Note: Descriptions are shown in the official language in which they were submitted.
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WO 98/14556 PCT/US97I09?94
PROCESS FOR MAKING A DETERGENT COMPOSITION BY NON-TOWER
PROCESS
10 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// 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 procEas, the various detergent components
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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 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. White
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 difi'icult 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.
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WO 98114556 PCT/US97109794
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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. VVhile 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 8~ Gamble); Hollingsworth et
al,
European Patent Application 351,937 (Unilever); Swatting et al, U.S. Patent
No.
5,205,958; Dhalewadikar et al, Laid Open IVo.W096/04359 (Unilever).
For example, the Laid-open No.VV093123,523 (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.
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_1~_
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 andlor inorganic
solutionslorganic 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) I 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, there is provided a non
tower 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 100 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 agglomerates are formed; and
(b) granulating the agglomerates in one or more fluidizing apparatus
wherein conditions of each of the fluidizing apparatus include (i) from about
1 to
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about 10 minutes of mean residence time, (ii) from about 100 to 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;
wherein the agglomerates comprise from 54% to 86% by weight of the
fine powder in step (a) and the fine powder is selected from the group
consisting
of soda ash, powdered sodium tripolyphosphate, hydrated tripolyphosphate,
sodium sulphate, phosphates, precipitated silicates, polymers, citrates,
nitrilotriacetates, powdered surfactants and mixtures thereof and optionally
further includes from 0 to about 60% by weight of the composition of an
internal
recycle stream of powder.
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, granular detergent agglomerates having a density of at least about
600 g/1. 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)1
In the first step of the process, surfactant, i.e., one or more of aqueous
and/or non-aqueous surfactant(s), which is/are in the form of powder, paste
and/or liquid, and fine powder having a diameter from 0.1 to 500 microns,
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preferably from about 1 to about 100 microns are fed into a mixer, 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,
having a diameter of about 0.1 to about 300 microns generated from fluidizing
apparatus which is described hereinafter in the second step, 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 the final product from the process of
the
present invention.
In another embodiment of the invention, the surfactants) 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 mixer is in
range from about 2 to about 50 seconds and tip speed of the mixer is in range
1 S from about 4 m/s to about 25 m/s, the energy per unit mass of the mixer
(energy
condition) is in range from about 0.15 kj/kg to about 7 kjlkg, more
preferably, the
mean residence time of the mixer is in range from about 5 to about 30 seconds
and tip speed of the mixer is in range from about 6 mls to about 18 m/s, the
energy per unit mass of the mixer (energy condition) is in range from about
0.3
kjlkg to about 4 kjlkg, and most preferably, the mean residence time of the
mixer
is in range from about 5 to about 20 seconds and tip speed of the mixer is in
range from about 8 m/s to about 18 mls, the energy per unit mass of the mixer
(energy condition) is from about 0.3 kj/kg to about 4 kjlkg.
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 Lt~dige CB Mixer manufactured
by the LtSdige Company (Germany). As the result of the first step, resultant
product (agglomerates having fine powder on the surface of the agglomerates)
is
then obtained.
Second Step
In the second step of the process, the resultant product of the first step
(the agglomerates) is fed into a fluidized apparatus, such as fluidized bed,
in
order to enhance granulation for producing free flowing high density granules.
The second 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
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bed cooler ). In the second step, the resultant product from the first step is
fluidized thoroughly so that the granule's from the second step have a round
shape. Optionally, about 0 to about 10% , more preferably about 2-5% of
powder detergent materials of the kind used in the first step andlor 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 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/1, condition of a tluidized 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 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 second step in tatal 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
the fluid bed cooler or fluid bed dryer andJor (2) the coating agent may be
added
between the fluid bed dryer and the fluid bed cooler. 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
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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.
Startin Deter ent 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 andlor the second step of
the
present invention.
Detergent Surfactant (Aoueous /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, Laughti~ et al.,
issued December 30, 1975. Useful cationic surfactants also include those
described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and
in
U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Of the surfactants,
avionics and nonionics are preferred and avionics are most preferred.
