Process for preparing a phosphate-reduced granular detergent

A phosphate-reduced, granular free-flowing detergent containing (a) from 5 to 40% nonionic surfactant, (b) from 3 to 20% anionic surfactant, (c) from 15 to 50% zeolite, (d) from 0.5 to 15% homopolymeric or copolymeric carboxylic acid or alkali metal salts thereof and (e) from 10 to 72.5% detergent constituents which are stable under spray-drying conditions, with the proviso that the detergent comprises a mixture of two powder components (A) and (B) in a weight ratio of from 1:5 to 3:1, component (A) containing from 50 to 100% of constituent (a), from 80 to 100% of constituent (c) and from 50 to 100% of constituent (d). Component (A) has an average particle size of from 0.4 to 0.8 mm and a powder density of from 500 to 800 g/l. Component (B) contains from 80 to 100% of constituent (b) and 100% of constituent (e), has a powder density of from 300 to 500 g/l and differs in its particle size distribution by at most 50% from the particle size distribution of component (A).

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a phosphate-reduced detergent consisting of 
several granular powder components and containing finely-divided 
crystalline zeolites, nonionic surfactants selected from the group 
consisting of polyglycolether derivatives, anionic surfactants, and 
homopolymeric or copolymeric carboxylic acids as its essential 
constituents, and optionally sodium tripolyphosphate, in a particular 
powder distribution. 
2. Discussion of Related Art 
Finely-divided zeolites of the NaA and NaX type have been repeatedly 
proposed as phosphate substitutes in detergent compositions. However, it 
has been found that they must be present in the detergent in quantities of 
at least 20% by weight, and preferably in quantities of at least 25% by 
weight, in order to obtain a good detergent effect and, in particular, to 
minimize fabric incrustation. Unfortunately, considerable problems are 
involved in incorporating quantities as large as these in a detergent 
composition by spray drying. In the interests of energy conservation and 
efficient utilization of the hot spray drying towers, it is desirable to 
keep the water content of the mixture to be spray-dried as low as 
possible. The mixtures to be spray-dried normally contain from 30 to at 
most 45% by weight water, of which from 8 to 15% by weight remains in the 
product after spray drying. The synthetic zeolites are generally processed 
in the form of a filter-moist, stabilized suspension containing about 50% 
water which is particularly suitable for further processing. The addition 
of further, sprayable detergent constituents frequently containing water 
may then lead to a further increase in the water content of the slurry 
and, hence, to an increased energy demand and to a loss of capacity in the 
spray-drying plants. 
If the zeolite is added to the slurry as a predried powder in order o 
reduce the water content of the slurry, zeolite agglomerates may be formed 
which tend to deposit on the textiles during the washing process. These 
problems may especially occur when the compositions contain water-soluble 
silicates like sodium waterglass. 
Additional problems arise during spray-drying of phosphate-reduced washing 
compositions. As it is known, a certain percentage of the tripolyphosphate 
incorporated into the slurry is hydrolyzed to orthophosphate and 
pyrophosphate in the course of the spray drying process. These hydrolyzed 
phosphates favor the formation of incrustations on the washed textiles. It 
has been found that with decreasing phosphate content in the composition, 
the portion of the undesirable ortho- and pyrophosphates increases to the 
disadvantage of the tripolyphosphate content. Therefore, particularly in 
low-phosphate compositions the portion of the phosphates that induce 
incrustation is particularly high. Removing the phosphate from the 
spraying process and post-dosing it to the separately prepared powder will 
create new problems, especially if also the zeolite is not processed via 
spray-drying. In this case, the amount of inorganic carrier substance in 
the slurry would be too low with respect to the organic ingredients. Thus, 
the risk of dust explosions in the hot spray tower would increase and the 
formation of dry, free-flowing beads would be made more difficult. 
Another problem is created by the use of nonionic surfactants. These 
compounds, which are distinguished by very high detergency, undesirably 
increase the viscosity of the spray-dried slurry where anionic surfactants 
are simultaneously present. In addition, they give rise to aerosol 
formation, so-called "pluming", in the offgases from the spray-drying 
tower. According to German Application No. 22 04 842-A 1, the nonionic 
surfactants are applied to a carrier powder which contains, inter alia, 
bentonite and microfine silicon dioxide, a particularly effective binder. 
This premix may then be added to a spray-dried detergent powder. However, 
silicon dioxide is not a washing-active constituent, i.e., it merely 
results in additional costs and makes no contribution to the detergent 
effect. The premix is prepared by granulating the powder-form carriers 
with the liquid or molten nonionic surfactant. The production of uniform 
granulates having a defined grain spectrum and powder density by this 
process involves considerable difficulties. Accordingly, mixtures of these 
granulates with spray-drying powders of low specific gravity also have a 
more or less irregular grain spectrum and show a tendency towards 
separation. 
According to German Application No. 25 07 926-B 1, finely-divided 
crystalline aluminosilicates which, in regard to their composition include 
zeolites of the NaA and NaX type, are proposed for use as carrier material 
for the nonionic surfactants. In this case, too, the starting material 
used is a powder-form zeolite. There is nothing in this literature 
reference either to suggest that, to prepare this premix, it is necessary 
to start out with a prepared granulate having a certain grain 
specification and, as described hereinafter, certain additives and 
quantitative ratios in order to avoid subsequent separation of the 
granulate and to obtain optimal detergent properties. 
