CH624914A5 - Process for preparing cation-exchanging alkali metal alumosilicates - Google Patents

Description

The invention now relates to the production of new, cation-exchanging, water-insoluble, bound water-containing and X-ray amorphous alkali alumino-15 silicates. The method for producing these products is defined in claim 1. Suspensions according to claim 7 can be produced from these products.

The surfactant content of the new compounds is preferably in the range from 0.01 to 50, in particular from 0.1 to 35,% by weight of surfactant, based on the mixture of surfactant and anhydrous inorganic active substance (= AS). In addition, the new compounds preferably contain 0.7-1.5, in particular 0.9-1.3 mol of Kat2 / nO (cat = a cation of valence n) and 0.8-6, in particular 1.3, per mol of A1203 -4.0 moles of 25 SiO 2. The calcium binding capacity of these compounds is preferably in the range of 50-200, in particular 80-160 g CaO / g AS.

Sodium is the preferred cation; but it can also be replaced by hydrogen, lithium, potassium, ammonium 30 or magnesium and the cations of water-soluble organic bases, e.g. those of primary, secondary or tertiary amines or alkylolamines having a maximum of 2 carbon atoms per alkyl radical or a maximum of 3 carbon atoms per alkyl radical.

35 For the sake of simplicity, the new compounds are referred to below as “aluminum silicates”. Sodium aluminum silicates are preferably used. All statements made regarding their properties, their manufacture and use apply mutatis mutandis to the other 40 compounds claimed.

The new compounds are distinguished from the known ones by an increased rate of cation exchange; their aqueous suspensions are more stable than those of corresponding aluminum silicates containing no surfactants.

It has proven expedient to dissolve the surfactants in the silicate solution. Furthermore, it is advantageous to submit the surfactant-containing silicate solution and to mix in the aluminate solution.

The formation of the water-insoluble aluminum silicates in the presence of the surfactants mentioned makes it possible to slow down or prevent the crystallization of the aluminum silicates, which were initially precipitated in the X-ray amorphous state, and thereby to keep the particle size of the aluminum silicates very small. This is usually below 30 //, the maximum of the particle size distribution curve being significantly lower, e.g. is in the range of 3-8fi, but can also extend down to the range of real colloids. Therefore, the suspensions of these X-ray-amorphous products obtained during the precipitation are more stable in suspension than the suspensions obtained in the absence of surfactants.

The concentration of the suspensions obtained is preferably in the range from 2-50, in particular from 5-35,% by weight surfactant-containing aluminum silicate. The concentration information above relates to the product dried for 3 hours at 80 ° C. and 100 torr, but which still contains bound water.

The dried precipitation products still contain bundled

denes water, which can only be completely removed by heating to 800 ° C for one hour, which of course also destroys the organic components. The products treated in this way are referred to here as “anhydrous inorganic active substances” (AS); the values for the calcium binding capacity given in the examples refer to this anhydrous active substance.

During the precipitation, the surfactants are built into the X-ray-amorphous aluminum silicate that forms and, depending on the nature of the surfactant, is more or less slowly released from it when these aluminum silicates are introduced into surfactant-free water. When cleaning the precipitated raw products, it may therefore be expedient to use aqueous solutions of the built-in surfactant to wash out the mother liquor.

For the purposes of the invention, “hardness-resistant ionic surfactants” are anionic, cationic or zwitterionic water-soluble organic substances which noticeably reduce the surface tension of aqueous solutions even in low concentrations and in the presence of dissolved hardness formers and which have an aliphatic hydrocarbon residue in the molecule with 8-26, preferably 10 -22 and in particular 12-18 carbon atoms or an alkyl aromatic radical having 6-18, preferably 8-16 aliphatic carbon atoms and an anionic and / or cationic water-solubilizing group. Zwitterionic surfactants are those that contain anionic and cationic groups in the molecule at the same time.

The anionic surfactants include those of the sulfonate, sulfate, phosphonate and phosphate type; There are also hardness-resistant compounds among the synthetic carboxylate-type surfactants.

Suitable surfactants of the sulfonate type are alkylbenzenesulfonates (C9_15-alkyl) or mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of sulfonia products. Also suitable are alkane sulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or bisulfite addition to olefins. Other useful surfactants of the sulfonate type are the esters of a-sulfofatty acids, e.g. the a-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or table fatty acid.

