Agglomeration of High Active Pastes to Form Surfactant Granules Useful in Detergent Compositions

The present invention relates to a process for preparing compositions comprising condensed detergent granules.

Granular detergent compositions have so far been principally prepared by spray drying. In the spray drying process the detergent components, such as surfactants and builders, are mixed with as much as 35-50% water to form a slurry. The slurry obtained is heated and spray dried, which is expensive. A good agglomeration process, however, could be less expensive.

Spray drying requires 30-40 wt. % of the water to be removed. The equipment used to produce spray dry is expensive. The granule obtained has good solubility but a low bulk density, so the packing volume is large. Also, the flow properties of the granule obtained by spray drying are adversely affected by large surface irregularities, and thus the granulate has a poor appearance. There are other known disadvantages in preparing granular detergents by spray drying.

There are many prior art nonspray-drying processes which produce detergent granules. They have drawbacks as well. Most require more than one mixer and a separate granulation operation. Others require use of the acid form of the surfactant to work. Some others require high temperatures which degrade the starting materials. High active surfactant paste is avoided in these processes because of its stickiness.

EP-A-0 345 090, published Dec. 6, 1989, discloses a process for manufacturing particulate detergent compositions comprising contacting detergent acid with neutralizing agents and providing particulates by contacting the detergent acid with a particulate neutralizing agent or detergent salt with carrier in an absorption zone.

EP-A-0 349 201, published Jan. 3, 1990, discloses a process for preparing condensed detergent granules by finely dispersing dry detergent builders and a high active surfactant put into a uniform dough which is subsequently chilled and granulated using fine dispersion to form uniform, free flowing granular particles.

EP-0 390 251, published Oct. 3, 1990, discloses a process for the continuous preparation of a granular detergent or composition comprising steps of treating, firstly, particulate starting material of detergent surfactant and builders in a high-spead mixer, secondly in a moderate-speed granulator/densifier and thirdly in a drying/cooling apparatus, with the addition of powder in the second or between the first and second step to reduce the amount of oversize particles.

A. Davidsohn and B. M. Mildwidsky, Synthetic Detergents, John Wiley & Sons 6th edition, 1978, discloses general detergency teachings, including the manufacturing of finished detergent products.

High shear and cold mixing processes per se are known, but they require an extra grinding step or some other action. E.g., some use a dry neutralization technique of mixing an acid form of the surfactant with sodium carbonate. See U.S. Pat. No. 4,515,707, Brooks, issued May 7, 1985; Japanese laid-open Appln. No. 183540/1983, Kao Soap Co., Ltd., filed Sept. 30, 1983; and Japanese Sho. 61-118500, Lion K. K., Jun. 5, 1986. Typically, excess carbonate is required (2-20 molar excess) to assure reasonable conversion of the surfactant acids. Excess carbonate adversely drives up the wash water pH to the very alkaline range which can be undesirable, particularly for some low-phosphate formulas.

The use of a surfactant acid generally requires immediate use or cool temperature storage, for highly reactive acids such as the alkyl sulfate acids are subject to degradation unless cooled, they tend to undergo hydrolysis during storage, forming free sulfuric acid and alcohol. In practical terms, such prior art processes require close-coupling of surfactant acid production with granulation which requires an additional capital investment.

A second route, well known in the field and described in the patent literature, is the in-situ neutralisation of the anionic surfactant acid with caustic solutions (e.g. 50% NaOH) or caustic powders (e.g. Na.sub.2 CO.sub.3) right before or in the course of the granulation step. In this situation, precautions are needed to ensure complete neutralisation of the acid to avoid undesirable effects on the rest of the surfactant matrix upon storage/or during the wash. The resulting particle is a highly dense granule which can be incorporated into granular detergents.

While this second route uses lower temperatures and less drastic shear conditions than crutching and spray drying, it has many limitations. On one side the need to carry out a chemical reaction (neutralization) during or right before the granulation step limits considerably the range of processing conditions that can be used (temperature, chemicals, 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 those anionic surfactants which are not chemically stable in the acid form or physically unstable, this process requires the close coupling of the sulphation/sulphonation unit with the neutralization/granulation step. This results in considerable limitations in the logistics and/or the design of the facilities for these processes as well as an important increase in the complexity and difficulty of the control systems for the overall process.

