preferably from 0.1 to 30 seconds, even more preferably 0.1 to 15 seconds.
  • Other preferred conditions of the high-speed mixer include from 3 to 90 m/s of tip speed, and more preferably from 10 to 70 m/s of tip speed, and from 0.005 W/kg to 100 W/kg of power draw, more preferably from 0.05 W/kg to 80 W/kg of power draw.
  • choppers can be used inside the mixer to break up undesirable oversized particles at an rpm of from 0 to 5000 rpm, more preferably from 100 to 3000 rpm.
  • the wall temperature is from ambient to 80°C and the spacing between the mixer elements and the wall is from 0.1 cm to 25 cm.
  • Examples of a high-speed mixer having a mean residence time of from 0.1 to 60 seconds are Lödige Recycler CB 30TM, by Lödige Company, or mixers made by Drais, Schugi, or a similar brand mixer.
  • the mean residence time is from 30 to 1800 seconds, more preferably from 30 to 1200 seconds, more preferably from 30 to 600 seconds.
  • Other preferred conditions of the moderate-speed mixer include from 0.1 to 30 m/s of tip speed, and more preferably from 1 to 25 m/s of tip speed, and from 5 W/kg to 1000 W/kg of power draw, more preferably from 20 W/kg to 500 W/kg of power draw.
  • choppers can be used inside the mixer to break up undesirable oversized particles at an rpm of from 0 to 5000 rpm, more preferably from 100 to 4000 rpm.
  • the wall temperature is from -20°C to 80°C and the spacing between the mixer elements and the wall is from 0.1 cm to 25 cm.
  • a moderate-speed mixer having a mean residence time of from 30 to 1800 seconds are Lodige Recycler KM "Ploughshare" 300TM and 600TM, by Lödige Company, the Drais K-T 160TM mixer, or mixers made by Fukae.
  • the Lödige KM "Ploughshare" 600TM moderate-speed mixer is a particularly preferred mixer, which comprises a horizontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached.
  • the shaft rotates at a speed of from 15 rpm to 140 rpm, more preferably from 80 rpm to 120 rpm.
  • the grinding or pulverizing is accomplished by cutters, generally smaller in size that the rotating shaft, which preferably operate at 3600 rpm.
  • the mean residence time is from 30 seconds to 1800 seconds, more preferably from 30 seconds to 1200 seconds, and even more preferably from 30 seconds to 600 seconds.
  • the tip speed is preferably from 0.1 m/s to 10 m/s, more preferably from 0.2 m/s to 7 m/s, and even more preferably from 0.2 m/s to 3.5 m/s.
  • preferred low-speed mixers include rotating bowl agglomerators, drum agglomerators, pan agglomerators, fluid bed granulators, and extruders.
  • An example of an extruder is a multiple-screw extruder by Werner-Pfliedder (Germany).
  • Fluid bed granulators are particularly preferred. Typical fluid bed granulators are operated at a superficial air velocity of from 0.1 to 4 m/s, either under positive or negative pressure. Inlet air temperatures generally range from -10°C or 5°C up to 250°C. However, inlet air temperatures are generally below 150°C, or even below 100°C or 80°C.
  • Other conditions include (i) from 30 seconds to 20 minutes of mean residence time, (ii) from 100 to 600 mm of depth of unfluidized bed, (iii) a droplet spray size of less than 2 times the particle size, preferably not more than 100 microns, more preferably less than 50 microns, (iv) from 150 to 1600 mm of spray height from the fluid bed plate, (v) from 0.1 to 4.0 m/s of fluidizing velocity and (vi) from 12°C to 200°C of bed temperature, more preferably from 12°C to 150°C, even more preferably from 12°C to 100°C.
  • Other operating conditions for the fluidized bed granulator may be for example as described in WO98/58046.
  • One of ordinary skill in the art will recognize that the conditions in the fluid bed may vary depending on a number of factors.
  • the conditioning step can be at any point in the process.
  • the conditioning step can follow mixing in the initial mixer, or the pre-mixer. If there is a series of mixers and/or combinations of mixers, the conditioning step can fall between two mixers, as well as also following the last mixer in the series. Such step is useful for many benefits, including improving the flow properties of the particles.