A detergent product consisting of three powder-form or granular powder 
components is known from German Application No. 27 53 680 A2. The first 
powder component consists of a spray-dried powder and contains anionic 
and/or nonionic surfactants, builder salts, including phosphates, 
zeolites, alkali metal silicates and carbonates. The second component 
consists of builder salts serving as carrier material and silicone foam 
inhibitors adsorbed thereon. The third component consists of a granulate 
prepared from perborate or another per compound and one or more builders, 
preferably phosphates, using nonionic surfactants as binder. However, the 
uptake capacity of perborate for nonionic surfactants is very limited, 
although this is not critical in the present case because the third powder 
component only performs the function of improving the wetting properties 
and, hence, the flush-in behavior of the powder mixture in washing 
machines. However, relatively small amounts of nonionic surfactant or of 
the third powder component are sufficient for this purpose. The notion of 
using a prepared, phosphate-free carrier granulate which, by virtue of its 
special composition and method of production, is capable of taking up 
large amounts of nonionic surfactants is foreign to this publication. In 
addition, there is nothing in the cited application to show how the 
aluminosilicates, polycarboxylates and surfactants optionally used should 
be distributed among the individual powder components in order to obtain 
optimal detergency with phosphate-free detergents. 
The object of the present invention is to solve the following problems or 
to bring a solution nearer to fruition. 
1. Providing a phosphate-reduced detergent which is comparable with a 
conventional phosphate-containing detergent in its soil removal, i.e., 
primary detergency, and incrustation prevention, i.e., secondary 
detergency. 
2. Decreasing the hydrolyzing rate of the tripolyphosphate (if present) and 
reducing the amount of organic compounds in the slurry and the hot 
spraying tower. 
3. Increasing the percentage of zeolite in the detergent while, at the same 
time, easing the load on the spray-drying towers and avoiding an excessive 
energy demand. 
4. Avoiding the formation of zeolite agglomerates. 
5. Developing a carrier material having a high abrasive resistance and 
being completely dispersible in water without forming coarse particles, 
which carrier material is capable of taking up large amounts of nonionic 
surfactants and of increasing the percentage of zeolite in the final 
detergent and converting it into a premix which, by virtue of its grain 
spectrum, is suitable for mixing with a spray-dried powder. 
6. Influencing the weight per liter of the final detergent by 
correspondingly formulating the premix with the object of reducing the 
packing volume by increasing the weight per liter of the product. 
7. Improving the powder properties in regard to grain strength and dust 
formation, avoiding separation, obtaining good flow properties both 
immediately after production and also after storage for several months and 
obtaining favorable disintegration and dissolving properties on 
introduction into the wash liquor and on flushing into the washing machine 
with cold tapwater. 
8. Maintaining the suitability of the multicomponent mixtures for taking up 
further powder components, for example those containing bleaches, per-acid 
precursors, enzymes and foam inhibitors. 
DESCRIPTION OF THE INVENTION 
Other than in the operating examples, or where otherwise indicated, all 
numbers expressing quantities of ingredients or reaction conditions used 
herein are to be understood as modified in all instances by the term 
"about". 
The present invention relates to a detergent composition containing less 
than 5% by weight phosphorous in the form of phosphates comprising a 
mixture of at least two granular powder components (A) and (B), wherein 
component (A) comprises finely-divided crystalline synthetic zeolites of 
the NaA type and, optionally, the NaX type, and also nonionic surfactants 
selected from the group consisting of polyglycolether derivatives, and 
component (B) comprises a spray-dried detergent, wherein the mixture of 
the two components comprises the following constituents: 
(a) from 4 to 40% by weight of nonionic surfactants; 
(b) from 3 to 20% by weight of anionic surfactants, the ratio by weight of 
(a) to (b) being from 3:1 to 1:2; 
(c) from 15 to 50% by weight of finely-divided crystalline zeolite; 
(d) from 0.5 to 15% by weight, expressed as free acid, of homopolymeric or 
copolymeric carboxylic acids having a molecular weight of from 1000 to 
120,000 and the sodium or potassium salts thereof; 
(e) from 0 to 20% by weight of sodium tripolyphosphate; and 
(f) from 10 to 72.5% by weight of other detergent constituents which are 
stable under the spray-drying conditions; 
with the proviso that the ratio by weight of component (A) to component (B) 
is from 1:5 to 3:1, and powder component (A) contains from 50 to 100% of 
constituent (a), from 80 to 100% of constituent (c) and from 50 to 100% of 
constituent (d) and has a powder density of from 500 to 800 g/l and an 
average particle size of from 0.4 to 0.8 mm, the percentage of particles 
larger than 1.6 mm and of particles smaller than 0.1 mm not exceeding 1% 
by weight in either case, and with the further proviso that powder 
component (B) contains from 80 to 100% of constituent (b) and 100% of 
constituent (e) and has a powder density of from 300 to 550 g/l and a 
particle size distribution which differs by not more than 50% from that of 
component (A) for the same boundary conditions. 
The starting material for powder component (A) is a granular adsorbent 
having the following composition: 
(A 1) from 20 to 30 parts by weight of finely-divided crystalline, 
synthetic zeolite NaA and, optionally NaX containing bound water, 
(A 2) from 0.5 to 7.5 parts by weight of a homopolymeric or copolymeric 
carboxylic acid having a molecular weight of from 1000 to 120,000 in the 
form of the sodium or potassium salt, 
(A 3) from 3 to 6 parts by weight of water which is removable at a drying 
temperature of 145.degree. C., 
(A 4) from 0 to 10 parts by weight of sodium sulfate, sodium carbonate or 
mixtures thereof, 
(A 5) from 0 to 2 parts by weight of a nonionic surfactant selected from 
the group consisting of polyglycolether derivatives, and 
(A 6) from 0 to 10 parts by weight of sodium nitrilotriacetate. 
