Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02268060 1999-03-31
WO 98/14553 PCT/fJS97/09791
1
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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-2-
(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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-3-
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
CA 02268060 2002-O1-17
-4-
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;
CA 02268060 2002-O1-17
-5-
(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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-6-
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
600
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
CA 02268060 2002-O1-17
_7_
the first mixer (energy condition) is in range from about 0.15 kj/kg to about
5
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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
_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
CA 02268060 2002-O1-17
_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.
CA 02268060 2002-O1-17
-10-
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,
CA 02268060 1999-03-31
WO 98/i4553 PCT/US97/09791
-11-
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;
C16-18
acylamidodimethylbetaine; C1z-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 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,
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, aluminosilicates, crystalline layered
silicates,
CA 02268060 2002-O1-17
-12-
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
CA 02268060 2002-O1-17
-13-
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.
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-14-
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:
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-9 5-
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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-16-
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 .
~___ ... _..~.
CA 02268060 2002-O1-17
_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
CA 02268060 2002-O1-17
_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,
CA 02268060 2002-O1-17
-19-
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.
CA 02268060 2002-O1-17
-20-
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
15
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 -
20
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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-21-
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
CA 02268060 1999-03-31
WO 98/14553 PCT/US97/09791
-22-
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.
