CA2268060C - Process for making a detergent composition by non-tower process - Google Patents

Abstract

A non-tower process for continuously preparing granular detergent compositio n having a density of at least about 600 g/l is provided. The process comprises the steps of: (a) dispersing a surfactant, and coating the surfactant with fine powder having a diameter from 0.1 to 500 microns, while wetting the surfactant coated with the fine powder with finely atomized liquid, in a mixer, and (b) thoroughly mixing the agglomerates in a mixer. Step (b) can also be followed by further step (c), i.e., granulating the agglomerates from step (b) in one or more fluidizing apparatus.

Description

WO 98/14553 PCT/fJS97/09791 PROCESS FOR MAKING A DETERGENT COMPOSITION BY NON-TOWER
PROCESS
FIELD OF THE INVENTION
The present invention generally relates to a non-tower process for producing a particulate detergent composition. More particularly, the invention is directed to a continuous process during which detergent agglomerates are produced by feeding a surfactant and coating materials into a series of mixers.
The process produces a free flowing, detergent composition whose density can be adjusted for wide range of consumer needs, and which can be commercially sold.
BACKGROUND OF THE INVENTION
-. Recently, there has been considerable interest within the detergent industry for laundry detergents which are "compact" and therefore, have low dosage volumes. To facilitate production of these so-called low dosage detergents, many attempts have been made to produce high bulk density detergents, for example with a density of 600 g/1 or higher. The low dosage detergents are currently in high demand as they conserve resources and can be sold in small packages which are more convenient for consumers. However, the extent to which modern detergent products need to be "compact" in nature remains unsettled. In fact, many consumers, especially in developing countries, continue to prefer a higher dosage levels in their respective laundering operations.
Generally, there are two primary types of processes by which detergent granules or powders can be prepared. The first type of process involves spray drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules (e.g., tower process for low density detergent compositions). fn the second type of process, the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (e.g., agglomeration process for high density detergent compositions). in the above finro processes, the important factors which govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the various starting materials, the shape of the various starting materials, and their respective chemical composition.
There have been many attempts in the art for providing processes which increase the density of detergent granules or powders. Particular attention has been given to densification of spray-dried granules by post tower treatment.
For example, one attempt involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer~. This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder. This process, however, is essentially a batch process and is therefore less suitable for the large scale production of detergent powders. More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules. Typically, such processes require a first apparatus which pulverizes or grinds the granules and a second apparatus which increases the density of the pulverized granules by agglomeration. While these processes achieve the desired increase in density by treating or densifying "post tower" or spray dried granules, they are limited in their ability to go higher in surfactant active level without subsequent coating step. In addition, treating or densifying by "post tower" is not favourable in terms of economics (high capital cost) and complexity of operation. Moreover, all of the aforementioned processes are directed primarily for densifying or otherwise processing spray dried granules. Currently, the relative amounts and types of materials subjected to spray drying processes in the production of detergent granules has been limited. For example, it has been difficult to attain high levels of surfactant in the resulting detergent composition, a feature which facilitates production of detergents in a more efficient manner. Thus, it would be desirable to have a process by which detergent compositions can be produced without having the limitations imposed by conventional spray drying techniques.
To that end, the art is also replete with disclosures of processes which entail agglomerating detergent compositions. For example, attempts have been made to agglomerate detergent builders by mixing zeolite andlor layered silicates in a mixer to form free flowing agglomerates. While such attempts suggest that their process can be used to produce detergent agglomerates, they do not provide a mechanism by which starting detergent materials in the form of pastes, liquids and dry materials can be effectively agglomerated into crisp, free flowing detergent agglomerates.
Accordingly, there remains a need in the art to have an agglomeration {non-tower) process for continuously producing a detergent composition having high density delivered directly from starting detergent ingredients, and preferably the density can be achieved by adjusting the process condition. Also, there remains a need for such a process which is more efficient, flexible and economical to facilitate large-scale production of detergents (1) for flexibility in the ultimate density of the final composition, and (2) for flexibility in terms of incorporating several different kinds of detergent ingredients, especially detergent ingredients in the form of liquid, into the process.
The following references are directed to densifying spray-dried granules:
Appel et al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al, U.S. Patent No.
5,160,657 (Lever); Johnson et al, British patent No. 1,517,713 (Unilever); and Curtis, European PatentApplication451,894.
The following references are directed to producing detergents by agglomeration: Beujean et al, Laid-open No.W093/23,523 (Henkel), Lutz et al, U.S. Patent No. 4,992,079 (FMC Corporation); Porasik et al, U.S. Patent No.