Other suitable surfactants of the sulfonate type are the fatty acid esters or fatty acid amides of lower oxyalkanoic or aminoalkane sulfonic acids. Fatty alcohol esters of lower sulfocarboxylic acids, e.g. Sulfoacetic acid, sulfosuccinic acid, sulfobenzoic acid, sulfosalicylic acid and sulfophthalic acid are useful.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol), those of secondary alcohols and the sulfuric acid monoesters and diesters of terminal or internal alkane diols. Sulfated fatty acid monoglycerides are also suitable. Other suitable surfactants of the sulfate type include sulfated nonionics, under "nonionics" the addition products of 1-40, preferably 4-20 moles of ethylene oxide and / or propylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty acid amide or alkylbenzene or Alkanesulfonamide are to be understood. The sulfated addition products of 2-8 mol of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18, carbon atoms, and with mono- or dialkylphenols with 6-14 carbon atoms are particularly important in the alkyl residues.

There are also hardness-resistant substances among the surfactants of the synthetic carboxylate type, especially

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ter the compounds with one or more carboxymethyl ether groups in the molecule. Examples include the carboxymethyl ethers of the nonionics listed above, in particular the ethoxylated fatty alcohols (3-8 glycol ether groups per molecule). Further examples are carboxymethyl ethers of terminal or internal alkane diols, of fatty alcohol glycerol or pentaerythritates.

All of these anionic surfactants are preferably used as salts, and the cations mentioned at the beginning for the aluminum silicates can be present.

Like the anionic surfactants, the cationic surfactants to be used according to the invention contain a straight-chain or branched-chain aliphatic or cycloaliphatic hydrocarbon radical having 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl- or cycloalkyl-aromatic radical 6-18, preferably 8-16 aliphatic carbon atoms. Basic nitrogen atoms are preferred as basic groups. Accordingly, the cationic surfactants can be aliphatic, cycloaliphatic, alkyl or cycloalkylaromatic amines of primary, secondary or tertiary nature, guanidine or biguanidine derivatives, compounds with hetero nitrogen, e.g. derivatives of morpholine, pyridine, imidazoline, piperidine, etc. It is preferably quaternary ammonium bases.

The hydrophobic radical and the part of the molecule carrying the water-solubilizing group can be connected to one another directly or via heteroatoms or via heteroatom groups, e.g. by ether or thioether atoms, amine nitrogen atoms, carboxylic acid ester, carboxylic acid amide or sulfonic acid amide groups, etc.

The cationic surfactants contain, especially if they are secondary, tertiary or quaternary ammonium bases, in addition to the hydrophobic radical (s), lower alkyl radicals containing 1-4 C atoms and 2-4 alkyl atoms containing alkyl radicals bound to the basic nitrogen -ste or aromatic residues, such as Phenyl or benzyl radicals.

Examples of cationic surfactants which can be used according to the invention include:

N-dodecyl-N ', N', N'-trimethyl-diamino-propane-l, 3,

Octyl or dodecyl trimethylammonium bisulfate,

Hexadecyl- or octadecyl-trimethyl-ammonium methosulfate, di-C i2-i8-alkyl-dimethylammonium chloride,

Dibutyl-allyl- or ethyl-cyclohexyl-allyl-dodecylammonium-

chloride,

Ethyl-crotyl-diethylaminoethyl-dodecylammonium chloride,

Orthophosphate one by reacting one mole of sebum

amine with 10 mol of ethylene oxide quaternary base obtained,

C10_16-alkyl-dimethyl-benzyl-ammonium chloride,

C10_i6-alkyl-dimethyl-dichlorobenzyl-ammonium bromide,

Dodecyl- / 3-phenoxyethyl-dimethyl-ammonium bromide,

C9_1s-alkyltoluyl-trimethyl-ammonium chloride,

p-octylphenoxy-ethoxyethyl-dimethyl-benzyl-ammonium

chloride,

Cio-i6-alkyl-dimethyl-naphthomethyl-ammonium chloride, dodecyl-o-dimethylbenzyl-dimethylammonium bromide, C9_15-alkyl-phenyl-trimethylammonium chloride,

also organic bases or their salts in which the hydrophobic radicals contain heteroatoms or heteroatom groups, such as e.g.