The present invention brings solutions to the problems mentioned above and provides with a more flexible and versatile route to the processing of granular detergents. The present invention is based on an agglomeration/granulation step that is completely uncoupled from the sulphation/sulphonation process. The basis of the invention is the introduction of the anionic surfactant in an aqueous, highly concentrated solution of its salt, most preferably of its sodium salt. These high active (low moisture) surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable. This guarantees the ability to transport and transfer the chemical from the manufacturing location to the granulation site and to be able to have adequate storage facilities prior to the formation of a particle. For those cases where both the sulphation/sulphonation is already immediately preceding the granulation step, it provides the possibility to install intermediate buffer tanks that simplifies the control of the whole unit. In the case of some anionic surfactants or mixtures of them where highly viscous liquid crystal phases occur, this technology requires that either lower viscous phases can be formed (e.g. neat phases) or that some viscosity modifiers are used (e.g. hydrotropes).

An important object of the present invention is to make a dense, concentrated detergent granular product by an agglomeration process as opposed to a spray-drying process. It is another object of the invention to provide for a granular detergent product having a good solubility and good dispersion properties, and improved dispensing from a washing machine.

Other objects of the present invention will be apparent in view of the following.

The present invention relates to an economical process for making a dense, concentrated detergent granular product, and particularly, compositions comprising very high active condensed detergent granules.

FIG. 1 shows a graph of viscosity versus shear rate for

a) a nil-surfactant slurry, comprising a relatively small amount of zeolite.

b) a similar, typical detergent slurry containing surfactant and a relatively high proportion of zeolite.

c) a nil-surfactant slurry comprising no zeolite at all.

FIG. 2 shows the solubility of a spray-dried nil-surfactant powder having a relatively low level of zeolite, compared to the solubility of the powder produced from a surfactant-containing slurry.

The present invention comprises a process for making a free flowing granular detergent comprising: mixing an effective amount of an aqueous surfactant paste having a detergency activity of at least 40% and an effective amount of a dry detergency powder, said surfactant paste active and builder or powder having a ratio of 0.05:1 to 19:1 to form a mix; rapidly forming a uniform mixture from said mix at a temperature of from about 0.degree. C. to about 80.degree. C.; granulating said mixture into discrete detergent granules using a high speed mixing at a tip speed of about 5-50 m/sec; and wherein said surfactant paste is comprised of at least one anionic surfactant, and any other surfactants, if present, are selected from the group of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants and mixtures thereof; and wherein said mixing and granulating are conducted simultaneously, or immediately sequentially.

The present invention is based on an agglomeration/granulation step that is completely uncoupled from the sulphation/sulphonation process. In one embodiment of the present invention, the introduction of the anionic surfactant in an aqueous, highly concentrated solution of its salt, preferably its sodium salt. These high active (and, preferably, low moisture) surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable. In other embodiments of the present invention, anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur, requires that either lower viscous phases be formed or that some viscosity modifiers are used.

In a further embodiment of the present invention, a process for making a free flowing detergent composition is provided, wherein the granulated surfactants herein are admixed with the remainder of the detergent ingredients, which are typically spray-dried into a blown powder from a slurry. Preferably said slurry comprises between 15% and 55% by weight of a builder, the spray-dried slurry being mixed with the agglomerated surfactant. The viscosity of the nil-surfactant slurry having low amounts of builder (detergency powder), preferably zeolite, has been found to be in the same range as the viscosity of aqueous slurries comprising surfactant, at the same moisture content and in the relevant shear-rate range. Therefore, spray-drying the nil-surfactant slurry using pressure nozzles under standard conditions is possible. The advantage of lower amounts of builder powder in the nil-surfactant slurry, is that viscosity-increasing components such as polymers or minors, can be included in the nil-surfactant slurry. Using relatively low amounts of builder powder in the nil-surfactant slurry, the main part of the total amount of builder powder being used for agglomeration of the active paste, provides space for the use of other admixed builders such as layered silicate or citrate. The spray-dried powder formed from the nil-surfactant slurry containing relatively little amounts of builder, has good solubility compared to detergent compositions formed by spray-drying a slurry containing surfactant. By mixing the spray-dried nil-surfactant powder with the granulated active paste, and other dry ingredients such as bleach, bleach activators, anti foaming agents, enzymes and stabilizers, a finished product is obtained having good dispensing and dispersion properties in the wash solution. Spray drying the aqueous nil-surfactant slurry comprising a part of the total amount of builder used, results in a powder having improved absorption properties compared to the builder in its raw material state. Hereby larger amounts of a non-ionic surfactant can be sprayed onto the spray-dried nil-surfactant slurry.