The granular adsorbent has an average particle size of from 0.4 to 0.8 mm, 
wherein the percentage having a particle size of smaller than 0.1 mm and 
the percentage having a particle size of larger than 1.6 mm does not 
exceed 1% by weight in either case. The powder density is from 400 to 700 
g/l, and preferably from 450 to 650 g/l. 
Constituent (A 1) comprises synthetic sodium aluminosilicate containing 
bound water, preferably of the zeolite A type. Zeolite NaX and mixtures 
thereof with zeolite NaA may also be used. The suitable zeolites have a 
calcium binding power which is determined in accordance with German 
Application No. 24 12 837 and which is in the range of from 100 to 200 mg 
CaO/g. They are preferably used in the form of undried, stabilized 
suspensions still moist from their production. 
Constituent (A 2) comprises a homopolymeric and/or copolymeric carboxylic 
acid or a sodium or potassium salt thereof, sodium salts being preferred. 
Suitable homopolymers are polyacrylic acid, polymethacrylic acid and 
polymaleic acid. Suitable copolymers are those of acrylic acid with 
methacrylic acid and copolymers of acrylic acid, methacrylic acid or 
maleic acid with vinylethers, such as vinylmethylether or vinylethylether, 
and with vinylesters, such as vinylacetate or vinylpropionate, acrylamide, 
methacrylamide and also with ethylene, propylene or styrene. In 
copolymeric acids such as these, in which one of the components does not 
contain an acid function, the proportion thereof is no more than 70 mole % 
and preferably less than 60 mole % in the interests of adequate solubility 
in water. Copolymers of acrylic acid or methacrylic acid with maleic acid 
of the type described, for example, in European Application No. 25 551-B 1 
have proved to be particularly suitable. The copolymers in question 
contain from 40 to 90% by weight acrylic acid or methacrylic acid and from 
50 to 10% by weight maleic acid. Copolymers containing from 50 to 85% by 
weight acrylic acid and from 50 to 15% maleic acid are particularly 
preferred. 
It is also possible to use polyacetal carboxylic acids of the type 
described, for example, in U.S. Pat. Nos. 4,144,226 and 4,146,495 and 
obtained by polymerization of esters of glycolic acid, introduction of 
stable terminal groups and saponification to the sodium or potassium 
salts. Polymeric acids obtained by polymerization of acrolein and 
disproportionation of the polymer pursuant to Canizzaro reaction using 
strong alkalis are also suitable. They are essentially made up of acrylic 
acid units and vinylalcohol units or acrolein units. 
The molecular weight of the homopolymers or copolymers comprising 
constituent (A 2) is generally from 1000 to 120,000 and preferably from 
1500 to 100,000. They are present in the adsorbent in a quantity of from 
0.5 to 7.5 parts by weight and preferably in a quantity of from 1 to 5 
parts by weight. The abrasion resistance of the particles increases with 
increasing content of polyacid or polyacid salts. Optimal abrasion 
properties are provided by mixtures containing from 2 to 3 parts by weight 
polyacid or salts thereof, based in each case on the above-described 
granulate. 
The moisture content removable from the aluminosilicates at a drying 
temperature of 145.degree. C. comprises from 3 to 6 parts by weight and 
preferably from 3.5 to 5 parts by weight. Further amounts of water bound 
by the zeolite and released at higher temperatures are not included in 
this content. 
The optional constituent (A 4), which comprises sodium sulfate and/or 
sodium carbonate, preferably sodium sulfate, acts as a stabilizer in 
aqueous zeolite dispersions and can improve the dissolving rate of the 
granulates in cold water to a certain extent. Additions of from 0.2 to 5 
parts by weight have proved suitable for this purpose. 
The adsorbent may contain nonionic surfactants in quantities of up to 2 
parts by weight and preferably in quantities of from 0.2 to 1.5 parts by 
weight as further optional constituent (A 5). Suitable nonionic 
surfactants include, in particular, ethoxylation products of linear or 
methyl-branched (oxo residue) alcohols containing from 12 to 18 carbon 
atoms and from 3 to 15 and preferably from 4 to 6 ethylene glycolether 
groups. Other suitable nonionic surfactants include ethoxylation products 
of vicinal diols, amines, thioalcohols and fatty acid amides which 
correspond to the described fatty alcohol ethoxylates in regard to the 
number of carbon atoms in the hydrophobic residue and in regard to the 
glycolether groups. Alkylphenol polyglycolethers containing from 5 to 12 
carbon atoms in the alkyl group, and from 3 to 15, and preferably from 4 
to 6 ethylene glycolether groups are also suitable. Finally, block 
polymers of ethylene oxide and propylene oxide of the type commercially 
available under the trade name of Pluronics.RTM. may also be used. The 
nonionic surfactants are normally present when the granular adsorbents are 
prepared from aqueous zeolite dispersions in which the surfactants 
function as dispersion stabilizers. In individual cases, the nonionic 
surfactants may even be completely or partly replaced by other dispersion 
stabilizers of the type described in German Application No. 25 27 388. In 
addition, component (A) may contain optical brighteners to improve 
whiteness. In that case, the proportion of brighteners in component (B) 
may be reduced accordingly. 
A further optional constituent (A 6), which can partly substitute the 
compound (d), is sodium nitrilotriacetate (NTA). NTA may be used in 
amounts up to 10 parts by weight, preferably 0.5 to 6 parts by weight. It 
is well known that NTA increases the hygroscopic properties of detergent 
powders. Surprisingly it was found, that this disadvantage will be 
overcome if NTA is completely or largely present in powder component (A). 
Moreover, the granular adsorbent component (A) must be free of alkali metal 
silicates, preferably free of sodium silicate. Water soluble silicates 
tend to reduce the dispersing properties of zeolite in the washing liquor. 
