"An Agglomeration Process For Preparing A Granular Detergent Composition "
Abstract:
A non-tower process for continuously preparing granular detergent composition 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 in a mixer, wherein first agglomerates are formed, (b) thoroughly mixing the first agglomerates in a mixer, wherein second agglomerates are formed, and (c) granulating the second agglomerates in one or more fluidizing apparatus. The process can also comprise further step (b1), i.e., Spraying finely atomized liquid onto the second agglomerates in a mixer, between step (b) and step (c).
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Notices, Deadlines & Correspondence
Patent Information
Application #
Filing Date
03 October 1997
Publication Number
40/2005
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2008-02-20
Renewal Date
Applicants
1. THE PROCTER & GAMBLE COMPANY
ONE PROCTER & GAMBLE PLAZA, CINCINNATI, OHIO 45202, USA
Inventors
1. DEL GREKO, ANGELA GLORIA
PRES. TER. 202, 4-13-6, SHINOHARA KITAMACHI, NADA-KU, KOBE 657, JAPAN
2. BEIMESCH, WAYNE EDWARD
711 RED BUD DRIVE, COVINGTON, KY 41015, US
3. KANDASAMI, MANIVANNAN (NMN)
5-11, 501-2508 KOOYO-CHO, NAKA HIGASHINADA-KU, KOBE 658, JAPAN
Specification
FIELD OF THE INVENTION
The present invention generally relates to an agglomeration process for preparing a granular 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/l 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). In 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 two processes, the important factors which govern the derisity 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 and/or 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 liquid ingredients) 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 Patent Application 451,894.
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); Swatling et al, U.S. Patent No. 5,205,958; Dhalewadikar et al, Laid Open No.WO96/04359 (Unilever).
For example, the Laid-open No.WO93/23,523 (Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt% of the granules having a diameter over 2 mm. The U.S. Patent No. 4,427,417 (Korex) describes continuous process for agglomeration which reduces caking and oversized agglomerates.
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 heeds 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 uae spray drying towers which typically emit particulates and volatile organic compounds into the atmosphere.
As used herein, the tenn "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 "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 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, a process for preparing a granular detergent composition having a density at least about 600 g/1 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, in a mixer wherein conditions of the mixer include (i) from about 2 to about 50 seconds of mean residence time, (ii) from about 4 to about 25 m/s of tip speed, and (iii) from about 0,15 to about 7 kj/kg of energy condition, wherein first agglomerates are formed;
(b) thoroughly mixing the first agglomerates in a mixer wherein
conditions of the rnixer 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 in one or more fluidizing
apparatus 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.
Also provided is a process for preparing a granular detergent composition having a density at least about 600 g/l, 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, in a mixer wherein
conditions of the mixer include (i) from about 2 to about 50 seconds
of mean residence time, (ii) from about 4 to about 25 m/s of tip
speed, and (iii) from about 0.15 to about 7 kj/kg of energy condition,
wherein first agglomerates are formed;
(b) thoroughly mixing the first agglomerates in a 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;
(b') spraying finely atomized liquid onto the second agglomerates in a 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 third agglomerates are formed; and
(c) granulating the third agglomerates in one or more fluidizing
apparatus 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.
Also provided are the granular detergent compositions having a high density of at least about 600g/l, 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 den$ity 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.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow diagram of a process in accordance with one embodiment of the invention which includes the agglomeration process by the first mixer, followed by the second mixer, then fluidizing apparatus, to produce a granular detergent composition having a density of at least 600g/l.
FIG. 2 is a flow diagram of a process in accordance with one embodiment of the invention which includes the agglomeration process by the first mixer, followed by the second mixer, then third rnixsr, finally fluidizing apparatus, to produce a granular detergent composition having a density of at least 600g/l.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention is directed to a process which produces free flowing, granular detergent agglomerates having a density of at least about 600 g/l. 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.