The Pastes

One or various aqueous pastes of the salts of anionic surfactants is preferred 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, (that is, with the lowest possible moisture content possible that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable. While granulation using various pure or mixed surfactants is known, for the present invention to be of practical use in industry and to result in particles of adequate physical properties to be incorporated into granular detergents, an anionic surfactant must be part of the paste in a concentration of above 10%, preferably from 10-95%, more preferably from 20-95%, and most preferably from 40%-95%.

It is preferred that the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle. Preferably the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5 and 20% water. A highly attractive mode of operation for lowering the moisture of the paste prior to entering the agglomerator without problems with very high viscosities is the installation, in line, of an atmospheric or a vacuum flash drier whose outlet is connected to the agglomerator.

It is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying. Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.

Two important parameters of the surfactant pastes which can affect the mixing and granulation step are the paste temperature and viscosity. Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps. Preferably, the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps. The viscosity of the paste of this invention is measured at a temperature of 70.degree. C.

The paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40.degree.-60.degree. C.) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75.degree.-85.degree. C.). High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates. The use of in-line moisture reduction steps (e.g. flask drying), however, require the use of higher temperatures (above 100.degree. C.). In the present invention, the activity of the agglomerates is maintained high due to the elimination of moisture.

The introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size. The use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates. By combining both effects, and introducing the paste through holes (extrusion) small enough to allow the desired flow rate but that keep the pumping pressure to a maximum feasible in the system, highly advantageous results are achieved.

High Active Surfactant Paste

The activity of the aqueous surfactant paste is at least 30% and can go up to about 95%; preferred activities are: 50-80% and 65-75%. The balance of the paste is primarily water but can include a processing aid such as a nonionic surfactant. At the higher active concentrations, little or no builder is required for cold granulation of the paste. The resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations. The aqueous surfactant paste contains an organic 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" surfactant. Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975. Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980. However, cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions. The following are representative examples of surfactants useful in the present compositions.

Water-soluble salts of the higher fatty acids, i.e., "soaps" , are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C.sub.8 -C.sub.18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates 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. Nos. 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C.sub.11 -C.sub.13 LAS.

Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety. Although the acid salts are typically discussed and used, the acid neutralization cam be performed as part of the fine dispersion mixing step.

The preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting 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 paste discussed throughout this document. The sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.

Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends. A particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 1:1, more preferably about 0.05:1. Nonionics can be used up to an equal amount of the primary organic surfactant. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 4 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 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 moiety 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 one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.

Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.

Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein 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 wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from about 3 to 8 moles of ethylene oxide, and mixtures thereof.

Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R.sub.4 R.sub.5 R.sub.6 R.sub.7 N.sup.+ X.sup.-, wherein R.sub.4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R.sub.5, R.sub.6 and R.sub.7 are each C.sub.1 to C.sub.7 alkyl preferably methyl; X.sup.- is an anion, e.g. chloride. Examples of such trimethyl ammonium compounds include C.sub.12-14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.

Specific preferred surfactants for use herein include: sodium linear C.sub.11 -C.sub.13 alkylbenzene sulfonate; .alpha.-olefin sulphonates; triethanolammonium C.sub.11 -C.sub.13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g. C.sub.45, etc.); sodium alkyl sulfates; MES; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 4 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide; the condensation of a fatty alcohol containing from about 14 to about 15 carbon atoms with about 7 moles of ethylene oxide; the condensation product of a C.sub.12 -C.sub.13 fatty alcohol with about 3 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio) hexanoate; dodecyldimethylamine oxide; coconutalkyldimethylamine oxide; and the water-soluble sodium and potassium salts of coconut and tallow fatty acids.