The granular adsorbent is prepared by spray-drying an aqueous mixture of 
the ingredients generally containing from 50 to 65% by weight water by 
means of nozzles into a free-fall zone into which drying gases are 
introduced either in countercurrent or in parallel current flow, these 
drying gases having an entry temperature of from 150.degree. to 
280.degree. C. and an exit temperature of from 50.degree. to 120.degree. 
C. The dried particles should have a moisture content which is removable 
at 145.degree. C. of from 8 to 18 parts by weight. 
The water content of the aqueous slurry mixture is preferably from 55 to 
62% by weight. Its temperature is preferably in the range of from 
50.degree. to 100.degree. C., while its viscosity is preferably in the 
range of from 5000 to 20,000 mPa.s. The spraying pressure is generally in 
the range of from 20.degree. to 120 bar, and preferably in the range of 
from 30.degree. to 80 bar. The drying gas which is generally obtained by 
burning heating gas or fuel oil is preferably guided in countercurrent 
flow. Where so-called drying towers into which the aqueous mixture is 
sprayed in the upper part thereof through several high-pressure nozzles 
are used, the entry temperature as measured in the annular duct, i.e., 
immediately before entry into the lower part of the tower, is in the range 
of from 150.degree. to 280.degree. C., preferably in the range of from 
180.degree. to 250.degree. C. and more preferably in the range of from 
190.degree. to 230.degree. C. The moisture-laden offgas leaving the tower 
normally has a temperature of from 50.degree. to 120.degree. C. and 
preferably of from 55.degree. to 105.degree. C. 
The dried granular adsorbent consists essentially of rounded particles 
which show very good flow properties. These very good flow properties 
exist even when the particles are impregnated with large amounts of 
nonionic surfactants which may comprise up to 40% by weight, based on the 
adsorbate. In regard to these properties, the granular adsorbent is 
superior to the hitherto known carrier materials proposed as suitable for 
detergents and cleaning preparations. 
The granular adsorbent is subsequently impregnated with nonionic 
surfactants. These nonionic surfactants may be sprayed both onto the still 
warm spray-dried product and onto the already cooled spray-dried product 
or onto the spray-dried product reheated after cooling. Providing the 
described quantitative ratios and production conditions are observed, the 
abrasion resistance and dimensional stability of the particles is so high 
that even the freshly prepared particles, but especially the cooled and 
optionally reheated, aged particles may be treated with the liquid 
additives, mixed and transported under the usual spray-mixing conditions 
without any fines or relatively coarse agglomerates being formed. 
The nonionic surfactants applied to the granular adsorbent may be of the 
same type as those mentioned above for stabilizing the zeolite dispersion. 
Preferred nonionic surfactants are derived from primary fatty alcohols of 
natural or synthetic origin which may be saturated, mono-unsaturated, 
linear or methylbranched in the 2-position (oxo function) and may contain 
from 10 to 18 carbon atoms. Suitable fatty alcohols are lauryl alcohol, 
myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and 
mixtures thereof of the type present, for example, in coconut oil fatty 
alcohol or tallow fatty alcohol. The average number of glycolether groups 
present therein is from 3 to 16. Particularly suitable fatty alcohols are 
mixtures containing components of relatively low and relatively high 
degrees of ethoxylation, for example those having a degree of ethoxylation 
of from 4 to 6 and those having a degree of ethoxylation of from 9 to 14, 
the mixing ratio generally being from 4:1 to 1:4. 
The granular adsorbent is also suitable for taking up surface-active 
compounds containing amino or amide groups which may optionally be 
ethoxylated and which are insoluble or only sparingly soluble, but 
dispersible in water. In many cases, they enhance the primary detergency 
and are distinguished by a high fat removing power. Examples of compounds 
such as these, which also serve as nonionic surfactants, are fatty acid 
amides derived from ethanolamine, diethanolamine, propanolamine and 
isopropanolamine and also from alkylated diamines. Examples of diamines 
such as these are N,N-dimethylethylenediamine, 
N,N-dimethylpropylenediamine, N-methyl-N-ethylethylenediamine, 
N,N'-dimethylethylenediamine, N,N'-dimethylpropylenediamine, 
N-methyl-N'-ethylpropylenediamine and also mixtures of these alkylated 
alkylenediamines. The fatty acid residues present in the amides are 
derived from saturated or mono-unsaturated fatty acids containing from 10 
to 18 and preferably from 12 to 18 carbon atoms, fatty acids in which more 
than 50% by weight and preferably more than 65% by weight of the acyl 
groups consist of those containing from 12 to 14 carbon atoms being 
particularly preferred. Mixtures obtained from coconut oil fatty acids, 
from which the fraction containing 10 carbon atoms and less has largely 
been separated, are particularly suitable. 
Other nonionic surfactants belonging to this class are ethoxylated 
N-alkylamines containing on average from 1 to 3 ethylene glycolether 
groups and C.sub.10 -C.sub.18 and more especially C.sub.12 -C.sub.14 alkyl 
groups of the type present, for example, in cocosalkyl or oxo groups. 
The impregnation of the granular adsorbent does not significantly affect 
its particle size distribution. However, any fines present, i.e., having a 
particle size less than 0.1 mm, are generally bound and cemented with the 
other particles, so that their percentage content is virtually zero. 
However, the powder density increases with the amount of nonionic 
surfactant applied. A further increase in the powder density may be 
obtained by subjecting the adsorbate to a final powdering treatment. 