8 STATEMENT OF THE INVENTION
According to the present invention there is provided an agglomeration process for preparing a granular detergent composition having a density of at least 600g/l, comprising the steps of:
(a) dispersing a surfactant, and coating the surfactant with fine powder described
having a diameter from 0.1 to 500 microns, in a first mixer wherein conditions of the
mixer include (i) from 2 to 50 seconds of mean residence time, (ii) from 4 to 25 m/s of
tip speed, and (iii) from .15 to 7 kj/kg of energy condition, wherein first agglomerates
are formed; and
(b) thoroughly mixing the first agglomerates in a second mixer wherein
condition of the mixer include (i) from 0.5 to 15 minutes of mean residence time and
(ii) from 0.15 to 7 kj/kg of energy condition, wherein second agglomerates are
formed;
characterized in that the process comprises;(c) granulating the second agglomerates in fluidising bed apparatus while
spraying into the bed droplets of liquid detergent material such as herein described in
an amount of upto 20% and wherein conditions of the fluidising bed apparatus include
(i) from 1 to 10 minutes of mean residence time, (ii) from 100 to 300 mm of depth
of unfluidised bed (iii) not more than 50 micron of droplet spray size, (iv) from 175
to 250 mm of spray height, (v) from 0.2 to 1.4 m/s of fluidising velocity and (vi) from
12 to 100°C of bed temperature.
PROCESS
Reference is now made to (1) Fig.1 which presents a flow chart illustrating an embodiment of the present invention, i.e., process comprising the first step, the second step (i) and the third step below; and (2) Fig.2 which presents a flow chart illustrating an embodiment of the present invention, i.e., process comprising the first step, the second steps (i) and (ii), and the third step below. First Step [Stepte'il
In the first step of the process, surfactant 11, i.e., 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 12 having a diameter from 0.1 to 500 microns, 'preferably from about 1 to about 100 microns are fed into a first mixer 13, so as to make agglomerates. (The definition of the surfactants and the fine powder are described in detail hereinafter.) Optionally, an internal- recycle stream of powder 30, having a diameter of about 0.1 to about 300 microns generated from fluidizing apparatus 27, which are described hereinafter in the step 3, can be fed into the mixer in addition to the fine powder. The amount of such internal recycle stream of powder 30 can be 0 to about 60 wt% of final product 29.
In another embodiment of the invention, the surfactant 11 can be initially fed into a mixer or pre-mixer (e.g. a conventional screw extruder or other similar rnixer) 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 2 to about 50 seconds and tip speed of the first mixer is in range from about 4 m/s to about 25 m/s, the energy per unit mass of the first mixer (energy condition) is in range from about 0.15 kj/kg to about 7 kj/kg, more preferably, the mean residence time of the first mixer is in range from about 5 to about 30 seconds and tip speed of the first mixer is in range from about 6 m/s to about 18 m/s, the energy per unit mass of the first mixer (energy condition) is in range from about 0.3 kj/kg to about 4 kj/kg, and most preferably, the mean residence time of the first mixer is in range from about 5 to about 20 seconds and tip speed of the first mixer is in range from about 8 m/s to about 18 m/s, the energy per unit mass of the first mixer (energy condition) is in range from about 0.3 kj/kg to about 4 kj/kg.
The examples of mixers for the first step can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the first step, An Example can be Lodige CB Mixer manufactured
by the Lodige company (Germany). As the result of the first step, resultant product 16 (first agglomerates having fine powder on the surface of the agglomerates) is then obtained. Second Step [Step fb) / Step (b'tt
As one preferred embodiment, there are two types of choice, i.e., second step (i) only; or second step (i) followed by second step (ii).
Second Stepr (\)fStep (b)]: The resultant product 16 (the first agglomerates) is fed into a second mixer 17. Namely, the resultant product 16 is mixed and sheared thoroughly for rounding and growth of the agglomerates in tVie second mixer 17. Optionally, about 0-10% . more preferably about 2-5% of powder detergent ingredients of the kind used in the first step and/or other detergent ingredients 18 can be added to the second step (i). Preferably, choppers which are attachable for the second mixer can be used to break up undesirable oversized agglomerates. Therefore, the process including the second mixer 17 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 in range from about 3 to about 6 minutes and the energy per unit mass of the second mixer is in range from about 0.15 to about 4kj/kg.