(As used herein, the term "surfactant" means non-nonionic surfactants, unless otherwise specified. The ratio of the surfactant active (excluding the nonionic(s)) to dry detergent builder or powder ranges from 0.005:1 to 19:1, preferably from 0.05:1 to 10:1, and more preferably from 0.1:1 to 5:1. Even more preferred said surfactant active to builder ratios are 0.15:1 to 1:1; and 0.2:1 to 0.5:1).

Powder stream

Although the preferred embodiment of the process of the present invention involves introduction of the anionic surfactant in via pastes as described above, it is possible to have a certain amount via the powder stream, for example in the form of blown powder. In these embodiments, it is necessary that the stickiness and moisture of the powder stream be kept at low levels, thus preventing increased "loading" of the anionic surfactant and, thus, the production of agglomerates with too high of a concentration of surfactant. The liquid stream of a preferred agglomeration process can also be used to introduce other surfactants and/or polymers. This can be done by premixing the surfactant into one liquid stream or, alternatively by introducing various streams in the agglomerator. These two process embodiments may produce differences in the properties of the finished particles (dispensing, gelling, rate of dissolution, etc.), particularly, if mixed surfactants are allowed to form prior to particle formation. These differences can then be exploited to the advantage of the intended application for each preferred process.

It has also been observed that by using the presently described technology, it has been possible to incorporate higher levels of certain chemicals (e.g. nonionic, citric acid) in the final formula than via any other known processing route without detrimental effects to some key properties of the matrix (caking, compression, etc.).

The Fine Dispersion Mixing and Granulation

The term "fine dispersion mixing and/or granulation," as used herein, means mixing and/or granulation of the mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 50 m/sec., unless otherwise specified. The total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes. The more preferred mixing and granulation tip speeds are about 10-45 m/sec. and about 15-40 m/sec.

Any apparatus, plants or units suitable for the processing of surfactants can be used for carrying out the process according to the invention. Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc. For mixing/agglomeration any of a number of mixers/agglomerators can be used. In one preferred embodiment, the process of the invention is continuously carried out. Especially preferred are mixers of the Fukae.RTM. FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another and at separately variable speeds. The vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.

Other similar mixers found to be suitable for use in the process of the invention include Diosna.RTM. V series ex Dierks & Sohne, Germany; and the Pharma Matrix.RTM. ex T K Fielder Ltd., England. Other mixers believed to be suitable for use in the process of the invention are the Fuji.RTM. VG-C series ex Fuji Sangyo Co., Japan; and the Roto.RTM. ex Zanchetta & Co srl, Italy.

Other preferred suitable equipment can include Eirich.RTM., series RV, manufactured by Gustau Eirich Hardheim, Germany; Lodige.RTM., series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lodige Machinenbau GmbH, Paderborn Germany; Drais.RTM. T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth.RTM. RT 25 series, manufactured by Winkworth Machinery Ltd., Bershire, England.

The Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used. The "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred. The invention can be practiced as a batch or a continuous process.

Operating Temperatures

Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle. Preferably the temperature during the agglomeration is less than 80.degree. C., more preferably between 0.degree. and 70.degree. C., even more preferably between 10 and 60.degree. C. and most preferably between 20 and 50.degree. C. Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO.sub.2, and the like; with a preferred method being solid CO.sub.2, and the most preferred method being nitrogen cooling.

A highly attractive opinion in a preferred embodiment of the present invention to further increase the concentration of surfactant in the final particle, is accomplished by the addition to a liquid stream containing the anionic surfactant and/or other surfactant, of other elements that result in increases in viscosity and/or melting point and/or decrease the stickiness of the paste. In a preferred embodiment of the process of the present invention the addition of these elements can be done in line as the paste is pumped into the agglomerator. Example of these elements can be various powders, described in more detail later herein.

Final Agglomerate Composition

The present invention produces granules of high density for use in detergent compositions. A preferred composition of the final agglomerate for incorporation into granular detergents has a high surfactant concentration. By increasing the concentration of surfactant, the particles/agglomerates made by the present invention are more suitable for a variety of different formulations. These high surfactants containing particle agglomerates require fewer finishing techniques to reach the final agglomerates, thus freeing up large amounts of processing aids (inorganic powders, etc.) that can be used in other processing steps of the overall detergent manufacturing process (spray drying, dusting off, etc).