4,427,417 (Korex); Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble);
Capeci et al, U.S. Patent No. 5,366,652 (Procter & Gamble); Hollingsworth et al, European Patent Application 351,937 (Unilever); Swatting et ai, U.S. Patent No.

5,205,958; Dhalewadikar et al, Laid Open No.W096/04359 (Unilever).
For example, the Laid-open No.W093/23,523 {Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt% of the granules having a diameter over 2 mm. The U.S. Patent No. 4,427,417 (Korex) describes continuous process for ' agglomeration which reduces caking and oversized agglomerates.
None of the existing art provides all of the advantages and benefits of the ' present invention.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in the art by providing a process which produces a high density granular detergent composition.
The present invention also meets the aforementioned needs in the art by providing a process which produces a granular detergent composition for flexibility in the ultimate density of the final composition from agglomeration (e.g., non-tower) process. The process does not use the conventional spray drying towers currently which is limited in producing high surfactant loading compositions. In addition, the process of the present invention is more efficient, economical and flexible with regard to the variety of detergent compositions which can be produced in the process. Moreover, the process is more amenable to environmental concerns in that it does not use spray drying towers which typically emit particulates and volatile organic compounds into the atmosphere.
As used herein, the term "agglomerates" refers to particles formed by agglomerating raw materials with binder such as surfactants and or inorganic solutions/organic solvents and polymer solutions. As used herein, the term l5 "granulating" refers to fluidizing agglomerates thoroughly for producing free flowing, round shape granulated-agglomerates. As used herein, the term "mean residence time" refers to following definition:
mean residence time (hr) = mass (kg) / flow throughput (kg/hr) All percentages used herein are expressed as "percent-by-weight" unless :?0 indicated otherwise. All ratios are weight ratios unless indicated otherwise. As used herein, "comprising" means that other steps and other ingredients which do not affect the result can be added. This term encompasses the terms "consisting of and "consisting essentially of".
In accordance with one aspect of the invention, there is provided a non-tower >.5 process for preparing a granular detergent composition having a density of at least about 600 g/1, comprising the steps of:
(a) dispersing a surfactant, and coating the surfactant with fine powder having a diameter from 0.1 to 500 microns, while wetting the surfactant coated with the fine powder with finely atomized liquid, in a :~0 first mixer wherein conditions of the mixer include (i) from about 0.2 to about 5 seconds of mean residence time, (ii) from about 10 to about 30 m/s of tip speed, and (iii) from about 0.15 to about 5 kj/kg of energy condition, wherein first agglomerates are formed;