  • Conditioning the particles include drying, cooling, coating, grinding, and sieving the particle.
  • This conditioning step can be conducted in any piece of equipment known in the art such as a fluid bed dryer, air lift, fluid bed cooler, fluid bed granulator, bulk heat exchangers, grinder, and siever, or combinations of conditioning apparatus, and including series of conditioning apparatus.
  • Examples of a fluid bed dryer, fluid bed cooler, and fluid bed granulator's characteristics include fixed or vibrating; rectangular bed or round bed; and straight or serpentine apparatus. Some apparatus have multiple internal “stages” or “zones", which are discrete areas within the apparatus. Process conditions for these apparatus could be different or similar to the other stages in the apparatus. Manufactures of such conditioning apparatus include Wurster AG, Niro, Bepex, Spray Systems and Glatt.
  • apparatus such as a fluid bed or fluidized bed cooler/dryer/granulator, including combinations thereof, can be used for drying while an airlift can be used for cooling should it be necessary. The air lift can also be used to force out the "fine" particles so that they can be recycled. Both air and gas can be used to dry and/or cool.
  • a fluid bed granulator is especially preferred as an apparatus for the conditioning step.
  • the preferred operating conditions of the fluid bed granulator is described in detail above, and such conditions are also preferred in the conditioning step.
  • Examples of apparatus (including the fluid bed granulator) that can be used for coating the particles include Wurster Fluid Bed manufactured by Wurster AG (Germany), Glatt Fluid Bed manufactured by Glatt AG (Germany), Niro Fluid Bed manufactured by Niro Aeromatic.
  • Examples of apparatus that can be used for grinding the particles include the Two-cage disintegrator by Stedman Foundry and Machine Co. (USA), Hammer crusher by Jeffrey Mfg. Co. (USA).
  • sieves include Grizzly screens made by W.S.Tyler Company (USA), mechanically vibrated Screens made by Mogensen Co. (USA), Gyratory Screens made by Allis-Chalmers Manufacturing Co. (USA).
  • the process of the present invention may additionally include a finishing step as part of the conditioning step including but not limited to, admix and/or spray-on of additional ingredients such as enzymes, bleach, perfumes, etc., or a packaging step.
  • a finishing step as part of the conditioning step including but not limited to, admix and/or spray-on of additional ingredients such as enzymes, bleach, perfumes, etc., or a packaging step.
  • Another optional step is that the particles may be further processed by adding a coating agent to improve the particle color, increase the particle "whiteness", or improve the particle flowability after the particles exit the mixer or the conditioning apparatus to obtain the granular detergent composition produced by the present invention.
  • Yet another optional processing step includes continuously adding a coating agent such as zeolites and fumed silica to the mixer to facilitate free flowability of the resulting detergent particles and to prevent over granulation.
  • the resultant composition after mixing at least two materials from the group form a granular detergent composition having at least 95% by weight of particles having a geometric mean particle diameter of from 500 microns to about 1500 microns with a geometric standard deviation of from 1 to 2.
  • Fines or "fine” particles are defined as particles that have a geometric mean particle diameter that is less than 1.65 standard deviations below the chosen geometric mean particle diameter of the granular detergent composition at a given geometric standard deviation.
  • the granular detergent composition made by the process of the present invention achieves the desired benefits of solubility, improved aesthetics and flowability via optimal selection of the geometric mean particle diameter of certain levels of particles in the composition.
  • improved aesthetics it is meant that the consumer views a granular detergent product which has a more uniform appearance of particles as opposed to past granular detergent products which contained particles of varying size and composition. To that end, at least 95%, by weight of the total particles in the detergent product, have the selected mean particle size diameter. In this way, a substantial portion of the granular detergent product will have the uniform size so as to provide the aesthetic appearance desired by consumers.
  • the geometric mean particle diameter of the particles is from 500 microns to 1500 microns, more preferably from 600 microns to 1200 microns, and most preferably from 600 microns to 1000 microns.
  • the particle size distribution is defined by a relative tight geometric standard deviation or "span" so as not to have too many particles outside of the target size. Accordingly, the geometric standard deviation is preferably is from 1 to 2, more preferably is from 1.0 to 1.7, even more preferably is from 1.0 to 1.4, and most preferably is from 1.0 to 1.2.