The granules made according to the present invention are large, low dust and free flowing, and preferably have a bulk density of from about 0.5 to about 1.0 g/cc, more preferably from about 0.6 to about 0.8 g/cc. The weight average particle size of the particles of this invention are from about 200 to about 1000 microns. The preferred granules so formed have a particle size range of from 200 to 2000 microns. The more preferred granulation temperatures range from about 10.degree. C. to about 60.degree. C., and most preferably from about 20.degree. C. to about 50.degree. C.

Drying The desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers. If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.

For detergent applications, the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk. The exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 2-4%.

Detergency Builders and Powders

Any compatible detergency builder or combination of builders or powder can be used in the process and compositions of the present invention.

The detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula

wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formul a

wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO.sub.3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.

The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO.sub.3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g. The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca.sup.++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.

The amorphous aluminosilicate ion exchange materials usually have a Mg.sup.++ exchange of at least about 50 mg eq. CaCO.sub.3 /g (12 mg Mg.sup.++ /g) and a Mg.sup.++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula

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 can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature. The builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.

Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. The alkali metal, and especially sodium, salts of the above are preferred. Sodium sulfate is typically used in detergent 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 as long as it is chemically compatible with the rest of the agglomerate composition.

Other useful water-soluble salts include the compounds commonly known as detergent builder materials. Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhyroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of 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. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.

Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO.sub.2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. The compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr. 1, 1980, and is preferably free of the latter.

As mentioned above powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch, can be used in preferred embodiments of the present invention.

Polymers

Also useful are various organic polymers, some of which also may function as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.

Polymeric polycarboxyate builders are set forth in U.S. Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Optionals

Other ingredients commonly used in detergent compositions can be included in the compositions of the present invention. These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.

Optically brighteners may be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by way of the spray-dried slurry, or via both of these routes.

Particulate suds suppressors may also be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by dry adding. Preferably the suds suppressing activity of these particles is based on fatty acids or silicones.

The terms "LAS" and "AS" as used herein mean, respectively, "sodium lauryl benzene sulfonate" and "alkyl sulfate." "MES" means sodium methyl ester sulphonate. The terms like "C.sub.45 " mean C.sub.14 and C.sub.15 alkyl, unless otherwise specified. TAS means Tallow alkyl sulphate. Dobanol 45E7 is a C.sub.14 /C.sub.15 alcohol ethoxylate with 7 units of ethylene oxide and is manufactured by Shell Co.

The invention will be better understood in view of the following nonlimiting examples. The percentages are on an after drying weight basis, unless otherwise specified. The tables are followed with additional processing disclosure.

An aqueous surfactant LAS paste having a detergent activity of 78% and a water content of 21% is pumped via a positive displacement pump into a Lodige CB 55 at a rate of 20 T/hr. The viscosity of the paste is 25,000 cps at a temperture of 70.degree. C. At the same time, a powder stream containing a mixture of 1:1 ratio by weight of Zeolite A to citrate dihydrate finely divided, is also fed to the Lodige CB 55 mixer at a rate of 4 T/hr. Also flowing into the same mixer are two streams containing the recycle of the classification of the agglomerates, one containing wet coarse particles and the other dry fine particles. The agglomerates leaving the Lodige CB 55 mixer are dried in a controlled temperature fluid bed with air exit temperatures of 50.degree.-55.degree. C. After drying for an average residence time of approximately 15 minutes, the agglomerates are cooled in a second fluid bed to powder exit temperatures below 45.degree. C. The cool dry product leaving the cooler is classified through mesh sieves and the desired particle sizes stored in a silo. The agglomerates made during this Example have a detergent activity of 25% and a density of 780 g/L.

Example 2 is similar to Example 1. In this case, an aqueous surfactant C.sub.45 AS paste with a detergent activity of 70% and a water content of 25% is used at a rate of 2.0 T/hr. The viscosity of the paste is 35,000 cps at a temperature of 70.degree. C. The powder stream consists of a mixture of a 2:1 ratio by weight of Zeolite A and sodium carbonate finely divided and is fed at a rate of 2.0 T/hr. The agglomerates made during this Example have a detergent activity of 39% and a density of 675 g/L.

