PT100371A - CHEMICAL STRUCTURATION OF TENSIOACTIVE PASTES FOR THE FORMATION OF HIGH ACTIVITY TENSIOACTIVE GRANULES - Google Patents

Description

1 64,565 Case CM 367 M

FIELD OF THE INVENTION The present invention relates to a process for the preparation of compositions comprising condensed detergent granules. 10ti 15

Mod. 71-20,000 ex. BACKGROUND OF THE INVENTION Granular detergent compositions have heretofore been prepared primarily by spray-drying. In the spray drying process the detergent components, such as surfactants and adjuvants, are mixed with as much as 35-50% water to form a slurry. The obtained sludge is heated and spray-dried, which is expensive. However, a good agglomeration process can be less expensive. Spray drying requires the removal of 30-40% by weight of water. Equipment used to produce spray drying is expensive. The obtained granule has good solubility, but a low bulk density, so that the packaging volume is large. In addition, the flow properties of the granule obtained by spray-drying are adversely affected by large surface irregularities and, consequently, the granule has a poor appearance. Other disadvantages are known in the preparation of granular detergents by spray drying. There are in the prior art many different spray drying processes which produce detergent granules. They also have drawbacks. Most require more than one blender and a separate granulation operation. Others require the use of the acid form of the surfactant to result. Some others require 2-35

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Mod. 71-20,000 ex. High temperatures that degrade the starting materials. In these processes, a high activity surfactant paste is avoided because of its stickiness. EP-A-0 110 731, issued August 13, 1984, describes processes for the production of detergent powders by mixing solutions of surfactant in an undiluted phase with adjuvant powders to form a solid without any evaporation drying. Processes for bars or solid blocks for milling are disclosed, but nothing is taught with respect to the conditioning of the pulp to directly form high activity granules by agglomeration. EP-A-0 345 090 issued December 6, 1989 discloses processes for the manufacture of particulate detergent compositions comprising contacting detergent acid with neutralizing agents and providing particulate compositions by contacting the detergent acid with a detergent salt or a particulate neutralization agent with carrier in an absorption zone. EP-A-0 349 201, published January 3, 1990, discloses processes for the production of detergent granules condensed by the fine dispersion of dry detergent builders and a high-active surfactant put in the form of a uniform mass which is subsequently cooled and granulated using fine dispersion to form uniform free flowing granular particles. EP-0 390 251, published October 3, 1990, discloses a process for the continuous preparation of a detergent or granular composition comprising the steps of firstly treating the particulate detergent surfactant starting material and adjuvants in a high speed mixer, secondly in a moderate speed granulator / densifier and, thirdly, in a drying / cooling device, with the addition of powder in the second or between the first and second steps to reduce the amount of particles too large -3- 35

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Mod. 71-20,000 ex.-90/08 20 J 25 30 A. Davidsohn and B.M. Mildwidsky, Synthetic Detergent, John Wiley & Sons, 6ã. edition, 1978, describe general detergency teachings, including the manufacture of finished detergent products. High shear and cold blending processes are known per se, but they require an extra grinding step or some other action. Some use a dry neutralization technique which consists in mixing an acid form of the surfactant with sodium carbonate. See U.S. Pat. 4,515,707, BrooKs, issued May 7, 1985; Japanese Application No. 183540/1983, Kao Soap Co., Ltd., filed September 30, 1983; and Japanese Application 61-118500, Lion K.K., June 5, 1986. Typically, excess carbonate (2-20 molar excess) is required to ensure a reasonable conversion of the acids of surfactants. Excess carbonate adversely elevates the pH of the wash water to the very alkaline range which may be undesirable, particularly for some low-phosphate formulas. The use of a surfactant acid generally requires immediate use or low storage temperatures for highly reactive acids, such as alkyl sulfate acids, which are subject to degradation unless cooled, they tend to undergo hydrolysis during the storage forming free sulfuric acid and alcohol. In practical terms, such prior art methods require the proximity of the production of surfactant acid and granulation which requires an additional capital investment. A second route, well known in the art and described in patent literature, is the in situ neutralization of the anionic surfactant acid with caustic solutions (eg, 50% NaOH) or caustic powders (eg, Na2 CO3) immediately before or during the course of granulation step. In this situation precautions are required to ensure neutralization

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Mod. 71-20,000 e *. To avoid undesirable effects on the remainder of the surfactant matrix during storage or during washing. The resulting particle is a highly dense granule that can be incorporated into granular detergents. Although this second route utilizes lower temperatures and less drastic cutting conditions than mixing and spray drying, it has many limitations. On the one hand the need to perform a chemical reaction (neutralization) during or just before the granulation step considerably limits the range of processing conditions that can be used (temperature, chemical etc.). The very low pH of the anionic surfactant acid prevents the incorporation of chemicals sensitive to these acidic conditions. But above all, in the case of these anionic surfactants which are not chemically stable in acid or physically unstable form, this process requires the proximity of the sulfation / sulphonation unit of the neutralization / granulation step. This results in considerable constraints on logistics and / or facility planning for these processes as well as a significant increase in the complexity and difficulty of control systems for the overall process. The present invention provides solutions to the above-mentioned problems and provides a more flexible and versatile route for the processing of granular detergents. The present invention is based on a agglomeration / granulation step which is completely disconnected from the sulfation / sulfonation process. In order to obtain the greatly increased surfactant activity of the agglomerates, the present invention allows for increasing the pulp to powder ratio that can be formed in the brittle granules. This is achieved by a chemical and / or physical structuring of the paste, such as the addition of specific chemical structuring and / or removal and moisture agents and temperature control. The base of the invention is the introduction of the anionic surfactant