  • the bulk density of the particles is preferably in the range of from 400 g/l to 850 g/l, more preferably from 550 g/l to 800 g/l, and even more preferably from 600 to 750 g/l.
  • solubility is enhanced as a result of the particles in the detergent composition being more of the same size.
  • the actual "contact points" among the particles in the detergent composition is reduced which, in turn, reduces the "bridging effect" commonly associated with the "lump-gel” dissolution difficulties of granular detergent compositions.
  • Previous granular detergent compositions contained particles of varying sizes which leads to more contact points among the particles. For example, a large particle could have many smaller particles in contact with it rendering the particle site ripe for lump-gel formation.
  • the level and uniform size of the particles in the granular detergent composition of the present invention avoids such problems.
  • the particles have better chemical homogeneity, e.g. the particles are more uniform in quality.
  • the detergent composition contains a detersive surfactant and/or a detergent builder to provide the fundamental building blocks of a typical detergent composition.
  • the various surfactants and builders as well as their respective levels in the composition are set forth hereinafter.
  • the detergent composition will contain from 1% to 50% by weight of a detersive surfactant and from 1% to 75% by weight of a detergent builder.
  • a particularly important attribute of detergent powders is color. Color is usually measured on a Hunter Colorimeter and reported as three parameters "L", "a” and "b". Of particular relevance to the powdered detergent consumer is the whiteness of the powder determined by the equation L-3b. In general, whiteness values below 60% are considered poor. Whiteness can be improved by a number of means known to those of ordinary skill in the art. For example, coating granules with Titanium Dioxide.
  • Shape can be measured in a number of different ways known to those of ordinary skill in the art. One such method is using optical microscopy with Optimus (V5.0) image analysis software. Important calculated parameters are:
  • the granular detergent compositions produced by the process of the present invention have circularities less than 50, preferably less than 30, more preferably less than 23, most preferably less than 18. Also preferred are granular detergent compositions with aspect ratios less than 2, preferably less than 1.5, more preferably less than 1.3 most preferably less than 1.2.
  • the granular detergent compositions of this invention have a standard deviation of the number distribution of circularity less than 20, that is preferably less than 10, more preferably less than 7 most preferably less than 4.
  • the standard deviation of the number distribution of aspect ratios is preferably less than 1, more preferably less than 0.5, even more preferably less than 0.3, most preferably less than 0.2.
  • granular detergent compositions are produced wherein the product of circularity and aspect ratio is less than 100, preferably less than 50, more preferably less than 30, and most preferably less than 20. Also preferred are granular detergent compositions with the standard deviation of the number distribution of the product of circularity and aspect ratio of less than 45, preferably less than 20, more preferably less than 7 most preferably less than 2.
  • the detergent components described herein may be used as a detergent adjunct ingredient in the process of the invention.
  • the surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • Detergent surfactants are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975.
  • Cationic surfactants 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.
  • Nonlimiting examples of surfactant systems include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and 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, the C 10 -C 18 alkyl alkoxy sulfates (“AE x S”; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 eth
  • 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 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the surfactant system.
  • 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 sudsmg.
  • 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.
  • Hydrophobic secondary alkyl sulfates are also preferred. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • the detergent composition can, and preferably does, include a detergent builder.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • the alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, silicates, C 10-18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
  • 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.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, 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 1.0 to 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 acid.
  • 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 methylenemalonic acid.
  • Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the nonsoap anionic surfactant.
  • polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al.
  • These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, 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.
  • Water-soluble silicate solids represented by the formula SiO 2 ⁇ M 2 O, M being an alkali metal, and having a SiO 2 :M 2 O weight ratio of from about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8%.
  • Anhydrous or hydrated particulate silicate can be utilized, as well.
  • any number of additional ingredients can also be included as components in the granular detergent composition.
  • these include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder 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.
  • 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.
  • 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.
  • the spray-dried granule is comprised of 11% surfactant, 74% inorganic salts, 5% polyacrylate polymer, 5% soap, and 5% moisture.
  • the dry agglomerate composition is comprised of 30% surfactant, 62% inorganic salts, 4% sodium aluminosilicate, and 4% moisture.