Suitable powdering agents having a particle size of from 0.001 to at most 
0.1 mm, and preferably of less than 0.05 mm, may be used in quantities of 
from 0.03 to 5% by weight and preferably in quantities of from 0.05 to 2% 
by weight, based on the impregnated adsorbent. Suitable powdering agents 
include, for example, finely powdered zeolites, silica aerogel 
(Aerosil.RTM.), colorless or colored pigments such as titanium dioxide, 
and other powder materials of the type already proposed for powdering 
granules or detergents particles, such as finely powdered sodium 
tripolyphosphate, sodium sulfate, magnesium silicate and carboxymethyl 
cellulose. The powdering treatment further improves the flow properties of 
the product and provides for even closer packing of the granulate 
particles. The powder component (A) may be provided with a powder density 
of from 450 to 800 g/l, depending on the choice of the granular adsorbent, 
the proportion of nonionic surfactants and the aftertreatment. By varying 
the quantitative ratio between the powder component (A) and the 
spray-dried powder component (B), the powder density of the mixture 
according to the invention may be adjusted within a wide range. 
Starting out with the above composition of the granular adsorbent and the 
proportion of adsorbed nonionic surfactant, the powder component (A) has 
the following composition: 
from 40 to 75% by weight and preferably from 45 to 70% by weight zeolite, 
from 2 to 15% by weight and preferably from 3 to 12% by weight 
(co)polymeric carboxylic acid, 
from 8 to 20% by weight and preferably from 10 to 18% by weight water 
removable at 145.degree. C., 
from 0 to 20% by weight and preferably from 0 to 10% by weight sodium 
sulfate or sodium carbonate, 
from 10 to 50% by weight and preferably from 15 to 35% by weight nonionic 
surfactant, 
from 0 to 10% by weight and preferably 0.5 to 6% by weight of sodium 
nitrilotriacetate, 
from 0 to 5% by weight finely-divided powdering agent, and 
from 0 to 1% by weight optical brightener. 
The granular powder component (B) contains anionic surfactants (constituent 
b). These anionic surfactants contain at least one hydrophobic hydrocarbon 
radical and a water-solubilizing sulfonate or sulfate group in the 
molecule. The hydrophobic radical may be an aliphatic C.sub.10 -C.sub.20 
and preferably C.sub.12 -C.sub.18 hydrocarbon radical, which may be linear 
or methyl-branched in the 2-position, or an alkyl-aromatic radical 
containing from 8 to 14 and preferably from 10 to 12 aliphatic carbon 
atoms. 
Preferred surfactants of the sulfonate type include linear alkylbenzene 
sulfonates (C.sub.9 -C.sub.14 alkyl), mixtures of alkene and hydroxyalkane 
sulfonates and also disulfonates of the type obtained, for example, from 
mono-olefins containing a terminal double bond by sulfonation with gaseous 
sulfur trioxide and subsequent alkaline or acidic hydrolysis of the 
sulfonation products. Alkane sulfonates obtainable from alkanes by 
sulfochlorination or sulfoxidation and subsequent hydrolysis or 
neutralization or by addition of bisulfites onto olefins are also 
suitable. Other suitable surfactants of the sulfonate type are the esters 
of -sulfofatty acids, for example the -sulfonic acids of hydrogenated 
methyl or etbylesters of coconut oil, palm kernel oil or tallow fatty 
acid. 
Suitable surfactants of the sulfate type are the sulfuric acid monoesters 
of primary alcohols, for example, coconut oil fatty alcohols, tallow fatty 
alcohols or oleyl alcohol, and those of secondary alcohols. Sulfated 
reaction products of from 1 to 3 moles ethylene oxide with primary or 
secondary fatty alcohols are also suitable. 
Soaps may also be used as anionic surfactants. Suitable soaps include, in 
particular, the sodium salts of saturated fatty acids containing from 12 
to 18 carbon atoms, such as lauric, myristic, palmitic and stearic acid, 
and of oleic acid and mixtures thereof. Suitable mixtures are soaps 
obtained, for example, from tallow, coconut oil or palm kernel oil fatty 
acids. Where soaps are used, it is important to bear in mind that they 
intensify the expansion of the sprayed particles in the spraying tower. 
The result is that spray-drying mixtures rich in soap lead to particularly 
loose powders of low specific gravity. 
Nonionic surfactants, which correspond in their constitution to the 
ethoxylates present in component (A), may also be used. However, it is 
preferred to use in component (B) only those nonionic surfactants which 
have a degree of ethoxylation of at least 5 or of which the hydrophobic 
radical contains at least 16 carbon atoms or which are characterized by 
both features. Nonionic surfactants such as these show very little 
tendency, if any, towards pluming. The weight per liter of the spray-dried 
powder component (B) may be increased by an addition of nonionic 
surfactants to the spray-drying mixture, i.e., these surfactants have the 
opposite effect of soaps. An addition of paraffins or silicone oils has 
the same effect. It is possible in this way to vary the weight per liter 
of component (B) to a certain extent, for example within limits of from 
300 to 550 g/l and preferably within limits of from 320 to 500 g/l. On the 
other hand, the proportion of nonionic surfactants in component (B) should 
not be too high because, as already mentioned, this results in an increase 
in the viscosity of the slurry and in poorer flow of the spray-dried 
powder. Accordingly, a powder component (B) which contains very little, if 
any, nonionic surfactant, for example less than 5% by weight and more 
especially less than 2% by weight, based on component (B), is preferred. 
Powder component (B) may contain zeolite corresponding to the above 
description as a constituent (c). This zeolite may also preferably be used 
in the form of a stabilized aqueous dispersion (of constituent A 1 of the 
granular adsorbent). Powder component (B) should be free of zeolite if 
powder component (B) contains water-soluble alkali metal silicates. 