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Mod. 71-20,000 ex. In a highly concentrated / aqueous solution of the salts thereof, more preferably from its sodium salt. These high activity surfactant (low moisture) slurries are high viscosity but remain pumpable at temperatures at which the surfactant is stable. This ensures the ability to transport and transfer the chemical product from the manufacturing site to the granulation site and the possibility of having suitable storage media prior to particle formation. For those cases where the sulfation / sulfonation already precedes the granulation step immediately, the possibility of installing intermediate buffer tanks is provided which simplifies control of the entire unit. In the case of some anionic surfactants or mixtures thereof where highly viscous liquid crystalline phases occur, this technology requires that low viscosity (e.g., single phases) phases be formed or that some viscosity (e.g., hydrotrope) modifiers be used. The present invention also describes a process for conducting paste conditioning. It has been found that the addition of chemical structuring agents, temperature control and / or water removal from the pulp are crucial for physical properties such as viscosities, melting point and stickiness which in turn determine the cavities, characteristics of the detergent granules produced by mixing / granulating the paste. It has been found that a very effective way to achieve this paste conditioning is the use of an extruder. An important object of the present invention is to make a dense, concentrated granular detergent product by a agglomeration process as opposed to a spray drying process. Other objects of the present invention will become apparent in view of the following. -6- 35 1 5

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The present invention relates to an economical process for producing a concentrated, dense detergent granular product and, in particular, to compositions comprising high activity detergent granules, wherein said process comprises agglomeration steps of high activity coupled to chemical treatment of the resulting slurry. The present invention is particularly applicable to all neutralized AS aqueous slurries. They can be shown to apply to a wide variety of surfactants. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of a free flowing granular detergent comprising: mixing an effective amount of a chemical structuring agent and an effective amount of an aqueous slurry of surfactant having an activity detergency of at least 40%; rapidly forming a uniform rigid paste from said blend at a pulp temperature of from 20 to 90 ° C; granulating said paste after mixing with a dry detergent powder wherein said surfactant slurry is comprised of at least one anionic surfactant and any other surfactants, if present, are selected from the group of anionic surfactants, nonionic, zwitterionic, ampholytic and cationic and mixtures thereof. In a preferred process said chemical structuring agent is added in a continuous process. The present invention is based on a process for producing high activity surfactant pastes having a agglomeration / granulation step which is completely depleted from the sulfation / sulphonation process and, additionally, a chemical conditioning of the slurries produced 1 5 10 > 15

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CV of said process for obtaining high activity granules. Conditioning a slurry means modifying its physical characteristics to form agglomerates of higher activity which otherwise are not readily obtainable under normal operating conditions. The present invention is particularly applicable to all neutralized AS aqueous slurries. It can be shown that it is applicable to a wide variety of surfactants (e.g., Coco, Tallow, ... etc). In one embodiment of the present invention, the anionic surfactant is introduced into a highly concentrated aqueous solution of its salt, preferably its sodium salt. These high activity (and preferably low moisture) surfactant pastes are high viscous but remain pumpable at temperatures at which the surfactant is stable. In other embodiments of the present invention, anionic surfactants or mixtures comprising at least one anionic surfactant in which highly viscous liquid crystalline phases occur, less viscous phases are formed or the use of viscosity modifiers is required. In a more preferred embodiment organic and / or inorganic compounds are added thereto which alter the physical structure and / or physical characteristics of the surfactant slurry. It has been found that addition to the surfactant slurry reduces tackiness of the slurry, increases its viscosity and increases the break point. This allows additional pulp to be added during the agglomeration process thereby leading to the most active agglomerates, i.e., more than 50%. This method of treating the surfactant slurry can be carried out in a batch and continuous, preferably continuous, manner. In a preferred embodiment of the invention an extruder is used to condition the paste. The extruder is a versatile piece of equipment which allows the blending of two or more pastes and / or the addition or blending of structuring agents with the viscous slurry. In addition it allows the humidifier to be heated to the desired temperature. 15

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64.565 Case CM 367 M is removed under vacuum and allows pulp temperature control. The conditioning of the paste, as defined herein, means: a) increasing its apparent viscosity, b) increasing its effective melting point, c) increasing the " hardness " of the paste and d) reducing the tackiness of the formed granules. The hardness / softness of the slurry may be measured by a softness penetrometer according to ASTM D 217-IP50 or ISO 2137. The hardness of the slurry thus measured should be less than 2 cm, preferably less than 1 cm. This pulp conditioning can be achieved by i) cooling, ii) drying, iii) adding structurants (usually electrolytes) to the high activity detergent slurry. A useful binder for this invention will be at least 40% by weight of salts of anionic surfactants having a viscosity of 10 Pa.s, when measured at 70 ° C and a cut-off ratio of 25 s "L.

Chemical Structuring Agents Various chemical structuring agents, when added to the surfactant slurry, result in a modification of the chemical and / or physical characteristics of the pulp to form high activity agglomerates. These agents may be in solid, liquid or solution form, depending on their specific chemical properties. Examples of agents useful in the present invention include 50% NaOH, 50% KOH, NaCl, phosphonate, silicate, silica, starch, polymers and copolymers, nonionic surfactants and urea. The foregoing agents may be used independently or in combination with each other, in accordance with their compatibility.

The Folders

One or more aqueous slurries of the above-mentioned products are preferred.