(b) thoroughly mixing the first agglomerates in a second mixer wherein conditions of the mixer include (i) from about 0.5 to about 15 minutes of mean residence time and (ii) from about 0.15 to about 7 kj/kg of energy condition, wherein second agglomerates are formed; and (c) granulating the second agglomerates with a liquid detergent ingredients in one or more fluidizing apparatus selected from the group consisting of fluidized bed coolers, fluidized bed dryers, or both, wherein conditions of each of the fluidizing apparatus include (i) from about 1 to about 10 minutes of mean residence time, (ii) from about 100 to about 300 mm of depth of unfluidized bed, (iii) not more than about 50 micron of droplet spray size, (iv) from about 175 to about 250 mm of spray height, (v) from about 0.2 to about 1.4 m/s of fluidizing velocity and (vi) from about 12 to about 100 'C of bed temperature and (d) adding a coating agent selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof in one or more of the following locations:
1 ) directly after the fluidized bed cooler or fluidized bed dryer;
2) between the fluidized bed dryer and the fluidized bed cooler; or 3) directly to the fluidized bed dryer, whereby over-agglomeration is minimized.
Also provided are the granular detergent compositions having a high density of at least about 600g/1, produced by any one of the process embodiments described herein.
Accordingly, it is an object of the invention to provide a process for continuously producing a detergent composition which has flexibility with respect to density of the final products by controlling energy input, residence time condition, and tip speed condition in the mixers. It is also an object of the invention to provide a process which is more efficient, flexible and economical to facilitate large-scale production. These and other objects features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is directed to a process which produces free flowing, granutar detergent agglomerates having a density of at least about g//. The process produces granular detergent agglomerates from an aqueous and/or non-aqueous surfactant which is then coated with fine powder having a diameter from 0.1 to 500 microns, in order to obtain low density granules.
Process First Step [Step(a)]
In the first step of the process, one or more of aqueous and/or non aqueous surfactants) which is/are in the form of powder, paste and/or liquid, and fine powder having a diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns are fed into a first mixer, so as to make agglomerates.
During the process, surface of the surfactant which is coated by the fine powder is wet by finely atomized liquid so as to add more fine powder on the surface of the agglomerates. (The definition of the surfactants and the fine powder, finely atomized liquid are described in detail hereinafter.) Optionally, an internal recycle stream of powder having a diameter of about 0.1 to about 300 microns generated in the fluidizing apparatus (e.g., fluid bed dryer and/or fluid bed cooler) can be fed into the mixer in addition to the fine powder. The amount of such internal recycle stream of powder can be 0 to about 60 wt% of final product.
In another embodiment of the invention, the surfactant for the first step can be initially fed into a mixer or pre-mixer (e.g. a conventional screw extruder or other similar mixer) prior to the above, after which the mixed detergent materials are fed into the first step mixer as described herein for agglomeration.
Generally speaking, preferably, the mean residence time of the first mixer is in range from about 0.2 to about 5 seconds and tip speed of the first mixer of the first mixer is in range from about 10 m/s to about 30 m/s, the energy per unit mass of the first mixer (energy condition) of the first mixer is in range from about 0.15 kj/kg to about 5 kj/kg, more preferably, the mean residence time of the first mixer is in range from about 0.2 to about 5 seconds and tip speed of the first mixer is in range from about 10 m/s to about 30 mls, the energy per unit mass of _7_ the first mixer (energy condition) is in range from about 0.15 kj/kg to about kj/kg; the most preferably, the mean residence time of the first mixer is in range from about 0.2 to about 5 seconds, tip speed of the first mixer is in range from about 15 m/s to about 26 m/s, the energy per unit mass of the first mixer (energy condition) is from about 0.2 kj/kg to about 3 kj/kg.
The examples of the mixer can be any types of mixer known to the skilled in ,the art, as long as the mixer can maintaTM the above mentioned condition for the first step. An Example can be Flexomic Model manufactured by the Schugi Company (Netherlands). As the result of the first step, first agglomerates are then obtained.