The examples of the second mixer 17 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 (i). An Example can be Lbd'tge KM Mixer manufactured by the Lfldige company (Germany), As the result of the second step (i), a resultant product 20 (second agglomerates) with round shape is then Obtained. The resultant product 20 is then subjected to either the second step (ii) or the third step below.
Second Step (ii) rStepfb'IV. The resultant product 20 (second agglomerates) Is fed into a third mixer 21, and then finely atomized liquid 22 is sprayed on the second agglomerates in the mixer 21. Optionally, excessive fine powder formed in the first step and/or the second step (i) is added to the second step (ii). If the excessive fine powder is added to the second step (ii), spraying
the finely atomized liquid is useful in order to bind the excessive fine powder onto the surface of agglomerates. About D-10% , more preferably about 2-5% of powder detergent ingredients of the kind used in the first step, the second step (i) and/or other detergent ingredients can be added to the mixer 21.
Generally speaking, preferably, the mean residence time of the third mixer is in range from about 0.2 to about 5 seconds and tip speed of the third mixer is in range from about 10 m/s to about 30 m/s, the energy per unit mass of the third mixer (energy condition) is in range from about 0.15 kj/kg to about 5 kj/kg, more preferably, the mean residence time of the third mixer is in range from about 0.2 to about 5 seconds and tip speed of the third mixer is in range from about 10 m/s to about 30 m/s, the energy per unit mass of the third mixer is in range from about 0.15 kj/kg to about 5 kj/kg, the most preferably, the mean residence time of the third mixer is in range from about 0.2 to about 5 seconds, tip speed of the third mixer is in range from about 15 m/s to about 26 m/s, the energy per unit mass of the third mixer (energy condition) is in range from about 0.2 kj/kg to about 3 kj/kg.
The examples of the mixer 21 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 (ii). An Example can be Rexornic Model manufactured by the Schugi company (Netherlands). As the result of the second step, a resultant product 24, i.e., agglomerates with excessive fines on them can be obtained. The resultant product 24 (third agglomerates) is then subjected to the third step below. Th,ird Step [ Step (c)
In the third step of the process, the resultant product 20 the second agglomerates) or the resultant product 24 (the third agglomerates), is fed into a fluidized apparatus 27, such as fluidized bed, in order to enhance further granulation for producing free flowing high density granules. The third step can proceed in one or more than one fluidized apparatus (e.g., combining different kinds of fluidized apparatus such as fluid bed dryer and fluid bed cooler). In the third step, the resultant product from the second step is fluidized thoroughly so that the granules from the third step have a round shape (i.e., granulation is conducted in the third step). Optionally, about 0 to about 10%, more preferably about 2-5% of powder detergent materials of the kind used in the first step, the second step (i), the second step (ii) and/or other detergent ingredients can be
added to the third 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 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/l, preferably more than 650g/1. condition of a fiuidized apparatus can be;
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 mmFluidizing 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 0C.
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 andAsr 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 the fluid bed cooler or fluid bed dryer; (2) the coating agent can be added between the fluid bed dryer and the fluid bed cooler; and/or (3) the coating agent can be added directly to the third mixer 21 and the 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.
In the case that the process of the present invention is carried out by using (1) CB mixer which has flexibility to inject at least two liquid Ingredients; (2) KM mixer which has flexibility to inject at least a liquid ingredient! (3) Schugi Mixer which has flexibility to inject at least two liquid ingredients; (4) Fluidized (Fluid) Bed which has flexibility to inject at least two liquid ingredients, the process can incorporate seven different kinds of liquid ingredients in the process. Therefore, the proposed process is beneficial for the person skilled in the art in order to incorporate into a granule making process starting detergent materials which are in liquid form and are rather expensive and sometimes more difficult in terms of handling and/or storage than solid materials.