Nonlimiting examples of the preferred anionic surfactants useful in the
present invention include the conventional C11-C1g alkyl benzene sulfonates
("LAS"), primary, branched-chain and random C1p-C2p alkyl sulfates ("AS"), the
C1p-C1g secondary (2,3) alkyl sulfates of the formula CH3(CH2?x(CHOS03-M+)
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-9-
CH3 and CH3 (CH2)y(CHOS03-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-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 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 C1p-C18 alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl
polyglycosides and the corresponding sulfated polyglycosides, and C12-C1g
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surfactants such as the C12-C1g alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxyiates and C6-C12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxylpropoxy), C10-C1g amine
oxides, and the like, can also be included in the overall compositions. The
C10-
C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include the C12-C1g N-methylglucamides. See WO 92/06154. Other sugar-
derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such
as
C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-
C18 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-C16,
preferably Cg-C~1 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
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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 Cg-C1g hydrocarbyl group, preferably a C10-
C16 alkyl group or C1p-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-C2 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; C16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethylbetaine; and
[C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18
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 Cg-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 hydrocarbyi 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 suitaine
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
CA 02268067 2002-O1-29
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 8~ 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 aiuminosilicate 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
Nazl(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
Nal2I(~1102)12~(Si02)12~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
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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 CaC03
hardness/gram, calculated on an anhydrous basis, and which is preferably in a
range from about 300 to 352 mg equivalent of CaC03 hardnesslgram.
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++Igallon/minute/-gramlgallon, and more preferably in a range from about 2
grains Ca++lgallonlminutel-gramlgallon to about 6 grains Ca++Igallonlminutel
-gramlgallon.
FineI~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. The aqueous or non-aqueous polymer solution is
dispersed in
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 aad
(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 ftnely atomized liquid herein
and suitable quaternary ammonium surfactants are selected from mono Cg-Clg,
preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein remaining N
positions are substituted by melhyl, 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:
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-13-
H
( f"~-~r~ 1-(N-Rim-[N-F~rrN~
having a modified polyamine formula Vin+~ )WmYnZ or a
polyamine backbone corres~>onding to the formula:
having a modified polyamine formula V~n_k+~)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 ace backbone units having the formula:
X..
-N-~' or -N~ R- or -N-R
iii) Y units are branching units having the formula:
EX
or -N~ R~-- or -N_~--
I ; and
iv) Z units are terminal unnts having the formula:
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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)xRb(OR1)x-,
-(CH2CH(OR2)CH20)z(R10)yR1(OCH2CH(OR2)CH2)H,-,
-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 alkyiene, C4-C12 alkenylene, Cg-
C12 arylalkylene, Cg-C10 arylene, and mixtures thereof; R5 is C1-C12 alkylene,
Cg-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12 dialkylarylene,
-C(O)-, -C(O)NHR6NHC(O)-, -R1(OR1)-, -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, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22
hydroxyalkyl, -(CH2)pC02M, -(CH2)qS03M, -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, -P03M, 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 poiycarboxytate dispersants which can be prepared by
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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
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 Acrylic/maleic-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 solutian to be pre-complexed with anionic
surfactant such as LAS .
CA 02268067 2002-O1-29
Adjunct Detergent (nqredients
The starting detergent material in the present process can include
additional detergent ingredients andlor, any number of additional 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, anti-tarnish
and
anticorrosion agents, soil suspending agents, soil release agents, germicides,
pH
adjusting agents, non-builder alkalinity sources, chelating agents, smectite
clays,
enzymes, enzyme-stabiti2ing agents and perfumes. See U.S. Patent 3,936,537,
issued February 3, 1976 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 polycarboxytates. Preferred are the alkali
metal.
especially sodium, salts of the above. Preferred for use herein are the
phosphates, carbonates, C1~18 fatty acids, potycarboxytates, 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 alt
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
CA 02268067 2002-O1-29
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 acrd, 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, aconitic acid, citraconic acid and methylene
maionic 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 polyacetal
carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to
Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to
Crutchfield et al. These polyacetal carboxylates can be
prepared by bringing together under polymerization conditions
an ester of glyoxylic acid and a polymerization initiator.
The resulting polyacetal carboxylate ester is then attached to chemically
stable
end groups to stabilize the polyacetai carboxylate against rapid
depolymerization
in alkaline solution, converted to the corresponding salt, and added to a
detergent composition. Particularly preferred polycarboxylate builders are the
ether carboxylate builder compositions comprising a combination of tartrate
monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071,
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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 Stens
Optionally, the process can comprise the step of spraying an additional
binder in the mixer for the present invention. A binder is added for purposes
of
enhancing agglomeration by providing a "binding" or "sticking" agent for the
detergent components. The binder is preferably selected from the group
consisting of water, anionic surfactants, 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. 5,108,64fi (Procter 8 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.