Second Step jSte~ (b)1 The resultant from the first step (i.e., the first agglomerates) is fed into a second mixer. Namely, the first agglomerates are mixed and sheared thoroughly for rounding and growth of the agglomerates in the second mixer . Optionally, about 0-10°r6 , more preferably about 2-5% of powder detergent ingredients of the kind used in the first step andlor other detergent ingredients can be added to the second step. Preferably, choppers which are attachable for the third mixer __ can be used to break up undesirable oversized agglomerates. Therefore, the process including the second with choppers is useful in order to obtain reduced amount of oversized agglomerates as final products, and such process is one preferred embodiment of the present invention.
Generally speaking, preferably, the mean residence time of the second mixer is in range from about 0.5 to about 15 minutes and the energy per unit mass of the second mixer (energy condition) is in range from about 0.15 to about 7 kj/kg, more preferably, the mean residence time of the second mixer is from about 3 to about 6 minutes and the energy per unit mass of the second mixer (energy condition) is in range from about 0.15 to about 4kjlkg.
The examples of the second can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step. An Example can be LddigeM KM Mixer manufactured by the LBdige Company (Germany). As the result of the second step, the second agglomerates with round shape are then obtained.
Third Step t Step lc j If the second agglomerates are less than 600 g/1, or if further _g_ agglomeration is preferred to meet the optimum condition as the final product from the process of the present invention, the second agglomerates are fed into a fluidized apparatus, such as fluidized bed, in order to enhance granulation for producing free flowing high density granules. The third step can proceed in one S or more than one fluidized apparatus (e.g., combining different kinds of fluidized apparatus such as fluid bed dryer and fluid bed cooler). Optionally, about 0 to about 10% , more preferably about 2-5% of powder detergent materials of the kind used in the first step and/or other detergent ingredients can be added to the second step. Also, optionally, about 0 to about 20%, more preferably about 2 to about 10% of liquid detergent materials of the kind used in the first step, the second step and/or other detergent ingredients can be added to the step, for enhancing granulation and coating on the surface of the granules.
Generally speaking, to achieve the density of at least about 600 g//, preferably more than 650g//, condition of a fluidized apparatus can be;
1 S Mean residence time : from about 1 to about 10 minutes Depth of unfluidized bed : from about 100 to about 300 mm Droplet spray size : not more than about 50 micron Spray height: from about 175 to about 250 mm Fluidizing velocity : from about 0.2 to about 1.4 m/s Bed temperature : from about 12 to about 100 °C, more preferably;
Mean residence time : from about 2 to about 6 minutes Depth of unfluidized bed : from about 100 to about 250 mm Droplet spray size : less than about 50 micron Spray height: from about 175 to about 200 mm Fluidizing velocity : from about 0.3 to about 1.0 m/s Bed temperature : from about 12 to about 80 °C.
If two different kinds of fluidized apparatus would be used, mean residence time of the third step in total can be from about 2 to about 20 minutes, more preferably,~from about 2 to 12 minutes.
A coating agent to improve flowability and/or minimize over agglomeration of the detergent composition can be added in one or more of the following locations of the instant process: (1) the coating agent can be added directly after fluid bed cooler or fluid bed dryer; (2) the coating agent may be added between filuid bed dryer and the fluid bed cooler; and/or (3) the coating agent may be ~_._~ ._._.. ~_. _... . _ ._.~ _ _.
r _g_ added directly to fluid bed dryer. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping for detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
Starting Detergent Materials The total amount of the surfactants in products made by the present invention, which are included in the following detergent materials, finely atomized liquid and adjunct detergent ingredients is generally from about 5% to about 60%, more preferably from about 12% to about 40%, more preferably, from about 15 to about 35%, in percentage ranges. The surfactants which are included in the above can be from any part of the process of the present invention., e.g., from either one of the first step, the second step and/or the third step of the present invention.
Detergent Surfactant (Agueous /Non-aqueous) The amount of the surfactant of the present process can be from about 5% to about 60%, more preferably from about 12% to about 40%, more preferably, from about 15 to about 35%, in total amount of the final product obtained by the process of the present invention.
The surfactant of the present process, which is used as the above mentioned starting detergent materials in the first step, is in the form of powdered, pasted or liquid raw materials.
:?5 The surfactant itself is preferably selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975.
Useful cationic surfactants also include those described in U.S. Patent 4,222,905, :i0 Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.