This Example describes the process in batch mode in a pilot plant scale high shear mixer, an Eirich RV02. The mixer is filled first with a mixture of the powders to be used, in this particular case a 2:1 ratio of Zeolite A and finely divided sodium carbonate (3 kg). An aqueous surfactant MES paste with a detergent activity of 65% and a water content of 33% is then added on top of the powder mixture while the mixer is being operated at 1600 rpm. Enough paste is added until granulation is achieved (in this case, 1.6 kg of the MES paste). The agglomerates are discharged onto a fluid bed drier and then classified through adequate sieves. The resulting agglomerates are made with a detergent activity of 22% and a density of 750 g/L.

This Example is similar to Example 3. The powder mixture is again a 2:1 ratio of Zeolite A to finely divided carbonate. The surfactant is an aqueous paste of C.sub.45 AS with a detergent activity of 78% and a water content of 13%. In this Example, both the powders (1.05 kg) and the paste (3 kg) are added to the mixer (the Eirich RV02) before starting the granulation. A certain amount (2 kg) of dry ice is also added to the mixer to lower the temperature below -15.degree. C. The mixer is then started at a speed of 1600 rpm. At first, at the low temperature achieved, the mixture is in the form of a fine powder. The mixer is operated until the temperature raises to the point (12.degree. C.) where granulation occurs. The process is then stopped and the agglomerates are dried in a fluid bed and classified through mesh sieves. The agglomerates made have a detergent activity of 60% and a density of 625 g/L. They show excellent physical properties.

An aqueous surfactant C.sub.45 AS paste with a detergent activity of 71% and a water content of 28% is pumped via a positive displacement pump into a Lodige CB 30. At the same time, a powder stream containing a mixture of 2:1 ratio by weight of Zeolite A finely divided sodium carbonate, is also fed to the lodige CB 30. The rate of the powder stream is maintained constant at 400 Kg/hr. The rate of the paste stream is varied until agglomerates of an adequate particle size distribution (a maximum yield between 200 .mu.m and 1800 .mu.m) are obtained. Operation at ambient conditions required a rate of 245 kg/hr. of the surfactant paste being pumped, resulting in agglomerates (after drying) of a detergent activity of 27%. A liquid nitrogen stream is then flown into the Lodige CB 30 at the point of entrance of the powder stream, at a rate of 4.5 kg/hr. In order to make agglomerates of an adequate particle size distribution, the paste flow rate needs to be increased to 346 kg/hr, resulting in agglomerates (after drying) of a detergent activity of 32.0%.

In this Example, a Braun Multipractic food processor is used to manufacture agglomerates containing a full detergent formula for use in laundry cleaning. First, all the powder components of the formula are weighed and added to the food processor. This mixture contains:

All the powders are in a finely divided form prior to addition to the mixer. The mixer is then operated at a low speed for a period of about 1 minute to ensure good mixing of the powders. A mixture of surfactant pastes is prepared in a separate food processor. This mixture contains:

The pastes are well mixed by operating the food processor at high speed for a period of about 1 minute. After this, the powder premix is added on top of the paste premix and the food processor is operated at medium speed until granulation occurs (about 1 minute). The agglomerates made are dried in a fluid bed, and classified using mesh sieves. These agglomerates have excellent physical properties and very good solubility, showing excellent performance in laundry cleaning.

This example demonstrates that for a granular detergent composition of which one part consists of an agglomerated active paste, the spray-dried nil-surfactant components have improved solubility and dispensing properties over typical detergent products which are commercially available granular detergents that are obtained by spray-drying an active slurry comprising an anionic surfactant. A nil-surfactant slurry of the composition as given under A and C herebelow and a slurry comprising surfactant of the compositions as given under B herebelow were spray-dried using a pressure nozzle under standard conditions, the inlet temperature of the drying air being between 250.degree. C. and 320.degree. C., the outlet temperature of the drying air being between 80.degree. C. and 120.degree. C. and the pressure of the nozzle being between 50 and 100 bar. The ingredients of the slurries, by weight % are:

FIG. 1 shows that in the range of shear rates of 1000 to 10.000 s.sup.-1, the nil-surfactant slurry of composition A of the example has a viscosity that is comparable to the viscosity of the slurry of composition B, that contains surfactant and a larger amount of builder. Spray-drying of compositions having relatively low levels of zeolite using known pressure nozzles therefor presents no problems.