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Salts of anionic surfactants for use in the present invention, preferably the sodium salt of the anionic surfactant. In a preferred embodiment, the anionic surfactant is preferably as concentrated as possible (i.e., with the lowest possible moisture content allowing it to flow in the same manner as a liquid) in order to be pumped at temperatures at which it remains stable. While granulation is known using various pure or mixed surfactants, for the present invention to be of practical utility in the industry and result in particles of physical properties suitable for incorporation into granular detergents, an anionic surfactant should be part of the pulp at a concentration greater than 10%, preferably 10-95%, more preferably 20-95%, and most preferably 40-95%. It is preferred that the moisture in the aqueous slurry of surfactant is as low as possible, although pulp fluidity is maintained, since low moisture leads to a higher concentration of surfactant in the finished particle. Preferably the slurry contains between 5 and 40% water, more preferably between 5 and 30% water and even more preferably between 5 and 20% water. A highly attractive mode of operation for decreasing the moisture of the pulp prior to entering the agglomerator without problems with very high viscosities is the in-line installation of an atmospheric or vacuum flash dryer whose outlet is connected to the agglomerator. It is preferred to use highly active surfactant slurries to minimize the total water level in the system during mixing, granulation and drying. Lower water levels allow: (1) a higher adjuvant surfactant ratio, e.g., 1: 1; (2) more effluent levels of other liquids in the formula without causing formation of a granular mass or tack; (3) lower cooling, due to higher temperatures being allowed to -10- 35 ° 5

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64,565 Case CM 367 M 13 JUU992V / / Π / granulation; and (4) lower granular drying to achieve final moisture limits. Two important parameters of the surfactant pastes which may affect the mixing and granulation step are the temperature and viscosity of the slurry. Viscosity is a function, among others, of concentration and temperature, with a range in this application of about 10 to 10,000 Pa.s (10,000 to 10,000,000 cps). Preferably, the viscosity of the slurry entering the system is about 20 to 100,000 cps and more preferably about 30 to 70,000 cps. The viscosity of the slurry of this invention is measured at a temperature of 70 ° C. The slurry may be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60 ° C) and its degradation point (depending on the chemical nature of the slurry, eg, alkyl sulfate pulps tend to to degrade above 75-85 ° C). High temperatures reduce viscosity by simplifying slurry pumping, but result in lower activity agglomerates. However the use of in-line moisture reduction steps (e.g., flash drying) requires the use of higher temperatures (greater than 100øC). In the present invention, the activity of the agglomerates is kept high due to the elimination of moisture. The introduction of the slurry into the mixer can be done in many ways, from simply pouring to high pressure by means of small holes in the end of the conduit, prior to entry into the mixer. Although all these routes are feasible to make agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the slurry results in a better distribution in the mixer which improves the yield of the desired size particles. The use of high pumping pressures prior to entry into the mixer results in increased activity in the agglomerates f

64,565 Case CM 367 M 13 JUL892 - / "

nais. By combining both effects, and introducing the slurry through holes (extrusion) sufficiently small to allow the desired flow rate but maintaining the pumping pressure to a maximum practicable in the system, highly advantageous results are achieved.

High Activity Surfactant Folder

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Mod. 71-20,000 ex. The activity of the slurry aqueous slurry. active is at least 30% and can go up to 95%; the preferred activities are: 50-80% and 65-75%. The remainder of the paste is mainly water but may include a processing aid as a nonionic surfactant. At higher active concentrations, little or no adjuvants are required for cold granulation of the pulp. The resulting center-colored surfactant granules may be added to dry or powdered adjuvants or used in conventional agglomeration operations. The aqueous slurry of surfactant contains a surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof. Anionic surfactants are preferred. Nonionic surfactants are used as secondary surfactants or processing aids and are not included herein as an " active " active agent. &Quot;. Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Noirris, issued May 23, 1972, and U.S. Pat. No. 3,919,678, Laughlin et al., Issued December 30, 1975. Useful cationic surfactants further include those described in U.S. Pat. 4,222,905, Cockrell, issued September 16, 1980, and U.S. Pat. No. 4,239,659, Murphy, issued December 16, 1980. However, cationic surfactants are generally less compatible with the present aluminosilicate materials and thus are preferably used at low levels if used in the present compositions. The following are examples:

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64,565 Case CM 367 M surfactants useful in the present compositions. Water-soluble salts of the higher fatty acids, i.e., " soaps " are anionic surfactants useful in the present compositions. This includes alkaline soaps such as the sodium, potassium, ammonium and al-kammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms of carbon. Soaps can be produced by direct saponification of fats and oils: or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium soap of tallow and coconut. Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylammonium salts of organic sulfuric reaction products, having in their molecular structure an alkyl group containing from about 10 to about 20 atoms of carbon and a sulfonic acid or sulfuric acid ester group. (Included within the term " alkyl " is the alkyl moiety of acyl groups). Examples of this group of synthetic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher alcohols (C--C g átomos átomos carbon atoms) such as those produced by reduction of tallow glycerides or coconut oil; and sodium and potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. 2 220 099 and 2 477 383. Particularly valuable are straight-chain alkylbenzene sulfones in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C LAS-C LAS-alkyl. Other anionic surfactants included herein are the sodium alkyl glyceryl ether sulfonates, es ···

? " V 64.565 Case CM 367 M

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Mod. 71-20,000 ex. Especially the ethers of higher alcohols derived from coconut oil and tallow; sulfonates and sulfates of sodium coconut oil fatty acid monoglyceride; sodium or potassium salts of ethyl phenol alkylphenol ether sulfates containing from about 1 to about 10 ethylene oxide units per molecule and in which the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of ethylene oxide alkyl ether sulfates containing from about 1 to about 10 ethylene oxide units per molecule and in which the alkyl group contains from about 10 to about 20 carbon atoms . Other anionic surfactants useful herein include the water-soluble salts of alpha-sulfonated fatty acid esters containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the group ester; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane portion; alkyl ether sulfates containing from about 10 to about 20 carbon atoms in the alkyl group and from about 1 to about 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to about 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the group in the alkane moiety. Although the acid salts are typically discussed and used, acid neutralization can be performed as part of the fine dispersion mixing step. Preferred anionic surfactant pastes are mixtures of linear or branched alkyl benzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pulps are generally produced by reacting