Of the surfactants, anionics and nonionics are preferred and anionics are most preferred.
Nonlimiting examples of the preferred anionic surfactants useful in the present invention include the conventional C11-C18 alkyl benzene sulfonatea ("LAS"), primary, branched-chain and random C1 p-C20 alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y(CHOSOg M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C10-C1g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates).
Useful anionic surfactants also include water soluble salts of 2-acyioxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the aryl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms;
and beta-alkyloxy alkane sutfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety .
Optionally, other exemplary surfactants useful in the paste of the invention -- include C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10_1g glycerol ethers, the C1p-C18 alkyl poiyglycosides and the corresponding sulfated polyglycosides, and C12-C1g alpha-sutfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxyiates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C10-C1g amine oxides, and the like, can also be included in the overall compositions. The C1 p-C18 N-alkyl poiyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 92/06154 Other sugar derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1p-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C1g glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used, If high sudsing is desired, the branched-chain C1p-C1g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts.
Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono Cg-Clg, WO 98/i4553 PCT/US97/09791 preferably C6-C1 p N-alkyl or alkenyl ammonium surfactants wherein remaining N

positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines;

zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates;
water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R1)2N+R2C00-, wherein R is a C6-C1g hydrocarbyl group, preferably a C10-C16 alkyl group or C10-C16 acylamido alkyl group, each R1 is typically C1-C3 alkyl, preferably methyl and R2 is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C1-CZ alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine;
hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl betaine; 4[C14-16 acylmethylamidodiethylammonio]-1-carboxybutane;

acylamidodimethylbetaine; C1z-16 acylamidopentanediethylbetaine;
and [C12-16 acylmethylamidodimethylbetaine. Preferred betaines are dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R1)2N+R2S03- wherein R is a C6-C1g hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a C12-C13 alkyl group, each R1 is typically C1-C3 alkyl, preferably methyl, and R2 is a C1-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines include C12-C14 dimethylammonio-2-hydroxypropyl sulfonate, C14 amido propyl ammonio-2-hydroxypropyl sultaine, C12-C14 dihydroxyethylammonio propane sulfonate, and C16-18 dimethylammonio hexane sulfonate, with C12-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.

Fine Powder The amount of the fine powder of the present process, which is used in the first step, can be from about 94% to 30%, preferably from 86% to 54%, in total amount of starting material for the first step . The starting fine powder of the present process preferably selected from the group consisting of ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulphates, aluminosilicates, crystalline layered silicates, nitrilotriacetates (NTA), phosphates, precipitated silicates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkane sulfonic acids) and internal recycle stream of powder occurring from the process of the present invention, wherein the average diameter of the powder is from 0.1 to 500 microns, preferably from 1 to 300 microns, more preferably from 5 to 100 microns. In the case of using hydrated STPP as the frne powder of the present iwention, STPP which is hydrated to a level of not less than 50% is preferable.
The aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S.
Patent No. 4,605,509 (Procter & Gamble).
Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders. The term "particle size diameter' as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic detem~ination and scanning electron microscope (SEM). The preferred particle size diameter of the afuminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns.
Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula Naz[(A102)z.(Si02~,~xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na~2[(A102)~2.(Si02)~2]xH20 wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X. Alternatively, naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669.
The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC03 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaC03 hardness/gram.
Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca++/gallon/minutel-gram/gallon to about 6 grains Ca++/gallon/minute/-gram/gallon.
_Finely Atomized Liauid The amount of the finely atomized liquid of the present process can be from about 1 % to about 10% (active basis), preferably from 2% to about 6% (active basis) in total amount of the final product obtained by the process of the present invention. The finely atomized liquid of the present process can be selected from the group consisting of liquid silicate, anionic or cationic surfactants which are in liquid form, aqueous or non-aqueous polymer solutians, water and mixtures thereof.
The aqueous or non-aqueous polymer solution is dipersed with the surfactant in step (a).
Other optional examples for the finely atomized liquid of the present invention can be sodium carboxy methyl cellulose solution, polyethylene glycol (PEG), and solutions of dimethylene triamine pentamethyl phosphonic acid (DETMP').
The preferable examples of the anionic surfactant solutions which can be used as the finely atomized liquid in the present inventions are about 88 -97%
active HLAS, about 30 - 50% active NaLAS, about 28% active AE3S solution, about 40-50% active liquid silicate, and so on.