In addition, powder component (B) may contain polymeric carboxylic acids 
(constituent d) of the type described above (cf. constituent A 3 of the 
granular adsorbent). An addition such as this can improve the particle 
strength of the spray-dried product. However, where the overall content of 
this constituent in the detergent is small, i.e., less than 3%, it is of 
advantage for this constituent to be completely or largely present in 
powder component (A), because its particle-strengthening property is 
particularly pronounced in that component and of relevance to 
processibility. 
The powder component (B) may contain sodium tripolyphosphate as an optional 
constituent (e). The amount of constituent (e) is limited with respect to 
the phosphate content of the total washing agent, which is less than 20% 
by weight (=4.5% by weight of P). Preferably the amount of 
tripolyphosphate in the total washing agent is 0 to 18.5% by weight and 
more preferably 0 to 10% by weight. In the powder component (B) the amount 
of sodium tripolyphosphate may be in the range of 0 to 50% by weight, 
preferably 0 to 40% by weight. These amounts are related to anhydrous 
phosphate. It was found that the hydrolysis of tripolyphosphate to 
orthophosphate and pyrophosphate is comparatively low. 
The detergent auxiliaries which were collectively referred to as 
constituent (f) and which are stable and do not lose their activity under 
the spray-drying conditions include washing alkalis, sequestering agents, 
perborate stabilizers, neutral salts, redeposition inhibitors, optical 
brighteners and agents which reduce the viscosity of the slurry or which 
influence the powder density of the spray-dried product. 
Suitable washing alkalis include sodium silicates having the ratio 
composition Na.sub.2 O:SiO.sub.2 of 1:1 to 1:3.5, preferably 1:2 to 1:3.3, 
and most preferably 1:2.2 to 1:3. A further suitable washing alkali is 
sodium carbonate. Sodium bicarbonate and sodium borate may also be 
present. Sodium silicate increases detergency, has an anticorrosive effect 
and greatly improves the particle strength of the spray-dried product 
without, as in the case of powder component A, significantly reducing its 
dissolving rate. Accordingly, where the detergent according to the 
invention is required to contain sodium silicate, this should be present 
completely in component (B). Sodium carbonate present in component (B) 
improves the stability of the granular detergent mixture in storage, 
particularly under conditions of high humidity. Since, on the other hand, 
large amounts of sodium carbonate, for example above 15 to 20% by weight, 
promote incrustation of the washed fabrics, it is best to incorporate this 
optional constituent as far as possible, i.e., to an extent of from 75 to 
100%, in powder component (B). 
The group (f) constituent further includes the sequestering agents of the 
aminopolycarboxylic acid and polyphosphonic acid type which are generally 
present in relatively small amounts and which act as so-called cobuilders, 
stabilizers and precipitation inhibitors or threshold substances. The 
aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediamine 
tetraacetic acid, diethylenetriamine pentaacetic acid and higher homologs 
thereof. Suitable polyphosphonic acids are 1-hydroxyethane-1, 
1-diphosphonic acid, aminotri-methylenephosphonic acid, ethylenediamine 
tetra-methylenephosphonic acid and higher homologs thereof, such as for 
example diethylenetriamine tetramethylenephosphonic acid. The 
polycarboxylic acids and polyphosphonic acids mentioned are normally used 
in the form of their sodium or potassium salts. 
Suitable redeposition inhibitors include cellulose ethers, such as 
carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and 
mixed ethers, such as methyl-hydroxyethyl cellulose, methylhydroxypropyl 
cellulose and methylcarboxymethyl cellulose. Mixtures of various cellulose 
ethers, particularly mixtures of carboxymethyl cellulose and methyl 
cellulose, are also suitable. 
Suitable optical brighteners include alkali metal salts of 
4,4'-bis-(2'-anilino-4'-morpholino-1,3,5-triazinyl-6"-amino)-stilbene-2,2' 
-disulfonic acid or compounds of similar structure which contain a 
diethanolamino group instead of the morpholino group. Brighteners of the 
substituted diphenylstyryl type, for example the alkali metal salts of 
4,4'-bis-(2-sulfostyryl)-diphenyl, 
4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl and 
4-(4-chlorostyryl-4'-(2-sulfostyryl)-diphenyl, are also suitable. 
Neutral salts, particularly sodium sulfate, in amounts of 0 to 25% by 
weight, preferably 1 to 10% by weight, and textile softening layered 
silicates such as smectites in amounts of 0 to 22%, preferably 0 to 15% by 
weight may be used as further constituents of powder component (B). 
Further detergent auxiliaries include additives which improve the 
structure of the powder, for example alakli metal salts of toluene, cumeme 
or xylene sulfonic acid. 
Accordingly, powder component (B) preferably has the following composition: 
from 0 to 5% by weight nonionic surfactant; 
from 10 to 25% by weight and preferably from 12 to 20% by weight sulfonate 
or sulfate surfactant; 
from 0 to 6% by weight and preferably from 1 to 5% by weight soap; 
from 0 to 50% by weight and preferably from 0 to 40% by weight sodium 
tripolyphosphate; 
from 0 to 5% by weight and preferably from 0 to 3% by weight (co)polymeric 
carboxylic acid, in the form of sodium or potassium salts; 
from 0 to 12% by weight and preferably from 2 to 10% by weight sodium 
silicate; 
from 0 to 10% by weight and preferably from 0 to 5% by weight sodium 
carbonate; 
from 0.1 to 2% by weight and preferably from 0.2 to 1% by weight 
sequestering agent of the aminopolycarboxylic acid and aminopolyphosphonic 
acid type in the form of sodium or potassium salts; 
from 0.5 to 3% by weight redeposition inhibitors; 
from 0 to 1% by weight optical brighteners; 
from 0 to 20% by weight neutral salts, such as sodium sulfate, powder 
improving additives and stabilizers, such as magnesium silicate; and 
from 8 to 20% by weight adsorbed water. 