The proposed invention is also useful in view of industrial requirement, because the person skilled in the art can set a series of apparatuses in a plant, and by using divertors which are capable for connecting/disconnecting between each apparatus, so that the skilled in the art can select variations of the process to meet desired property {e.g., particle size, density, formula design) of the final product. Such variations include not only the process of the present inventions, i.e., (i) First Mixer- Second Mixer . Fluidizing Apparatus, (ii) First Mixer - Second Mixer - Third Mixer - Fluidizing Apparatus, but also include (Hi) First Mixer - Third Mixer - Fluidizing Apparatus, (iv) First Mixer - Third Mixer - Second Mixer -Fluidizing Apparatus, and (v) First Mixer - Fluidizing Apparatus.
Stgrtina.Petejrgient Matenals
The total amount of the surfactants in products made by the present invention, which are included rn 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.
Determent Surfactant (Aqueous /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.
The surfactant itself is preferably selected from anionic, nonionic, zwitterionic, amphoiytic 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, both of which are incorporated herein by reference. Useful cationic surfactants also include those described in U.S. Patent 4,222,605, Cockreil, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1080, both of which are also incorporated herein by reference. Of the surfactants, anionics and nonionics are preferred and anionics are most preferred.
Nonlirniting examples of the preferred anionic surfactants useful in the present invention include the conventional C11-C118 alKyl benzene sulfonates ("LAS"), primary, branched-chain and random Cio-C20 alkyl sulfates ("AS"), the
C10-C18 secondary (2,3) alky! sulfates of the formula CH3(CH2)x(CHOSO3-M+') CHs and CHs (CH2)y(CHOSO3~M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a waler-solubiiizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C10-C18 alkyl' afkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates).
Useful anionic surfactants also include water-soluble salts of 2-acyloxy-alkane'1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates -containing from about 1 to 3 carbon atoms in the alky! 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 C1018 glycsrol ethers, the C10-C18 alkyl
polyglycosides and the corresponding sulfated palyglycosides, andC12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("A2") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C10-C18 arnine oxides, and the like, can also be included in the overall compositions. The C^Q-CIB N-alkyl poiyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,200,154. Other $ugar-derived surfactants include the N-alkoxy poiyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamider The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used, ff high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are fisted in standard texts,
Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C6-C16, preferably C6-C10 N-alkyl or aikenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Ampholyttc surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of helerocyclic 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; aikyl ether suifates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R1)2N+R2COO", wherein R is a Ce-Cie hydrocarbyl group, preferably a C10-C16 aikyl group or C10-C16 acylamido alkyl group, each R1 is typically C1-C3 alky!, preferably methyl and R2 is a C1C5 hydrocarbyl group, preferably a Ci-GS alkylene group, more preferably a C1-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine;
C12-14 acylamidopropylbetaine; C8-14 acylamiriohexyldiethyl betaine; 4[Cl4-16acylmethylamidodiethylamrnonio]'1-carbtoxybuta[jc; C16-18 acylamidodimethylbetaine; C12-16 ar/lamidopentanediethytbetaine; and C12-16 acylmethylamtdodimethylbetaine. Preferred betaines ate C12-18 dlrnethyl-ammonio hexanoate and the G16-18 acyiamidopropane (or ethane)
dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R1)2N+R2SO3- wherein R is a C6-C18 hydrocarbyl group, preferably a C10-C16 a'ky! group, more preferably a C12-C13 alky' group, each R1 is typically C-|-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, C12-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, aluminosilicat.es, 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 fine powder of the present invention, 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), the disclosure of which is incorporated herein by reference.
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 determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula
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 Na12[(AI02)i2.(Si02)i2]xH20
wherein x is from about 20 to about 30, preferably about 27. These preferred alurninosilicates 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 disclosure of which is incorporated herein by reference.
The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCOs hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCOs 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/minute/-gram/gallon to about 6 grains Ca++/gallon/minute/ -gram/gallon.
Finely Atomized Liquid
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 solutions, water and mixtures thereof. Other optional examples for the finely atomized liquid of the present invention can be sodium carboxy methyl cellulose solution, 'polyethylene glycol (PEG), and solutions of dimethylene triamine pentamethy! 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 C6-C16. preferably C6-C10 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
having a modified polyamine formula V(n+i)WmYnZ or a polyamine backbone corresponding to the formula:
(Formula Removed)having a modified polyamine formula V(n.k+-t)WmYnY'[