Octadecoxy-carbomethyl-trimethyl-ammonium chloride,

Dodecoxy-carbomethyl-pyridinium methosulfate,

Naphthenoxy-carbomethyl-quinolinium chloride,

Abietyloxy-carbomethyl-quinolinium bromide,

Di (dodecoxy-carbomethyl) dimethyl ammonium methosulfate,

Octadecyl-aminocarbomethyl-trimethyl-ammonium chloride,

Octadecyl anilino carbomethyl pyridinium bisulfate,

Dodecoxymethyl trimethyl ammonium chloride,

Octadecyl-thiomethyl-triethyl-ammonium bisulfate,

3rd

s

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4th

Octadecyl-carbamino-methyl-pyridinium chloride, octadecyloxy-carbamino-methyl-pyridinium methosulfate.

The organic nitrogen bases mentioned can be replaced by appropriately constituted compounds with a quaternary phosphorus, arsenic, etc. atom or with a ternary sulfur atom.

Cationic surfactants are also understood here to mean compounds with a secondary or tertiary nitrogen atom which contain alkylol radicals bonded to the nitrogen atom, such as e.g. Ethoxylation products of long chain primary or secondary amines or reaction products of 1 mole of fatty acid or fatty acid ester with at least 2 moles of a dialkylol amine, e.g. of diethanolamine.

The zwitterionic surfactants to be used according to the invention each contain at least one of the above-mentioned anionic and cationic groups in the molecule; however, several anionic and / or cationic groups can also be present. The same number of anionic and cationic groups are preferably present in one molecule.

The hydrophobic radical and the anionic or the cationic group can be connected to one another directly or via heteroatoms or heteroatom groups, e.g. by ether or thioether atoms, amine nitrogen atoms, carboxylic acid ester, carboxamide or sulfonamide groups, etc.

In addition to the hydrophobic radical (s), the cationic groups also contain lower alkyl radicals containing 1-4 C atoms, alkylol radicals containing 2-4 C atoms or aromatic radicals, such as, for example, bound to the basic nitrogen, phosphorus, sulfur or oxygen. Phenyl or benzyl residues.

Suitable compounds of this class are e.g. Betaines, sulfate betaines, sulfobetaines and, in those cases where a low phosphorus content is not a problem, also phosphate betaines. They can be represented by the following formulas:

I)

II)

R_ -

C - N I I o z

- Rr -

R "-

III)

R, -

Y I

N I

-Ri

- R,

n h

NO,

? 3

NO.

I <

R2

R_

- N - R. I 4

R «

- X

- X

- X

In these formulas:

Ri is an aliphatic, cycloaliphatic or alkylaromatic radical having 10-22 carbon atoms, preferably a straight-chain alkyl radical having 12-22 carbon atoms,

R2 is an alkyl radical with 1-4 C atoms or a hydroxyalkyl radical with 2-4 C atoms or a polyether radical of the formula (CH2-CH2-0) m-H with m = 2-5,

R3 represents the radical R2 or a phenyl, benzyl or tolyl radical,

R4 is an alkylene or hydroxyalkylene radical having 2-4 C atoms,

R5 is an alkylene radical with 2-4 C atoms,

R6 is a saturated or monounsaturated, preferably straight-chain hydrocarbon radical with 9-21, in particular 11-17, carbon atoms,

X the groups -COO-, -0-S03 ~ or -S03 ~,

Y groups H or X,

Z the groups H or R2,

n integers from 1-100.

5 The betaines falling under formula I can be obtained by treating tertiary amines of the formula RiR2R3N with halocarboxylic acids, e.g. Chloroacetic acid, bromoacetic acid or a-chloro-propionic acid, or by quaternizing aminocarboxylic acids or reaction products of secondary amines with acrylic-io acid in a suitable manner. Sulfate betaines can be obtained in an analogous manner by reacting the tertiary amines with halogenoalkylsulfuric acid esters or their salts. Sulfobetaines are obtained by reacting the tertiary amines with haloalkylsulfonic acids or sultones, in particular with 15 propane sultone.