Cationic surfactants can also be used as finely atomized liquid herein and suitable quaternary ammonium surfactants are selected from mono Cg-C~6, preferably Cg-C~0 N-alkyl or alkenyl ammonium surfactants wherein remaining N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Preferable examples of the aqueous or non-aqueous polymer solutions which can be used as the finely atomized liquid in the present inventions are modified polyamines which comprise a polyamine backbone corresponding to the formula:
H
to [~-~nf-1-[N-~lrr,-[N-t~n-I~
having a modified polyamine formula Vin+~ )WmYnZ or a polyamine backbone corresponding to the formula:
H
fl-~'1-~rrk+t~f~ ~rrrf~ ~rr~~ F~k-f~-k having a modified polyamine formula Vin-k+1)WmYnY~kZ, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein i) V units are terminal units having the formula:
E X_ E-N-F~- or E-N~ F~- or E-N-F~
ii) W units are backbone units having the formula:
Ex- pp or -~=R- or -N-R-E E E
iii) Y units are branching units having the formula:

X_ - i -F~- or -fif"-f~-- or - i -R-- .
and iv) Z units are terminal units having the formula:
X
-N-E or N+
E
wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -(R10)xR1-, -(R10)xR5(OR1)x-, -(CH2CH(OR2)CH20)z(R1 O)yR1 (OCHZCH(OR2)CH2)~, -C(O)(R4)rC(O)-, -CH2CH(OR2)CH2-, and mixtures thereof; wherein R1 is C2-Cg alkylene and mixtures thereof; R2 is hydrogen, -{R10)xB, and mixtures thereof; R3 is C1-C1g alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, Cg-C12 aryl, and mixtures thereof; R4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, Cg-C10 arylene, and mixtures thereof; R~ is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -R1 (0R1 )-, -C(O)(R4)rC(O)-, -CH2CH(OH)CH2-, -CH2CH(OH)CH20(R10)yR10CH2CH(OH)CH2-, and mixtures thereof; R6 is C2-C12 alkylene or Cg-C12 arylene; E units are selected from the group consisting of hydrogen, C1-C22 alkyl, Cg-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)qSOgM, -CH(CH2C02M)C02M, -(CH2)pPOgM, -(R10)xB, -C(O)R3, and mixtures thereof; oxide; B is hydrogen, C1-Cg alkyl, -(CH2)qS03M, -(CH2)pC02M, -(CH2)q(CHS03M)CH2S03M, -(CH2)q-(CHS02M)CH2S03M, -(CH2)pP03M, -POgM, and mixtures thereof; M
is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; m has the value from 4 to about 400; n has the value from 0 to about 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value of 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1. One example of the most preferred polyethyleneimines would be a polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7). It is preferable for the above polymer solution to be pre-complex with anionic surfactant such as NaLAS.
Other preferable examples of the aqueous or non-aqueous polymer solutions which can be used as the finely atomized liquid in the present invention are polymeric polycarboxylate dispersants which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the 1 S polymer.
Homo-polymeric polycarboxylates which have molecular weights above 4000, such as described next are preferred. Particularly suitable homo _. polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from above 4,000 to 10,000, preferably from above 4,000 to 7,000, and most preferably from above 4,000 to 5,000. Water soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
Co-polymeric polycarboxylates such as a Acryliclmaleic-based copolymers may also be used. Such materials include the water-soluble salts of copolymers of acrylic acid and malefic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. It is preferable for the above polymer solution to be pre-complexed with anionic surfactant such as LAS .
~___ ... _..~.

_17_ AdLunct Detergent Ingiredients The starting detergent material in the present process can include additional detergent ingredients and/or, any number of addi5onal ingredients can be incorporated in the detergent composition during subsequent steps of the present process. These adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, antitamish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH
adjusting agents, non-bulkier alkalinity sources, chelating agents, smectite clays, enrymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1978 to Baskerville, Jr. et al.
Other builders can be generally selected from the various water soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sutfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Prefened for use herein are the phosphates, carbonates, C1 p..1 g fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate .mono- and di-succinates, and mixtures thereof (see below).
. In comparison with amorphous sodium silicates, crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity. In addition, the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water. These crystalline layered sodium silicates, however, are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously. Such crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509.
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 orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene _1~ .
diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
Examples of nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. .
Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. _ Such materials include the water soluble salts of homo- and copolymers of aliphatic carboxylic acids such as malefic acid, itaconic acid, mesaconic acid, fumaric acid, aconidc acid, citraconic acid and methylene malonic acid. Some of these materials are useful as the water soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant Other suitable polycarboxylates for use herein are the poiyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Cnrtchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Cnrtchfield et al. These polyaoetal carboxylates can be prepared by bringing together under polymerization condition an ester of glyoxylic acid and a polymerization initiator.
The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred poiycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987.
Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984. Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68.
Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S.
Patent 4,663,071, Bush et al, issued May 5, 1987.
_Optional Process Steps Optionally, the process .can comprise the step of spraying an additional binder in one or more than one of the first, second and/or the third mixers for the present invention. A binder is added for purposes of enhancing agglomeration by providing a "bindings" or "sticking" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants, ;?0 nonionic surfactants, liquid silicates, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof. Other suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No.
5,108,646 (Procter & Gamble Co.).
Other optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product. Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying by way of apparatus discussed previously.

Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients. For example, the finishing step encompasses spraying perfumes, brighteners and enrymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art.
Another optional step in the process involves surfactant paste structuring process, e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder, prior to the process of the present invention. The details of the surfactant paste structuring process are disclosed in CA 2,268,051.
In order to make the present invention more readily understood, reference is made. to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.
EXAMPLES
Examcle 1: -The following is an example for obtaining agglomerates having high density, using Schugi FX-160 Mixer, followed by LSdige KM mixer (KM-600), then Fluid Bed Apparatus for further granulations.
[Step 1] 120 - 160 kg/hr of HLAS (an acid precursor of C11-C~8 alkyl benzene sulfonate; 96% active) is dispersed in a highly turbulent air stream of the Schugi FX-160 mixer along with 220 kglhr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 280 kg/hr of ground soda ash (mean particle size of 15 microns), 80- 120 kglhr of ground sodium sulfate (mean particle size of microns), and the 200 kglhr of internal recycle stream of powder. The surfactant is fed at about 50 to 60 °C, and the powders are fed at room temperature. Then, kg/hr of HLAS (an acid precursor of C11-C1g alkyl benzene sulfonate; 94 -- 97°r6 active) is dispersed as finely atomized liquid in the FX-160 mixer at about 30 50 to 60°C. 20-80 kg/hr of soda ash (mean particle size of about 10 -microns) is added in the Schugi mixer. The condition of the Schugi mixer is as follows:
Mean residence time : 0.2 - 5 seconds Tip speed : 16 - 26 m/s .5 Energy condition : 0.15 - 2 kjlkg Mixer speed : 2000 - 3200 rpm [Step 2] The agglomerates from the Schugi FX-160 mixer are fed to the KM-600 mixer for further agglomeration, rounding and growth of agglomerates.
30 kg/hr ~of Zeolite is also added in the KM mixer. Choppers for the KM mixer can be used to reduce the amount of oversized agglomerates. The condition of the KM mixer is as follows:
Mean residence time : 3- 6 minutes Energy condition : 0.15 - 2 kj/kg Mixer speed : 100 - 150 rpm Jacket temperature: 30 - 40°C
[Step 3] The agglomerates from the KM mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 80 kg/hr of liquid silicate (43% solids, 2.0 R) can be also added in the fluid bed drying apparatus at 35°C. The condition of the fluid bed drying apparatus is as follows:
Mean residence time : 2 - 4 minutes Depth of unfluidized bed : 200 mm Droplet spray size : less than 50 micron Spray height: 175 - 250 mm (above distributor plate) Fluidizing velocity : 0.4 - 0.8 m/s Bed temperature : 40 - 70 °C
The resulting granules from the step 3 have a density of about 700 gll, and can be optionally subjected to the optional process of cooling, sizing andlor grinding.
Example 2:
The following is an example for obtaining agglomerates having high density, using Schugi FX-160 Mixer, followed by Lbdige KM mixer (KM-600).
[Step 1] 120 - 200 kg/hr of HLAS (an acid precursor of C11-C1g alkyl benzene sulfonate; 95 % active) at about 50 °C, is dispersed in a highly turbulent air stream of the Schugi FX-160 mixer along with 220 kg/hr of powdered STPP
(mean particle size of 40 - 75 microns), 160 - 280 kg/hr of ground soda ash (mean particle size of 15 microns), 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder. The condition of the Schugi mixer is as follows:
Mean residence time : 0.2 - 5 seconds Tip speed : 16 - 26 m/s Energy condition : 0.15 - 2 kj/kg Mixer speed : 2000 - 3200 rpm [Step 2] The agglomerates from the FX-160 mixer are fed to the KM-600 mixer for further agglomeration, rounding and growth of agglomerates. 60 kg/hr of ground soda ash (mean particle size of 15 microns) is also added in the KM
mixer. Choppers for the KM mixer can be used to reduce the amount of oversized agglomerates. The condition of the KM mixer is as follows:
Mean residence time : 3- 6 minutes Energy condition : 0.15 - 2 kj/kg Mixer speed : 100 - 150 rpm Jacket temperature: 30 - 40°C
The resulting granules from the step 2 have a density of 650g/1, and can be optionally subjected to the optional process of cooling, sizing an/or grinding.
Having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the IS scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims (7)