  • 360 kg/hr of a spray-dried granule (particle size of 400 microns, bulk density of 400 g/l) and 360 kgs/her of a dry agglomerate (particle size of 450 microns, bulk density of 780 g/l) is introduced into a moderate-speed KM-600TM Lodige Mixer with 8 serrated ploughs and 4 "christmas-tree" choppers mounted perpendicular to the ploughs along the length of the mixer.
  • the mixer is divided into four zones.
  • the gap between the ploughs and the wall of the mixer is about 3 cm.
  • the wall temperature is maintained at 30°C.
  • aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is dispersed by the first chopper into the moderate-speed mixer and 70 kg/hr of crystalline sodium aluminosilicate is added in the last zone of the mixer.
  • the surfactant paste is fed at 50°C and the powders are fed at room temperature.
  • the condition of the mixer is as follows: Mean residence time: 7.5-10 minutes Tip Speed: 2-3 m/s Power Draw: 20-500 W/kg Chopper RPM: 3600
  • the product from the moderate-speed is subjected to conditioning operations of gas-fluidized bed drying, gas-fluidized bed cooling and sizing.
  • the inlet air temperature in the dryer is 120°C and the air velocity is 1 m/s.
  • Inlet air humidity in the dryer is 10%.
  • the inlet air temperature in the cooler is 10°C, the air velocity is 1 m/s and the inlet air humidity is 40%.
  • Sizing takes place in a Mogensen Sizer with a top sieve of 1180-1900 micron spacing and a bottom sieve of 300-450 microns spacing.
  • the resulting granules have a bulk density of 800 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is injected into the mixer and dispersed with the action of the chopper blades on the powders over a period of 5 minutes.
  • the paste is at 50°C and the powders are at room temperature.
  • the contents are fed into a fluidized bed for drying.
  • the inlet air temperature is 105°C
  • air velocity is 0.6 m/s
  • drying time is 5 minutes.
  • the dried granules are sieved using a Ro-tap sieve shaker with a top sieve of 1180 microns and a bottom sieve of 300 microns.
  • the resulting granules have a bulk density of 650-680 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • 360 kg/hr of a spray-dried granule (particle size of 400 microns, bulk density of 400 g/l) and 360 kg/hr of a dry agglomerate (particle size of 450 microns, bulk density of 780 g/l) is introduced into a Schugi Mixer.
  • 40 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-18, 30% active) is sprayed on the powders using a SU 26 two-fluid nozzle (air pressure: 1-5 kg/cm 2 , liquid pressure: 2-3 kg/cm 2 ).
  • the liquid is sprayed on at 50°C and the powders are at room temperature.
  • the operating conditions of the high-speed Schugi Mixer are as follows: Tip Speed 24 m/s Mean residence Time 0.1-1 second Power Draw 1-5 kW/kg
  • the output from the high speed mixer is fed into a moderate speed KM-600TM Mixer and 60 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is dispersed by the first chopper into the moderate speed mixer and 70 kg/hr of crystalline sodium aluminosilicate is added in the last zone of the mixer.
  • the surfactant paste is fed at 50°C.
  • the condition of the moderate-speed mixer is as follows: Mean residence time: 2-3 minutes Tip Speed 2-3 m/s Power Draw 20-500 W/kg Chopper RPM 3600
  • the product from the moderate-speed mixer is subjected to conditioning operations of gas-fluidized bed drying, gas-fluidized bed cooling and sizing.
  • the inlet air temperature in the dryer is 120°C and the air velocity is 1 m/s.
  • Inlet air humidity in the dryer is 10%.
  • the inlet air temperature in the cooler is 10°C, the air velocity is 1 m/s and the inlet air humidity is 40%.
  • Sizing takes place in a Mogensen Sizer with a top sieve of 1180-1900 micron spacing and a bottom sieve of 300-450 microns spacing.
  • the resulting granules have a bulk density of 550-600 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • the undersize generated in the process can be recycled via the Schugi at 20% level and the ground overs via the fluid bed at 20% level.
  • 360 kg/hr of a spray-dried granule (particle size of 400 microns, bulk density of 400 g/l) and 360 kg/her of a dry agglomerate (particle size of 450 microns, bulk density of 780 g/l) is introduced into a high-speed Schugi Mixer.