Formula II contains examples of compounds with multiple betaine, sulfate or sulfobetaine groups. The starting point for their production is polyethyleneimine, polypropyleneimine or polybutyleneimine, which are alkylated and reacted in the aforementioned manner with halocarboxylic acids, haloalkylsulfonic acid esters, haloalkylsulfonic acids or sultones. The polyalkyleneimines can also first be reacted with derivatives of acrylic acid and then alkylated by introducing the R 1 group. Compounds of For-25 mei III can be obtained by condensing fatty acids of natural or synthetic origin with ethylenediamine, alkyl- or hydroxyalkylethylenediamine and then reacting them with halocarboxylic acids, haloalkylsulfonic acid esters or sulfonic acids or sultones. In addition to the 30 working methods indicated, other known production methods can also be used, e.g. the implementation of tertiary amines with epichlorohydrin and subsequent introduction of sulfate or sulfonate groups.

Examples include: 35 N-alkyl-N-dimethyl-ammonium acetate, N-alkyl-N-methyl-N-benzyl-ammonium acetate, N-alkyl-N-bis (2-hydroxyethyl) ammonium acetate, N-alkyl-N-diethylammonium propionate,

2-alkyl-1 - (2-hydroxyethyl) imidazolinium 1-acetate, 40 3- (N-alkyl-N-dimethylammonium) -2-hydroxypropyl sulfate, 1- (3-trimethylammonium) alkane sulfonate,

in which the alkyl or alkane groups are preferably straight-chain hydrocarbon radicals having 10-22, preferably 12-18, carbon atoms and can be derived, for example, from natural fat residues, such as coconut or tallow fat.

In the new compounds, the surfactants can be bound to the surface of the aluminum silicate particles, but they can also be embedded in the aluminum silicates. In most cases they are both adsorbed on the surface and embedded in the aluminum silicates.

It has been shown that surfactants with bulky hydrophobic residues (e.g. those with chain branches or ring systems) are more firmly anchored in the new compounds than those with straight-chain aliphatic residues. 55 If the new compounds or their suspensions are introduced into water, the latter surfactants are more easily dissolved out of the aluminum silicates than the former.

The new compounds made from cationic or zwitterionic surfactants are of particular interest: 60 these surfactants can also be bound to the surface of the aluminum silicates; but they can also be included in the aluminum silicates. In most cases, the cationic surfactants in particular are both adsorbed superficially (i.e. they form part of the cation “Kat” mentioned at the beginning in the composition of the aluminum silicates) and also included in the aluminum silicates.

The new substances release the bound surfactants in aqueous solution; therefore those with anionic are suitable

5

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or zwitterionic surfactants loaded types as additives for washing and cleaning liquors. The aluminum silicates loaded with cationic surfactants are characterized in aqueous suspension by a remarkable adsorption capacity for dissolved dyes or for dispersed pigments and can therefore be used as adsorbents for such substances. If the cationic surfactants have antimicrobial properties, the new compounds can be used wherever a gradual release of the cationic surfactants into the surrounding liquid is desired.

Examples

The aluminum silicates according to the invention were produced according to the following general procedure, unless another mode of operation is expressly described:

A solution of surfactant and alkali silicate in deionized water was placed in a vessel with 11 contents, and the aluminate solution was added in portions with simultaneous mixing using an intensive stirrer. The Na20 • 8 Si02 solution was prepared immediately before it was prepared from finely divided, slightly alkali-soluble silica and commercially available water glass. After stirring was continued for 30 minutes, an aliquot of the resulting aluminum silicate suspension was separated to isolate the aluminum silicate. For this purpose, the solution was suctioned off from the resulting solid and the filter residue was washed with deionized water. The filter residue was dried at 100 torr and 80 ° C for 3 hours and then analyzed. The products dried in this way were obtained in yields of 70-95% of theory.

The water content was determined according to Fischer, the anionic or cationic surfactants by dissolving 0.5 g of the new product in 50 ml in H2S04 at the boiling point and titration of the surfactant according to VW Reid, GF Longmann and E. Heinerth: "Tenside" volume 4 (1967), pages 292-304. The DGF standard method H III 4 (65) (DGF standard methods, Stuttgart 1969; DGF = German Society for Fat Science) was used to determine the zwitterionic surfactants.

All percentages are percentages by weight; the surfactant contents relate to the precipitation product which still contains bound water and is dried in the manner described above. If you converted them to the mixture of surfactant and anhydrous inorganic active substance, the results would be somewhat higher.