CA 02268067 2002-O1-29
Another optional step of the instant process entails finishing the resulting
detergent agglomerates by a variety of processes including spraying andlor
admixing other conventional detergent ingredients. For example, the finishing
step encompasses spraying perfumes, brighteners and enzymes 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 2,268,057.
!n 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
Example 1:
The following is an example for obtaining agglomerates having high
density, using L(idige CB mixer (CB-30), followed by Fluid Bed Apparatus for
further granulations.
(Step 1] 250 - 270 kglhr of aqueous coconut fatty alcohol sulfate
surfactant paste (C12-C18, 71.5% active) is dispersed by the pin tools of a CB-
mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75
microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15
microns),
25 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns),
and
the 200 kglhr of internal recycle stream of powder. The surfactant paste is
fed at
about 40 to 52°C, and the powders are fed at room temperature. The
condition
of the CB-30 mixer is as follows:
Mean residence time : 10-18 seconds
30 Tip speed : 7.5 -14 m/s
Energy condition : 0.5 - 4 kjlkg
Mixer speed : 550 - 900 rpm
Jacket temperature : 30°C
Step 2] The agglomerates from the CB mixer are fed to a fluid bed drying
apparatus for drying, rounding and growth of agglomerates. 20 - 120 kg/hr of
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liquid silicate (43% solids, 2.0R) 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 mls
Bed temperature : 40 - 70 °C]
The resulting granules from the step 2 have a density of about 600 g//, and
can
be optionally subjected to the optional process of cooling, sizing and/or
grinding.
Example 2:
The following is an example for obtaining agglomerates having high
density, using Lodige CB mixer (CB-30), followed by Fluid Bed Apparatus for
further granulaions.
[Step 1] 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C11-C1g alkyl
benzene sulfonate; 95% active) at about 50 °C, and 20 kg/hr of AE3S
liquid ,
(C10-C1g alkyl alkoxy sulfates, EO-3; 28% active) is dispersed by the pin
tools of
a CB-30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40
- 75 microns), f 60 - 200 kg/hr of ground soda ash (mean particle size of 15
microns), 80- 120 kglhr of ground sodium sulfate (mean particle size of 15
microns), and the 200 kg/hr of internal recycle stream of powder. The
surfactant
paste is fed at about 40 to 52°C, and the powders are fed at room
temperature.
The condition of the CB-30 mixer is as follows:
Mean residence time : 10-18 seconds
Tip speed : 7.5 - 14 m/s
Energy condition : 0.5 - 4 kjlkg
Mixer speed : 550 - 900 rpm
Jacket temperature : 30°C
[Step 2] The agglomerates from the CB-30 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
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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 2 have a density of about 600 g/1, and
can
be optionally subjected to the optional processes of cooling, sizing an/or
grinding.
Example 3:
The following is an example for obtaining agglomerates having high
density, using Lt~dige CB mixer (CB-30), followed by Fluid Bed Apparatus for
further granulations.
[Step 1] 15 kg/hr - 30kglhr of HLAS (an acid precursor of C11-C1g alkyl
benzene sulfonate; 95% active) at about 50 °C, and 250 - 270 kg/hr of
aqueous
coconut fatty alcohol sulfate surfactant paste (C12-Clg, 71.5% active) is
dispersed by the pin tools of a CB-30 mixer along with 220 kg/hr of powdered
STPP (mean particle size of 40 - 75 microns), 160 - 200 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 surfactant paste is fed at about 40 to 52°C, and the
powders are
fed at room temperature. The condition of the CB-30 mixer is as follows:
Mean residence time : 10 - 18 seconds
Tip speed : 7.5 - 14 m/s
Energy condition : 0.5 - 4 kj/kg
Mixer speed : 550 - 900 rpm
Jacket temperature : 30°C
[Step 2J The agglomerates from the CB-30 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
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The resultant from the fluid bed drying apparatus is fed to a fluid bed
cooling apparatus. The condition of the fluid bed cooling apparatus is as
follows:
Mean residence time : 2- 4 minutes
Depth of unfluidized bed : 200 mm
Fluidizing velocity : 0.4 - 0.8 m/s
Bed temperature : 12 - 60 °C]
The resulting granules from the step 2 has a density of about 600 g/1, and can
be
optionally subjected to the optional process of 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
scope of the invention and the invention is not to be considered limited to
what is
described in the specification.