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of a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid. The salt is the surfactant slurry discussed throughout this document. The sodium salt is preferred because of the ultimate performance and cost benefits of NaOH vs. others ager. but it is not required so that other agents such as KOH can be used. Water-soluble nonionic surfactants are also useful as a secondary surfactant in the compositions of the invention. In fact, preferred processes use anionic / nonionic mixtures. A particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of about 0.01: 1 to about 1: 1, more preferably about 0.05: 1: Nonionic surfactants to an equal amount of the primary organic surfactant. These nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be of aliphatic or alkylaromatic nature. The length of the polyoxyalkylene group which is condensed with a particular hydrophobic group can easily be adjusted to produce a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, eg, the condensation products of alkylphenols having an alkyl group containing from about 6 to about 16 carbon atoms, in the straight or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkylphenol. Preferred nonionic surfactants are condensation of aliphatic alcohols containing about 8 to 22 carbon atoms,

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Mod. 71-20,000 ex. In the straight chain or branched chain configuration with from about 4 to 25 moles of ethylene oxide per mole of alcohol Particularly preferred are the condensation products of alcohols having an alkyl group containing from 4 to 25 moles of ethylene oxide per mole of alcohol. about 9 to 15 carbon atoms with about 4 to 25 mole of ethylene oxide per mole of alcohol and the condensation products of propylene glycol with ethylene oxide Semi-polar nonionic surfactants include amine oxides soluble in water containing an alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water soluble phosphine oxides containing one alkyl portion of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms and water soluble sulfoxides containing an alkyl portion of about 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl moieties containing from 1 to about 3 carbon atoms. Ampholytic surfactants include aliphatic tribates of heterocyclic secondary and tertiary amines in which the aliphatic moiety may be straight or branched chain and in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least an aliphatic substituent contains an anionic solubilizing group in water. Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium and phosphonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms. Particularly preferred surfactants herein include linear alkylbenzene sulfonates having from about 11 to 14 carbon atoms in the alkyl group.

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and? / lo; tallow alkyl sulfates; alkyl glyceryl ether sulfone-coconut cough; alkyl ether sulfates in which the alkyl moiety contains from about 14 to 18 carbon atoms and in which the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; alkyldimethylamine oxides in which the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonium propanesulfonates and alkyldimethylammonium hydroxypropanesulphonates in which the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; products of the condensation of C6 -C15 alcohols with from about 3 to about 8 moles of ethylene oxide and their mixtures. Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form ## STR4 ## in which R 4 is alkyl having 10 to 20, preferably 12-18 carbon atoms and R 5, R 6 and R 7 are each a C7-alkyl, preferably methyl; X " is an anion, e.g., chloride. Examples of such tri-methyl ammonium compounds include (C 12 -C 14 alkyl) trimethylammonium chloride and coconut alkyltrimethylammonium methosulfate. Specific preferred surfactants for use herein include: (C11 -C13 linear alkyl) sodium benzenesulfonate; alkyl sulfates (tallow, coconut, palm, synthetic origin, eg, C45, etc.); sodium alkyl sulfates; MES; alkyl glyceryl ether sulfonates of (X-olefin) (C11-C13 alkyl) benzenesulfonate of triethanolammonium; the sodium salt of a sulphated condensation product of a tallow alcohol having about 4 moles of ethylene oxide the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; condensation product of a fatty alcohol of tallow with about 11 moles of ethylene oxide; the condensation product of a fatty alcohol containing from about 14 to about 15 carbon atoms;

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Carbon dioxide with about 7 moles of ethylene oxide; the condensation product of a C 12 -C 13 fatty alcohol with about 3 moles of ethylene oxide; 3 (N, N-dimethyl-N-cocoalkylammonio) -2-hydroxypropane-1-sulfonate; 3- (N, N-dimethyl-N-cocoalkylammonio) -propane-1-sulfonate; 6- (N-dodecylbenzyl-N; N-dimethylammonium) -hexanoate; dodecyldimethylamine oxide? coconut alkyldimethylamine oxide; and the sodium and potassium water soluble salts of coconut and tallow fatty acids. As used herein, the term " Active surfactant " means nonionic surfactants, unless otherwise specified. The ratio of the active surfactant (excluding the nonionic surfactant (s)) to powder or adjuvant detergent is in the range of from 0.005 to 19: 1, preferably from 0.05 to 10: 1, and more preferably from 0.1: 1 to 5: 1. The ratios of active adjuvant to active agent Preferred are 0.15: 1 to 1: 1 and 0.2: 1 to 0.5: 1).

THE EXTRUDER The extruder performs the pump-mixing and blending functions of the slurry of viscous surfactant on a continuous basis. A basic extruder consists of a drum with smooth cylindrical inner surface. Mounted inside this barrel is the extruder screw. There is a port of entry for the high activity pulp which, when the screw is turned, causes the pulp to move along the length of the drum. The detailed design of the extruder allows several functions to be performed. First, additional ports in the drum may allow other ingredients, including chemical structuring agents, to be added directly into the drum. Second, a vacuum pump and a seal around the screw shaft allow you to create a vacuum that allows you to reduce the level of humidity. Thirdly, heating means may be provided and 18-35 1 64,565