  • 40 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-18, 30% active) is sprayed on the powders using a SU 26 two-fluid nozzle (air pressure: 1-5 kg/cm 2 , liquid pressure: 2-3 kg/cm 2 ).
  • the liquid is sprayed on at 50°C and the powders are at room temperature.
  • the operating conditions of the high-speed Schugi Mixer are as follows: Tip Speed 24 m/s Mean residence Time 0.1-1 second Power Draw 1-5 kW/kg
  • the output from the Schugi is fed into a moderate speed KM-600TM Mixer and 40 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is dispersed by the first chopper into the moderate speed mixer and 50 kg/hr of crystalline sodium aluminosilicate is added in the last zone of the mixer.
  • the surfactant paste is fed at 50°C.
  • the condition of the moderate-speed mixer is as follows: Mean residence time 2-3 minutes Tip Speed 2-3 m/s Power Draw 20-500 W/kg Chopper RPM 3600
  • the product from the moderate speed is fed into a second high-speed Schugi Mixer.
  • 20 kg/hr of aqueous polyethylene glycol solution (mol.wt.:4000, 40% active) is sprayed on the powders using a SU 26 two-fluid nozzle (air pressure: 1-5 kg/cm 2 , liquid pressure: 2-3 kg/cm 2 ).
  • the liquid is sprayed on at 50°C.
  • the operating conditions of the Schugi Mixer are as follows: Tip Speed 24 m/s Mean residence Time 0.1-1 second Power Draw 1-5 kW/kg
  • the output from the Schugi is subjected to conditioning operations of gas-fluidized bed drying, gas-fluidized bed cooling and sizing.
  • the inlet air temperature in the dryer is 120°C and the air velocity is 1 m/s.
  • Inlet air humidity in the dryer is 10%.
  • the inlet air temperature in the cooler is 10°C, the air velocity is 1 m/s and the inlet air humidity is 40%.
  • Sizing takes place in a Mogensen Sizer with a top sieve of 1180-1900 micron spacing and a bottom sieve of 300-450 microns spacing.
  • the resulting granules have a bulk density of 500-550 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • 360 kg/hr of a spray-dried granule (particle size of 400 microns, bulk density of 400 g/l) and 360 kgs/her of a dry agglomerate (particle size of 450 microns, bulk density of 780 g/l) is introduced into a KM-600TM Mixer.
  • 60 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is dispersed by the first chopper into the moderate-speed and 50 kg/hr of crystalline sodium aluminosilicate is added in the last zone of the mixer.
  • the surfactant paste is fed at 50°C and the powders are at room temperature.
  • the condition of the KM-600TM mixer is as follows: Mean residence time 2-3 minutes Tip Speed 2-3 m/s Power Draw 20-500 W/kg Chopper RPM 3600
  • the output from the KM-600TM Mixer is fed into a high-speed Schugi mixer and 40 kg/h of aqueous polyethylene glycol solution (mol.wt.:4000, 40% active) is sprayed on the powders using a SU 26 two-fluid nozzle (air pressure: 1-5 kg/cm 2 , liquid pressure: 2-3 kg/cm 2 ). The liquid is sprayed on at 50°C.
  • the operating conditions of the Schugi Mixer are as follows: Tip Speed 24 m/s Mean residence Time 0.1-1 second Power Draw 1-5 kW/kg
  • the product from the Schugi mixer is subjected to conditioning operations of gas-fluidized bed drying, gas-fluidized bed cooling and sizing.
  • the inlet air temperature in the dryer is 120°C and the air velocity is 1 m/s.
  • Inlet air humidity in the dryer is 10%.
  • the inlet air temperature in the cooler is 10°C, the air velocity is 1 m/s and the inlet air humidity is 40%.
  • Sizing takes place in a Mogensen Sizer with a top sieve of 1180-1900 micron spacing and a bottom sieve of 300-450 microns spacing.
  • the resulting granules have a bulk density of 550-600 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • the output from the Schugi is fed into a moderate speed KM-600TM Mixer.
  • 360 kg/hr of a spray-dried granule (particle size of 400 microns, bulk density of 400 g/l) is fed into the mixer and 60 kg/hr of aqueous linear alkyl benzene sulphonate paste (C11-C18, 60% active) is dispersed by the first chopper into the moderate-speed mixer and 70 kg/hr of crystalline sodium aluminosilicate is added in the last zone of the mixer.