Component (B) may be prepared under the same conditions as described above 
for the production of the granular adsorbent. 
In addition to the granular powder components (A) and (B), the detergents 
may contain further powder components as mixture constituents. These 
further powder components contain substances which are unstable or which 
completely or partly lose their specific effect under the spray-drying 
conditions. The substances in question include, for example, enzymes, 
bleaches, bleach activators, foam inhibitors and perfumes. 
Suitable enzymes include those from the class of proteases, lipases and 
amylases and mixtures thereof. Enzymatic agents obtained from bacterial 
strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and 
Streptomyces griseus, are particularly suitable. The enzymes may be 
adsorbed on carriers and/or embedded in shell-forming substances to 
protect them against premature decomposition. The enzymes are also 
preferably present as granulates of comparable particle size distribution 
in order to prevent separation. 
Suitable bleaching components include the perhydrates and per compounds 
normally used in detergents and bleaches. Preferred perhydrates are sodium 
perborate which may be present as the tetrahydrate or even as the 
monohydrate, the perhydrates of sodium carbonate such as sodium 
percarbonate, of sodium pyrophosphate such as perpyrophosphate, of sodium 
silicate such as persilicate, and urea. Sodium perborate tetrahydrate or 
monohydrate is preferably used. 
Another optional powder component is the bleach activators. The bleach 
activators include in particular N-acyl compounds and O-acyl compounds. 
Examples of suitable N-acyl compounds are polyacylated alkylenediamines, 
such as tetraacetylmethylenediamine, tetraacetylethylenediamine and higher 
homologs thereof and also acylated glycolurils, such as 
tetraacetylglycoluril. Further examples include sodium-cyanamide, 
N-alkyl-N-sulfonyl carbonamides, N-acylhydantoins, N-acylated cyclic 
hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, 
cyanurates and imidazolines. In addition to carboxylic acid anhydrides, 
such as phthalic acid anhydride, and esters, such as sodium (iso)-nonanoyl 
pbenolsulfonate, suitable O-acyl compounds include, in particular, 
acylated sugars, such as glucose pentaacetate. Preferred bleach activators 
are tetraacetyl ethylenediamine and glucose pentaacetate. The bleach 
activators may also be granulated and coated with shell-forming materials 
to avoid any interaction with the per compounds. Since foam inhibitors, 
except for high molecular weight fatty acid soaps, frequently lose all or 
part of their effect on incorporation in the detergent slurry, they are 
best also added to the detergent as a separate powder component. Suitable 
foam inhibitors include organopolysiloxanes and mixtures thereof with 
micro-fine, optionally silanized silica, paraffins, waxes, 
microcrystalline waxes and mixtures thereof with silanized silica. 
Mixtures of various foam inhibitors, for example mixtures of silicones and 
paraffins, may also be used. The foam inhibitors are preferably fixed to a 
granular carrier soluble or dispersible in water and, in this form, have a 
particle size distribution corresponding to that of components (A) and 
(B). 
Where perfumes are used, they may be applied to one of the powder 
components. Likewise, one or more of the powder components may be colored 
or coated with pigments, for example to mask the natural color of active 
agents or to provide the powder mixture with a mottled appearance. 
The average particle size or the percentage of the individual sieve 
fractions of the granular powder components (A) and (B) should not differ 
from one another by more than 50% by weight. The content of fines, i.e., 
particle size below 0.1 mm, and of coarse grain, i.e., particle size above 
1.6 mm, should amount to no more than 1% by weight in either case. It has 
been found that, if these conditions are observed, there is no danger of 
the two powder components separating, for example during transport, even 
when the two components differ considerably in their respective weights 
per liter. The other powder constituents are also best used in a granular 
form which does not differ significantly, i.e., by more than 30% by 
weight, in its particle size distribution from that of components (A) and 
(B). 
The ratio in which components (A) and (B) are mixed is in the range of from 
1:5 to 3:1 and preferably in the range of from 1:4 to 2:1 and should be 
selected so that the distribution ratio of constituents (a), (c) and (d) 
remains within the definition according to the invention. The percentage 
content of the optional powder components may vary within relatively wide 
limits. In the final mixture, the percentage content of the per compound, 
preferably perborate, is from 5 to 30% by weight and preferably from 7 to 
25% by weight. Bleach activators may be present in quantities of from 0.2 
to 5% by weight. As already mentioned, both additives are preferably used 
in granulated form. Because they generally require only relatively small 
amounts of granulation aids (generally less than 10%, based on active 
substance) for conversion into stable granulates, their percentage content 
largely corresponds to the actual active substance content. Enzymes and 
foam inhibitors are normally used in quantities of from 0.01 to at most 2% 
by weight and preferably in quantities of from 0.05 to 1% by weight, based 
on active substance. However, in the active substance granulates, the 
percentage content of carrier, fillers and coating materials dominates by 
far, frequently amounting to more than 90% by weight. Accordingly, the 
percentage content of these granular powder constituents in the mixture as 
a whole is generally from 0.3 to 5% by weight in each case. 
The dosing and subsequent mixing of components (A) and (B) and the 
additional powder components may be carried out either in individual steps 
or even at the same time. Dosing and mixing are best carried out 
continuously, with automatic belt weighers in combination with free-fall 
mixers having proven to be particularly suitable for this purpose. There 
is generally no need for additional mechanically operated mixers. If they 
are used, it is advisable to provide for careful treatment of the powder 
mixture in order to avoid destruction of the hollow bead structure of the 
spray-dried powder and an undesirable increase in the proportion of fines 
and dust. 