Claims:

1. A non-tower process for preparing a granular detergent composition having a density of at least about 600 g/l, comprising the steps of:

(a) dispersing a surfactant, and coating the surfactant with fine powder having a diameter from 0.1 to 500 microns, while wetting the surfactant coated with the fine powder with finely atomized liquid, in a first mixer wherein conditions of the mixer include (i) from about 0.2 to about 5 seconds of mean residence time, (ii) from about 10 to about 30 m/s of tip speed, and (iii) from about 0.15 to about 5 kj/kg of energy condition, wherein first agglomerates are formed;

(b) thoroughly mixing the first agglomerates in a second mixer wherein conditions of the mixer include (i) from about 0.5 to about 15 minutes of mean residence time and (ii) from about 0.15 to about 7 kj/kg of energy condition, wherein second agglomerates are formed; and (c) granulating the second agglomerates with a liquid detergent ingredients in one or more fluidizing apparatus selected from the group consisting of fluidized bed coolers, fluidized bed dryers, or both, wherein conditions of each of the fluidizing apparatus include (i) from about 1 to about 10 minutes of mean residence time, (ii) from about 100 to about 300 mm of depth of unfluidized bed, (iii) not more than about 50 micron of droplet spray size, (iv) from about 175 to about 250 mm of spray height, (v) from about 0.2 to about 1.4 m/s of fluidizing velocity and (vi) from about 12 to about 100°C of bed temperature and (d) adding a coating agent selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof in one or more of the following locations:

1) directly after the fluidized bed cooler or fluidized bed dryer;
2) between the fluidized bed dryer and the fluidized bed cooler; or 3) directly to the fluidized bed dryer, whereby over-agglomeration is minimized.

2. The process according to claim 1 wherein said surfactant is selected from the group consisting of anionic surfactant, nonionic surfactant, cationic surfactant, zwitterionic, ampholytic and mixtures thereof.

3. The process according to claim 1 wherein said surfactant is selected from the group consisting of alkyl benzene sulfonates, alkyl alkoxy sulfates, alkyl ethoxylates, alkyl sulfates, coconut fatty alcohol sulfates and mixtures thereof.

4. The process according to claim 1 wherein an aqueous or non-aqueous polymer solution is dispersed with said surfactant in step (a).

5. The process according to claim 1 wherein the fine powder is selected from the group consisting of soda ash, powdered sodium tripolyphosphate, hydrated tripolyphosphate, sodium sulphates, aluminosilicates, crystalline layered silicates, phosphates, precipitated silicates, polymers, carbonates, citrates, nitrilotriacetates, powdered surfactants and mixtures thereof.

6. The process according to claim 1 wherein the finely atomized liquid Is selected from the group consisting of liquid silicates, anionic surfactants, cationic surfactants, aqueous polymer solutions, non-aqueous polymer solutions, water and mixtures thereof.

7. The process according to claim 1 wherein an internal recycle stream of powder from the fluidizing apparatus is further added to step (a).