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Mod. 71-20,000 e *. - 90/08 20 J 25 30 cooling the drum wall for temperature control. Fourth, the careful design of the extruder screw promotes the blending of the paste with itself and with other additives. A preferred extruder is a twin screw extruder. This type of extruder has two screws mounted in parallel within the same drum, which are rotated in the same direction (co-rotation) or in opposite directions (counter-rotation). The co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention. An extruder is particularly useful in this invention because the slurry can be efficiently cooled by addition of liquid nitrogen or solid carbon dioxide to the drum (this may be considered surprising because normally an extruder warms its contents as a result of the energy supply mechanical means for overcoming viscous cobalt forces) and at the same time pumps the increasingly viscous (colder) paste out of the extruder and into the agglomerator / painter where the granulation takes place. Double screw extruders suitable for use in the present invention include those provided by: APV Bakei (CP series); Werner and Pfleiderer, (Continuous Series); Wenger, (TF Series); Leistritz, (ZSE series); and Buss, (LR Series). The extruder allows the pulp to be conditioned by reduction of humidity and temperature. The moisture can be removed under vacuum, preferably between 0 mmHg (relative) and -55 mmHg (relative), (0-7.3 kPa below atmospheric pressure). The temperature can be reduced by the addition of solid carbon dioxide or liquid nitrogen directly to the extruder barrel. Preferably liquid nitrogen is used up to 30% by weight of the slurry. -19- 35

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While the preferred embodiment of the process of the present invention involves introducing the anionic surfactant into the pulps as described above, it is possible to have a certain amount through the stream of powder, for example in the form of blown powder. In these embodiments, the tackiness and moisture of the powder stream is required to be maintained at low levels, thereby preventing the build-up of " of the anionic surfactant and, consequently, the production of agglomerates with a too high concentration of surfactant. The liquid stream of a preferred agglomeration process may also be used to introduce other surfactants and / or polymers. This may be done by premixing the surfactant into a stream of liquids or alternatively by introducing various streams into the agglomerator. These two process embodiments can produce differences in the properties of the finished particles (breakdown, gel formation, dissolution rate, etc.), particularly if mixed surfactants are allowed to form prior to particle formation. These differences can be exploited as an advantage of the intended application for each preferred process. It has also been found that using the technology presently described, it was possible to incorporate high levels of certain chemicals (eg, nonionic compounds, citric acid) into the final formula, than through other known processing routes without detrimental effects to some key properties of the matrix (formation of lumps, compression, etc.) Mixtures and Fine Dispersion Granulation The term " fine dispersion blend " as used herein means blend and / or granulation of the blend above in a fine dispersion mixer

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64,565 Case CM 367 M r 2 JU 2 2 992 at a blade tip speed of about 5 m / s to about 50 m / s, unless otherwise specified. The total residence time of the mixing and granulating process is preferably in the range of about 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes. The most preferred blending and blending end speeds are about 10-45 m / s and about 15-40 m / s. The pulp ratio should be chosen so as to maintain discrete, visible particles at all stages of the process. These particles may be sticky at higher temperatures, but must be substantially free flowing so that the mixing and granulation steps can be performed simultaneously or immediately in sequence without causing blockage of the mixer / granulator. Any suitable devices, plants or units for processing surfactants may be used to carry out the process according to the invention. Suitable devices include, for example, down-stream sulphonation reactors, digestion tanks, esterification reactors, etc. Any of many mixers / agglomerators may be used for the mixing / agglomeration. In a preferred embodiment, the process of the invention is carried out in a continuous manner. Especially preferred are the FlukaeR FS-G series mixers manufactured by Fukae Powtech Kogyo Co., Japan; this device is essentially in the form of a bowl-shaped container, accessible through a top port, provided at its base with a stirrer having a substantially vertical axis and a positioning device positioned on the side wall. The cutting device and the agitator can be operated independently of each other and at independently variable speeds. The vessel may be equipped with a cooling jacket or, if necessary, with a cryogenic unit. 35 1 5 10 15

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64,565 Case CM 367 M:

Other similar blenders which have been found to be suitable for use in the process of the invention include the Diosna® Ex DierKs & Sohne, Germany; and Pharma Matrix® ex TK Fielder Ltd., England. Other mixers believed to be suitable for use in the inverting process are those of Fuji® VG-C series ex Fuji Sangyo Co., Japan; and RotoR ex Zanchetta & Co srl, Italy. Other suitable preferred equipment may include Eirich®, RV series, manufactured by Gustau Eirich Hardhein Germany; LodigeR, FM series for discontinuous mixing, Baud KM series for continuous mixing / agglomeration, manufactured by Lodige Machinenbau GmbH, Paderborn Germany; series DraisR T160, manufactured by Drais Werhe GmbH, Mannheim Germany? and WinkworthR RT 25 series, manufactured by Winhworth Ma. chinery Ldt., Bershire, England. 0 Littleford Mixer, Model 4 = FM-130-D-12, with internal cutter blades, the DCX-Plus Cui-sinart Food Processor with 7.75 inch (19.7 cm) blades are two examples of mixers. Any other mixer capable of mixing and fine dispersing granulation and having a residence time in the range of 0.1 to 10 minutes can be used. The "turbine-type" impeller is preferred, having several blades on a rotational axis. The invention may be practiced as a batch or continuous process.

Operating Temperatures Preferred operating temperatures should also be as low as possible as this leads to a higher concentration of surfactant in the finished particle. Preferably, the temperature during agglomeration is below 100øC, more preferably between 10ø and 90øC and most preferably between 20ø and 80øC. Lower operating temperatures useful in the process of the present invention may be achieved by a variety of

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64.565 Case Cm 367 M

methods known in the art such as cooling with nitrogen, coating the apparatus with a cold water jacket, dc> 2 solid, and the like; a preferred method being that of solid CO2 and the most preferred method being that of cooling with nitrogen. A highly attractive option in an embodiment of the present invention to further increase the concentration of surfactant in the final particle is achieved by the addition, to a liquid stream of anionic surfactant and / or other surfactant, of other elements resulting in increase in viscosity and / or melting point and / or decrease in tackiness of the slurry. In a preferred embodiment of the process of the present invention the addition of these elements may be done in-line as the slurry is pumped into the agglomerator. Examples of such elements may be various powders, described here in greater detail.