From FIG. 1, it is seen that for a slurry of composition C, containing no zeolite and larger amounts of polymer, the viscosity is higher, so that spray-drying is unpractical. A minimum amount of builder is therefor necessary in the nil-surfactant slurry for good spray-dryability.

FIG. 2 shows the solubility of the nil-surfactant spray-dried powder produced from the slurry of composition A, compared to the spray-dried active powder produced from the slurry of composition B. The spray-dried nil-surfactant powder has a slightly slower rate of dissolution and as a result gel formation is reduced and less residues remain after dispensing. In a comparative test using a Zanussi.RTM. laundry machine, at a water feed rate of 2 lmin.sup.-1 at 20.degree. C., conventional detergents with spray-dried surfactants showed 30-90% residue, whereas the granular detergent comprising the nil-surfactant spray-dried powder and the agglomerated surfactant paste showed less than 5% residues.

The particle size distribution of the nil-surfactant spray-dried powder is good for use in a detergent powder, the mass remaining on standard sieves being:

For spray-dried products it is desirable to have a low frangibility as this avoids break-up of the finished detergent powder during storage and handling. The frangibility of the nil-surfactant spray-dried powder was tested by placing the nil-surfactant spray-dried powder remaining on standard sieves no 22 and 36 in a ball mill for 5 minutes and determining the percentage falling through standard sieve 36 after the ball-mill treatment. The percentage passing through the sieve 36 after ball-mill treatment was 66.15% for the nil-active spray-dried powder, which is comparable with the frangibility of the conventional powder formed of the slurry of composition B of this example.

Granular detergent powders formed by agglomerating a high active paste using the larger part of the total amount of builder contained in the detergent powder, and mixing with nil-surfactant spray-dried powder and other ingredients, have in many aspects better performance than when some or all of the surfactant is spray-dried.

This example demonstrates that a high-density granular detergent is obtained by spray-drying a nil-surfactant slurry, subsequently spraying a non-ionic surfactant onto the nil-surfactant spray-dried slurry and mixing the resultant powder with the granulated surfactant and dry additives such as bleach and enzyme.

A nil-surfactant slurry was spray-dried using pressure nozzles at 50-100 bar pressure, the drying air having a inlet temperature of 250.degree. C.-320.degree. C. and an outlet temperature of 80.degree. C.-120.degree. C., the composition of the slurry being by weight %:

The spray-dried powder had a bulk density of 610 g/l. As a nonionic surfactant an alkyl alcohol ethylene oxide condensate (AE.sub.3) is sprayed onto the spray-dried powder. Subsequently the resulting powder is mixed with the agglomerated aninonic surfactant which is produced according to one of the examples 1 to 7, and further ingredients such as builder, bleach and enzyme are added.

The finished detergent composition, having the following components by weight %, has a density of 800 g/l.

This example demonstrates that spray-drying of the nil-surfactant slurry comprising builder, results in a powder having a relatively high absorption capacity for non-ionic surfactants compared to the absorption capacity of non-spray-dried builder powder. Therefore, more non-ionic surfactant can be incorporated in less builder powder, so that more builder powder is available for the agglomeration of the surfactant paste. This is contrary to the expectation that more efficient use of builder powders could be made by spray-drying slurries containing very low amounts, or no builder (detergency) powder at all and by spraying nonionic surfactant onto the resultant powder with simultaneous dry addition of builder (detergency) powders.

A powder having the following components by weight % was made by spray-drying:

The powders of the composition given under D and E were sprayed with an alcohol containing 25 carbon atoms ethoxylated with 3 moles of ethylene oxide per mole of alcohol (C.sub.25 AE.sub.3) as a nonionic surfactant.

Thereafter further zeolite-A was added where necessary to produce a handable powder. The resulting powder of the compositions given under D and E contained the following ingredients by mass:

clearly the composition given at E requires less Zeolite-A, so that the remaining Zeolite-A can be used for agglomeration of the surfactant paste or for dry-mixing.