  • the surfactant paste is fed at 50°C and the powder is at room temperature.
  • the condition of the KM-600TM mixer is as follows: Mean residence time 2-3 minutes Tip Speed 2-3 m/s Power Draw 20-500 W/kg Chopper RPM 3600
  • the product from the KM-600TM is subjected to conditioning operations of gas-fluidized bed drying, gas-fluidized bed cooling and sizing.
  • the inlet air temperature in the dryer is 120°C and the air velocity is 1 m/s.
  • Inlet air humidity in the dryer is 10%.
  • the inlet air temperature in the cooler is 10°C, the air velocity is 1 m/s and the inlet air humidity is 40%.
  • Sizing takes place in a Mogensen Sizer with a top sieve of 1180-1900 micron spacing and a bottom sieve of 300-450 microns spacing.
  • the resulting granules have a bulk density of 450-550 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.
  • the resulting granules have a bulk density of 450-550 g/l, a mean particle size of 600 microns, less than 3% of the granules are below 300 microns and less than 3% of the granules are above 1180 microns.

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  • 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)
  • Detergent Compositions (AREA)

Claims (12)

  1. Procédé de préparation d'une composition détergente granulaire comprenant l'étape consistant à mélanger des agglomérats secs et des granules séchés par atomisation dans au moins un mélangeur choisi dans le groupe constitué par un mélangeur à faible vitesse, un mélangeur à vitesse modérée, un mélangeur à haute vitesse, et des combinaisons de ces mélangeurs, pour former des particules, dans lequel la composition granulaire détergente comprend au moins 95 % en poids de particules ayant un diamètre moyen particulaire géométrique de 500 micromètres à 1500 micromètres avec une déviation géométrique standard de 1 à 2.
  2. Procédé selon la revendication 1, comprenant en outre l'étape de conditionnement des particules résultantes dans au moins un appareil de conditionnement.
  3. Procédé selon la revendication 1, dans lequel le temps de séjour moyen dans le mélangeur à faible vitesse est de 30 secondes à 1800 secondes, le temps de séjour moyen dans le mélangeur à vitesse modérée est de 30 à 1800 secondes, et le temps de séjour moyen dans le mélangeur à haute vitesse est de 0,1 à 60 secondes.
  4. Procédé selon la revendication 2, dans lequel l'étape de conditionnement comprend au moins un granulateur à lit fluidisé.
  5. Procédé selon la revendication 3, dans lequel la vitesse de pointe du mélangeur à faible vitesse est de 0,1 m/s à 10 m/s, la vitesse de pointe du mélangeur à vitesse modérée est de 0,1 m/s à 30 m/s, et la vitesse de pointe du mélangeur à haute vitesse est de 3 m/s à 90 m/s.
  6. Procédé selon la revendication 4, dans lequel les fines générées par le granulateur à lit fluidisé sont recyclées dans au moins un mélangeur.
  7. Procédé selon la revendication 1, dans lequel le mélangeur contient un rapport en poids des agglomérats secs aux granules séchés par atomisation de 5 : 95 à 95 : 5.
  8. Procédé selon la revendication 4, dans lequel le granulateur à lit fluidisé a un temps de séjour moyen de 30 secondes à 20 minutes.
  9. Procédé selon la revendication 1, dans lequel le mélangeur à faible cisaillement est un granulateur à lit fluidisé.
  10. Procédé selon la revendication 2, dans lequel le temps de séjour moyen dans le mélangeur à faible vitesse est de 30 secondes à 1800 secondes, le temps de séjour moyen dans le mélangeur à vitesse modérée est de 30 à 1800 secondes, et le temps de séjour moyen dans le mélangeur à haute vitesse est de 0,1 à 60 secondes.
  11. Procédé selon la revendication 10, dans lequel l'étape de conditionnement comprend au moins un granulateur à lit fluidisé.