Final Agglomerate Composition The present invention produces high density granules for use in detergent compositions. A preferred composition of the final agglomerate for incorporation into the granular detergents has high concentration of surfactant. By increasing the concentration of surfactant, the particles / agglomerates produced by the present invention are more suitable for a variety of different formulations. These high surfactant particles / agglomerates require less standardization techniques to achieve the final agglomerates, thereby releasing large amounts of processing aids (inorganic powders, etc.) which can be used in other processing steps of the agglomerate. detergent manufacturing process (spray drying, dust removal, etc.). The granules made in accordance with the present invention are large, low in dust and drains.

And preferably have a bulk density of from about 0.4 to about 1.2 g / cm 3, more preferably from about 0.6 to about of 0.8 g / cm 2. the particle size weighted average of the particles of this invention is from about 200 to about 1000 microns. Preferred granules thus formed have a particle size range of 200 to 2000 microns. The most preferred granulation temperature range is from about 10 ° C to about 60 ° C, and most preferably from about 20 ° C to about 50 ° C.

10 J

Drying 15

Mod. 71-20,000 ex. The desired moisture content of the free flowing granules of this invention can be adjusted to levels suitable for the intended application by drying in conventional powder drying equipment, such as fluidized bed dryers. If a hot air fluid bed dryer is used, care must be taken to avoid degradation of the heat sensitive components of the granules. It is also advantageous to have a cooling step prior to arming on a large scale. This step can also be carried out in a conventional fluidized bed operated with cold air. The drying / cooling of the agglomerates may also be performed in any other suitable equipment for drying powder such as rotary dryers, etc. For detergent applications, the final moisture of the agglomerates needs to be maintained below the levels at which the agglomerates can be stored and transported in bulk. The exact level of humidity depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e., water not associated with any crystalline species in the agglomerate), and very typically at 2-4%.

Adjuvants of Determination and Post-24- 35 10

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64.565 Case CM 367 M

X / -

Any detergent builder or combination of adjuvants and powders may be used in the process and compositions of the present invention. The present detergent compositions may contain crystalline ion exchange aluminosilicate material of formula

Naz [(A102) z (SiO2) yW.xH20 in which z and y are at least 6, the molar ratio z to y is from about 1/0 to about 0/4 and z is from about 10 to about 264 Hydrated / amorphous aluminosilicate materials have the empirical formula

Mz (zA102.ySiO2) in which M is sodium / potassium / ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having an ion exchange capacity of magnesium of at least , about 50 milligrams equivalent to the CaCO 3 hardness per gram of anhydrous aluminosilicate. The hydrated sodium Zeolite A is preferred, with a particle size of about 1 to about 10 microns. The ion exchange aluminosilicate builders included herein are in the hydrated form and contain from about 10% to about 28% by weight of water, if they are crystalline and, potentially, larger amounts if they are amorphous. Crystalline ion exchange aluminosilicate materials contain from about 18% to about 22% water in its crystalline matrix. The crystalline ion exchange aluminosilicate materials are further characterized by a particle diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., up to less than 0.01 micron. Preferred ion exchange materials have a particle diameter of from about 0.2 microns to about 4 microns. The term " particle diameter ", included herein represents the dia.

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64.565 Case CM 367 M

average particle by weight of a given ion exchange material, as determined by conventional analytical techniques, for example, microscopic determination using a scanning electron microscope. The crystalline ion exchange aluminosilicate materials included herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent to the CaCO 3 / water aluminosilicate water hardness, calculated on an anhydrous basis , and which is generally in the range of about 300 mg eq / g to about 352 mg eq / g. The ion exchange aluminosilicate materials included herein are further characterized by their calcium ion exchange rate, which is at least about 2 Ca + Varnish / / minute / gram / gallon aluminosilicate (anhydrous basis) and , is generally in the range of about 2 grains / gallon / minute / grams / gallon to about 6 grains / gallon / minute / gallium, based on the calcium ion hardness. The optimum aluminosilicate for adjuvant purposes exhibits a calcium ion exchange rate of at least about 2 grains / gallon / minute / grams / gallon. Amorphous ion exchange aluminosilicate materials generally have a Mg ++ exchange of at least 50 mg eq. CaC03 / g (12 mg Mg ++ / g) and a Mg ++ exchange rate of at least about 1 grain / gallium / minute / gram / gallon. Amorphous materials do not exhibit an observable dendrition pattern when examined by Cu radiation (1.54 Angstrom units). The ion exchange aluminosilicate materials useful in the practice of this invention are available commercially. The aluminosilicates useful in this invention may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived. A method for producing ion exchange aluminosilicate materials is described in U.S. Patent 3,985,669, Krummel et al., Issued October 12, 1976, incorporated herein by reference. Crystalline exchange aluminosilicate materials 35 to 35

10 J 16

64.565 Case CM 367 M

X

ionic, silicate materials useful herein are available under the designations Zeolite A, Zeolite B and Zeolite X. In an especially preferred embodiment, the crystalline ion exchange aluminosilicate material has the formula.