The detergents according to the invention are distinguished by high 
detergency, particularly with respect to difficult fatty soil. Despite 
their comparatively high content of liquid nonionic surfactants, they pour 
and flow freely and show no tendency to seep through cardboard packs.

EXAMPLES I-V 
An absorbent having the following composition (PBW=part by weight) was 
prepared by spray drying in accordance with German patent application No. 
P 34 44 960.4: 
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47.8 PBW zeolite NaA (based on anhydrous substance) 
5.2 PBW polycarboxylic acid (sodium salt) copolymer 
1.6 PBW ethoxylated tallow alcohol (part of com- 
ponent al) 
2.0 PBW sodium sulfate 
13.7 PBW water, including 7.4 PBW removable at 145.degree. C. 
70.3 PBW 
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The zeolite used had a particle size of from 1 to 8 microns, the proportion 
of particles larger than 8 microns amounting to 6% by weight. There were 
no particles larger than 20 microns. The polycarboxylic acid used was a 
copolymer of acrylic acid and maleic acid (molar ratio 7:3) having an 
average molecular weight of 70,000 in the form of the sodium salt. A 
tallow alcohol (30% cetyl alcohol, 70% stearyl alcohol) reacted with 5 
moles ethylene oxide (EO) was used as the ethoxylated fatty alcohol. 
The grain spectrum determined by sieve analysis produced the following 
weight distribution: 
______________________________________ 
Over Up to Up to Up to Up to Under 
mm 1.6 0.8 0.4 0.2 0.1 0.1 
______________________________________ 
% by 0 3 33 52 12 1.0 
weight 
______________________________________ 
The weight per liter was 550 g/l. 
82.9 parts by weight of the granulate were sprayed with 17.1 parts by 
weight of a molten nonionic surfactant mixture in a spray-mixing apparatus 
consisting of a cylindrical drum equipped with mixing elements and spray 
nozzles and inclined relative to the horizontal (LODIGE mixer). The 
temperature of the granulate was 20.degree. C. and the temperature of the 
surfactant melt was 50.degree. C. The surfactant mixture consisted of 16.7 
parts by weight of tallow alcohol containing 5 moles EO, and 13 parts by 
weight of a lauryl alcohol-myristyl alcohol mixture (2:1) containing 3 
moles EO. A non-tacky, granular product showing excellent flow properties 
was obtained after cooling. The powder density was 650 g/l; the grain 
spectrum was virtually unchanged except that the proportion of particles 
smaller than 0.1 mm was 0%. 
27 parts by weight of the granulate impregnated with the nonionic 
surfactant (powder component A) were mixed with 44.2 parts by weight of a 
spray-dried powder (powder component B). The spray-dried powder component 
(B) contained sodium dodecylbenzene sulfonate (Na-DBS), sodium tallow 
soap, sodium ethylenediamine tetramethylene phosphonate (EDTMP), cellulose 
ether (CMC), sodium silicate (Na.sub.2 O:SiO.sub.2 ratio of 1:3.3) and the 
other constituents shown in Table 1. Granulated enzymes, granulated 
silicone foam inhibitor containing 94.5% of a mixture of sodium carbonate 
(soda), sodium sulfate and sodium silicate as granulation aid, sodium 
perborate and granulated tetraacetyl ethylenediamine (TAED) containing 
5.8% CMC and sodium sulfate as granulation aid were added as further 
powder constituents. These powder-form or granular constituents are 
collectively referred to as "powder component C", of which the total 
quantity amounts to 15.3 parts by weight. 
The composition of the detergent and of other similarly prepared detergents 
is shown in Table 1 in % by weight. 
In Examples 3, 4 and 5, powder component (A) was powdered with 3% by weight 
(based on component A) of zeolite NaA powder after application of the 
nonionic surfactant. 
TABLE 1 
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Examples 
Component 1 2 3 4 5 
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C.sub.16 -C.sub.18 alcohol + 5 moles EO 
3.9 4.3 4.3 3.5 3.5 
C.sub.12 -C.sub.14 alcohol + 3 moles EO 
0.9 1.1 0.9 1.0 1.6 
Zeolite 14.1 24.3 18.4 16.3 16.0 
Copolymer 3.6 4.0 2.0 4.0 4.2 
Sodium-NTA -- -- 3.2 -- -- 
Sodium sulfate 0.5 -- 0.3 0.5 2.0 
Water 4.0 6.8 4.8 4.9 4.5 
B 
C.sub.16 -C.sub.18 alcohol + 5 moles EO 
0.4 -- -- 1.1 -- 
Na-DBS 7.0 6.0 7.5 7.0 7.5 
Soap 1.5 1.5 1.0 1.5 1.5 
Zeolite NaA 10.9 -- -- -- -- 
Sodium tripolyphosphate 
-- -- -- -- 16.0 
Copolymer 0.4 -- -- -- -- 
Sodium carbonate 7.1 10.0 7.0 8.0 5.0 
EDTMP 0.2 0.2 0.2 0.2 0.2 
Sodium sulfate 11.0 7.4 5.1 12.6 10.3 
Layered silicate -- -- 14.0 12.4 -- 
Water 5.7 3.0 7.2 4.7 4.0 
C 
Enzyme granulate 0.5 0.5 0.5 0.5 0.5 
Sodium perborate 25.0 20.0 15.0 18.0 15.0 
TAED granulate -- 2.0 2.0 2.1 2.0 
Foam inhibitor granulate 
3.1 3.0 3.1 3.1 3.0 
Perfume 0.2 0.2 0.2 0.2 0.2 
g/l of Component A 
650 630 670 710 730 
g/l of Component B 
340 330 330 530 440 
g/l of the mixture 
500 480 490 630 580 
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