  12. Procédé selon la revendication 11, dans lequel les conditions de fonctionnement du granulateur à lit fluidisé comprennent (i) de 30 secondes à 20 minutes de temps de séjour moyen, (ii) de 100 mm à 600 mm de profondeur du lit non fluidisé, (iii) pas plus de 100 micromètres de taille de gouttelette d'atomisation, (iv) de 150 mm à 1600 mm de hauteur d'atomisation, (v) de 0,1 à 4,0 m/s de vitesse de fluidisation et (vi) de 12°C à 200°C de température du lit.
EP00941566A 1999-06-21 2000-06-20 Procede de fabrication d'une composition granulaire detergente Revoked EP1187904B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14016099P 1999-06-21 1999-06-21
US140160P 1999-06-21
PCT/US2000/016917 WO2000078913A1 (fr) 1999-06-21 2000-06-20 Procede de fabrication d'une composition granulaire detergente

Publications (2)

Publication Number Publication Date
EP1187904A1 EP1187904A1 (fr) 2002-03-20
EP1187904B1 true EP1187904B1 (fr) 2004-08-11

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EP00941566A Revoked EP1187904B1 (fr) 1999-06-21 2000-06-20 Procede de fabrication d'une composition granulaire detergente

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EP (1) EP1187904B1 (fr)
JP (1) JP4786092B2 (fr)
CN (1) CN1200999C (fr)
AR (1) AR025846A1 (fr)
AT (1) ATE273378T1 (fr)
AU (1) AU5625800A (fr)
BR (1) BR0011796A (fr)
CA (1) CA2375488C (fr)
DE (1) DE60012928T2 (fr)
ES (1) ES2226865T3 (fr)
MX (1) MXPA02000066A (fr)
WO (1) WO2000078913A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3194540B1 (fr) 2014-09-18 2020-02-12 The Procter and Gamble Company Particules de détergent structurées et composition de détergent granulaire contenant ces dernières

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003044152A1 (fr) * 2001-11-19 2003-05-30 Unilever N.V. Sachets de detergent
JP2012122067A (ja) * 2010-11-19 2012-06-28 Kao Corp 洗剤粒子群の製造方法
EP3098295A1 (fr) * 2015-05-29 2016-11-30 The Procter and Gamble Company Procédé de fabrication d'une poche à compartiment(s) simple ou multiples

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
JPH04348197A (ja) * 1991-05-27 1992-12-03 Lion Corp 粒状洗剤の製造方法
DE4243704A1 (de) * 1992-12-23 1994-06-30 Henkel Kgaa Granulare Wasch- und/oder Reinigungsmittel
US5565137A (en) * 1994-05-20 1996-10-15 The Proctor & Gamble Co. Process for making a high density detergent composition from starting detergent ingredients
US5516448A (en) * 1994-09-20 1996-05-14 The Procter & Gamble Company Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate
ATE312901T1 (de) * 1996-07-04 2005-12-15 Procter & Gamble Verfahren zur herstellung von reinigungsmittelzusammensetzungen
EP0918843B1 (fr) * 1996-08-14 2002-09-11 The Procter & Gamble Company Procede de fabrication d'un detergent haute densite
MX219077B (en) * 1996-10-04 2004-02-10 Procter & Gamble Process for making a detergent composition by non-tower process
WO1999019454A1 (fr) * 1997-10-10 1999-04-22 The Procter & Gamble Company Procede de production d'une composition detergente granulaire contenant des tensioactifs ramifies en milieu de chaine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3194540B1 (fr) 2014-09-18 2020-02-12 The Procter and Gamble Company Particules de détergent structurées et composition de détergent granulaire contenant ces dernières

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ES2226865T3 (es) 2005-04-01
CA2375488C (fr) 2005-11-01
EP1187904A1 (fr) 2002-03-20
BR0011796A (pt) 2002-03-12
AR025846A1 (es) 2002-12-18
DE60012928T2 (de) 2005-08-18
CN1200999C (zh) 2005-05-11
WO2000078913A1 (fr) 2000-12-28
JP4786092B2 (ja) 2011-10-05
AU5625800A (en) 2001-01-09
CA2375488A1 (fr) 2000-12-28
ATE273378T1 (de) 2004-08-15
JP2003503548A (ja) 2003-01-28
MXPA02000066A (es) 2002-07-02
DE60012928D1 (de) 2004-09-16
CN1357036A (zh) 2002-07-03

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