Na12C (A102) 12. (SiO2) 12] .xH20

Mod. 71-20,000 ex. Wherein x is from about 20 to about 30, especially about 27, and has a particle size generally less than about 5 microns. The granular detergents of the present invention may contain neutral or alkaline salts having a solution pH of seven or greater and may be organic or inorganic in nature. The adjuvant salt helps to provide the desired density and body of the present detergent granules. Although some of the salts are inert, many of them also act as detergency builders in the wash solution. Examples of neutral salts, soluble in water, include the alkali metal, ammonium and substituted ammonium chlorides, fluorides and sulfates. The alkali metal and especially sodium salts of the above are preferred. Sodium sulfate is typically used in homogeneous granules and is a particularly preferred salt. Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention so long as they are chemically compatible with the remainder of the agglomerate composition. Other useful water-soluble salts include compounds commonly known as detergent builders. Adjuvants are generally selected from the various alkali metal, ammonium and substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates and polyhydroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above. 35 9 1 5 10 15

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64.565 Case CM 367 M

Specific examples of inorganic phosphate builders are tripolyphosphate, pyrophosphate, polymeric metaphosphate / having a degree of polymerization of about 6 to 21, and sodium or potassium orthophosphate. Examples of polyphosphonate adjuvants are the sodium and potassium salts of ethylenediphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane- 1,2-triphosphonic acid. Other phosphorus adjuvant compounds are disclosed in U.S. Pat. 3,159,581; 3,213,030; 3 422 021; 3,232,137; 3 400 176 and 3 400 148, incorporated herein by reference. Examples of inorganic adjuvants having no phosphorus are carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and sodium and potassium silicate having a molar ratio S102 to alkali metal oxide of about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. The compositions produced by the process of pre. The present invention does not require excess carbonate for processing and preferably contains no more than 2% finely divided calcium carbonate as disclosed in U.S. 4 196 093, Clarke et al., Issued April 1, 1980, and preferably does not contain the latter. As mentioned above, powders commonly used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. can be used. and process aids such as starch in the preferred embodiments of the present invention.

Polymers

Various organic polymers are also useful, some of which may also act as adjuvants to improve detergency. Included among these polymers can be mentioned sodium carboxy (lower alkyl) celluloses, sodium (lower alkyl) celluloses and hydroxy (lower alkyl) celluloses, such as carboxymethylcellulose.

1 64,565 Case CM 367 M sodium, sodium methylcellulose and sodium hydroxypropylcellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various polymers, such as those maleic and acrylic acids.The molecular weights of these polymers vary widely but most are within the range of 2000 to 100,000.

Polymeric polycarboxylate adjuvants are disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. These materials include the water soluble salts of homo or copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, table-conic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. 15

Mod. 71 -20,000 ex. - 90/08 20 J 25 30

Optional

Other ingredients commonly used in compositions may be included in the compositions of the present invention! detergents. These include flow aids, powders, bleaching agents and bleaching activities, foam regulators and / or suds suppressors, anti-fogging and anti-corrosion agents, soil suspending agents, soil release agents , pigments, fillers, optical brighteners, germicides, pH adjusting agents, non-adjuvant alkalinity sources, hydrotropes, enzymes, enzyme stabilizing agents, chelating alloys and perfumes.

The detergent granules of the present invention are particularly useful in a bag-pouch product ("pouched through-the-wash Products"). Granular detergent compositions of this invention may be included as pergo type materials -tetrahydrate, tetrahydrate or sodium monohydrate. Disclosed in the art are products which take the form of a pouch along the 1 1/1 10

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64,565 Case CM 367 Methyl, e.g., those disclosed in commonly assigned U.S. Pat. 4,740,326, Hortel et al., Issued April 26, 1988. Another useful pouch has at least one of its walls constructed of finely-drilled polymeric film. The terms " LAS " and " AS " as used herein mean respectively " sodium laurylbenzenesulfonate " and " alkyl sulfate. " MES " means sodium methyl sulfonate. Terms like " C45 " means C 14 and C 15 alkyl, unless otherwise specified. TAS stands for tallow alkyl sulfate. The invention will be better understood by considering the following non-limiting examples. The percentages are by weight before drying, unless otherwise specified. The tables are followed by further processing disclosures.

Example

This example describes the batch mode in a high shear pilot mixer, an Eirich RV02. The mixer is charged first with a mixture of the powders to be used, in this particular case a 2: 1 ratio of Zeolite A to finely divided carbonate or Zeolite A to finely divided citrate. The tensioactive agent is an aqueous C 45 AS slurry with a detergent activity of 78% and a water content of 13%. In this Example, a 50% solution of NaOH (0.6 kg) in the mixer (Eirich RV02) is added to the slurry (3 kg) prior to the start of the granulation. After mixing, the slurry solidifies and is milled by the mixer at 2500 rpm. The process is stopped and the powders (1.050 kg) are added. The mixer is run until the granulation takes place. The process is then stopped and the agglomerates are dried in a fluidized bed and sorted through mesh sieves. The agglomerates may have a detergent activity of 60% and a density of 600 g / L. They exhibit excellent physical properties. 35 64,565 *

Case CM 367 M

Example 25

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Mod. 71 -20,000 ex. 20

This example is similar to Example 1. The powder mixture again has a 2: 1 ratio of Zeolite A to finely divided carbonate. The surfactant is an AS C45 aqueous slurry with a detergent activity of 78% and water content of 13%. In this Example, the powders (1.05 kg) and the slurry (3 kg) are added to the mixer (Eirich RV02) prior to the start of the granulation. A certain amount (2 kg) of dry ice is also added to the mixer to lower the temperature to below -15 ° C. The mixer is then turned on at a speed of 1600 (2500) rpm. Initially, at reduced temperature which is achieved, the mixture is in the form of a fine powder. The mixer is operated until the temperature reaches the point (12 ° C) at which the granulation takes place. The process is then stopped and the agglomerates are dried in a fluidized bed and sieved through sieves. The agglomerates produced have a detergent activity of 60% and a density of 625 g / l. They exhibit excellent physical properties.

Example 3 J 25 30

This example describes the continuous process in a laboratory-scale high shear mixer (food processor). The mixer is first charged with a mixture of the powders to be used, in this particular case a 2: 1 ratio of Zeolite A to carbonate , finely divided. The surfactant is an aqueous C 45 AS slurry having a detergent activity of 72% and a water content of 24%. In this Example, silica powder (40 g) is added to the slurry (400 g) in the mixer before starting the granulation. After mixing, the paste hardens. The process is stopped and the powders (105 g) are added to the slurry (335 g). The blender is poured until the granulation takes place. The process is then stopped and the agglomerates are dried in a fluidized bed and sorted through mesh sieves. The agglomerates produced have

64.565 Case CM 367 M

a detergent activity of 55-60% and a density of 650 g / L. They exhibit excellent physical properties.

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Example 4 This example describes the pulp conditioning process in a continuous mode in a pilot installation double screw extruder, Werner and Pfleiderer C58, with a six section drum, followed by immediate granulation of the pulp leaving the extruder in a high speed mixer laboratory scale. The surfactant is an aqueous slurry of sodium linear alkyl benzene sulfonate (NaLAS with a detergent activity of 78% and a water content of 18%. The slurry is introduced into the extruder at a temperature of 70 ° C and a The slurry leaving the extruder is agglomerated in the laboratory scale high shear mixer with a ratio of 2: 1, by weight, of Zeolite A to finely divided carbonate powders. The slurry is added to the bed The pellets are then dried in a fluidized bed and analyzed for the LAS content (described herein as activity). The slurry is simply pumped through the pellets. of the extruder operating at 100 to 120 rpm. The slurry leaving the extruder is still at 70øC and the resulting agglomerates activity is 32%.

Example 5

Agglomerates are produced using the same equipment and weight ratios as in Example 4. In this example, the slurry is cooled as it is pumped through the extruder by means of cooling coils containing water from the network at 15øC in the first two sections and glycol -20 ° C in the last four sections of the drum. The pulp exit temperature under steady-state conditions is -32-

64,565 Case CM 367 M 13 JUL.1992 130 ° and the activity of the resulting agglomerates is 45%.

Example 6

Agglomerates are produced using the same equipment and weight ratios of example 4. In this example, a solid powder of maleic and acrylic acid copolymer is added to the slurry at the inlet of the extruder. Without any cooling, the temperature of the slurry leaving the extruder is 68øC and the activity of the resulting agglomerates is 38%. When cooling the extruder barrel in the same manner as in Example 5 of Example 5, the slurry outlet temperature is 30øC and the agglomerate action of the resulting pellets is 54%.

Example 7 15

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Agglomerates are produced using the same equipment and weight ratios of example 4. In this example, however, NaLAS is replaced by a surfactant slurry containing 60% by weight of sodium alkyl sulphate having a carbon chain length of C14-C15 and containing 25% water. The inlet temperature is again 70 ° C. The slurry is simply pumped through the extruder and exits at a temperature of 70 ° C. The activity of the resulting agglomerates is 36%.

Example 8

Agglomerates are produced using the same equipment and weight ratios of example 7, also using the alkyl sulfate pulp of this example. However, in this example, a vacuum is applied through a vacuum port on one of the drums using a vacuum capable of achieving 70 mbar vacuum. Simultaneously cooling is applied through the internal coils of the extruder with the use of glycol at -20 ° C in all sections of the drum. The paste that

1 64,565 Case CM 367 M

Exiting the extruder has an activity of 72%, a water content of 22% and a temperature of 25 ° C. The agglomerates produced with this paste have an alkyl sulphate activity of 60%.

Example 9

Agglomerates are produced using the same equipment and weight ratios of example 7, also using the alkyl sulfate pulp of this example. In this example the slurry is cooled by passing glycol at -20øC through the cooling coils and additionally by injecting liquid nitrogen into the fourth section of the drum at a flow rate of 15 kg / hr. The slurry leaving the extruder has a temperature of 15 ° C and the resulting agglomerates have a 65% alkyl sulfate activity.

Mod. 71-20,000 ex. - 90/08 20 J 25 30

Lisbon, 13 Μ. $ 32

By THE PROCTER & GAMBLE COMPANY

............ . of Propranolatry " Ate® dc Conca.

35-34-

Claims (2)

1 5 10 15 20 25 30 64,565 Case CM 367 M A production process for a concentrated granular detergent composition comprising the following steps; (i) neutralizing anionic surfactant (s) in an excess of base to give a high activity paste (at least 40% by weight anionic surfactant), said paste having a viscosity of at least 10 Pa.s, when measured at 70 ° C, and a cut-off rate of 25 s -1; (ii) conditioning said folder; (iii) forming high activity detergent granules in a high shear mixer / granulator / in the presence of an effective amount of detergent powder. 2 -. A process for carrying out the step (ii) of claim 1, comprising pumping and / or reducing the moisture and / or cooling and / or addition of chemical builders to said high activity slurry characterized in that an extruder is used. 3§. A process according to claim 2, characterized in that the slurry enters the extruder at a temperature between 40 ° C and 80 ° C and under a vacuum of 0 to 7,3 kPa (below atmospheric pressure). 4 ^. A process according to claim 2 or 3, characterized in that one or more entrances in the extruder drum allow the addition of additional powders and / or pastes which are then mixed in the extruder. 5ã. A process according to any one of claims 2 to 4, characterized in that the drum of the mixing section of the extruder is cooled by any suitable means, including the addition of up to 30% by weight of the pastry. of solid carbon dioxide or of direct liquid nitrogen 35-35 64,565 Case CM 367 M P n; /! Into the extruder drum. 6a. 2. A process according to any one of claims 2 to 5, characterized in that the extruder is a double screw extruder. A process according to any one of claims 1 to 6, characterized in that the chemical builder is in the form of a powder. 10 Lisboa, 13JUU982 15 Mod. 71-20,000 β *. - 90/08 20 25 30 By THE PROCTER & GAMBLE COMPANY Agt'-2 C; O! In this paper, we will discuss the results of this study. and, 35