Comparative substances were prepared under the same conditions, but in the absence of surfactant. The Ca binding capacity of these and the products according to the invention was determined by the following method:

1 g of the product to be tested and dried in the manner described above (based on AS) was stirred for 15 minutes in a solution of 0.7865 g CaCl2 • H20 / 1 (= 30 ° dH) adjusted to pH = 10 at 50 ° C . After filtering off the aluminum silicate, the residual hardness x of the filtrate was determined. From this, the calcium binding capacity in mg CaO / g AS was calculated according to the formula: (30-x) • 10.

The surfactants used were designated by the following abbreviations; the anionic surfactants were present as Na salts. It means:

"ABS" is the salt of an alkylbenzenesulfonic acid with 10-15, preferably 11-13, carbon atoms in the alkyl chain obtained by condensing straight-chain olefins with benzene and sulfonating the resulting alkylbenzene,

“TPS” is the salt of an alkylbenzenesulfonic acid with 9-15, preferably 12 carbon atoms in the alkyl chain, obtained by condensing technical tetrapropylene with benzene and sulfonating the resulting alkylbenzene,

“MS” is the salt of a mixture of alkane mono- and disulfonates (= mersolate) obtained from the sulfonate by sulfochlorinating a C12-C18 paraffin, saponifying the sulfochloride formed with lye and separating the unreacted paraffin mixture,

"FAS" the sulfate of dodecyl alcohol,

"KA-ÄO-S" the sulfate of an adduct of 2 moles of ethylene oxide with 1 mole of a coconut fatty alcohol,

"OS" is a sulfonate obtained from a-olefin mixtures with 15-18 C atoms by sulfonation with SO 3 and hydrolyzing the sulfonation product with alkali, which essentially consists of alkenesulfonate and hydroxyalkanesulfonate, but also contains small amounts of disulfonates,

"FA-ÄO-CMÄ" the carboxymethyl ether of an adduct of 4.5 moles of ethylene oxide with 1 mole of a coconut fatty alcohol.

"CTMA" = cetyl-trimethylammonium chloride

"CTMB" = cetyl-trimethylammonium bromide

"LTMA" = lauryl trimethyl ammonium chloride

"LPYC" = lauryl pyridinium chloride

"LBDM" = lauryl-benzyl-dimethylammonium chloride

“LDBD” = lauryl dichlorobenzyl dimethyl ammonium chloride

"TDMA" = Di-palmityl / stearyP

-dimethylammonium chloride

* Alkyl mixture of tallow fatty acid

Example AI

Precipitation conditions:

0.5 g ABS as a 20% technical solution and 90.4 g of a 25% aqueous solution of Na20 • 8 Si02 dissolved in 300 ml deionized water is dissolved with a solution of 27.4 g sodium aluminate (41% Na20; 54 % A1203) in 80 ml of water

Composition of the dried precipitate: 1.3 Na20 • A1203 • 2.9 Si02 • 5.1 H20 0.9% ABS concentration of the suspension:

9.1% solids of the above composition calcium binding capacity:

110 mg CaO / g AS

Example A2

Precipitation conditions:

As example AI, but using 1.0 g ABS composition of the dried precipitate:

1.2 Na20 • A1203 • 2.8 Si02 • 6.4 H20 1.5% ABS

Concentration of the suspension:

9.5% solids of the above composition

109 mg CaO / g AS

Example A3

Precipitation conditions:

As example AI, but using 2.5 g ABS composition of the dried precipitate:

1.2 Na20 • A1203 • 2.9 Si02 • 4.8 HzO 3.5% ABS

Concentration of the suspension:

9.3% solids of the above composition calcium binding capacity:

114 mg CaO / g AS

Example A4

Felling conditions:

As example AI, but using 5 g ABS

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Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.9 Si02 ■ 4.2 H20 6.3% ABS concentration of the suspension:

9.4% solids of the above composition

107 mg CaO / g AS

Example A5

Precipitation conditions:

As example AI, but using 10 g ABS composition of the dried precipitate:

1.2 Na20 • A1203 • 3.2 SiOz • 6.3 HaO 11.5% ABS

Concentration of the suspension:

10.2% solids of the above composition

110 mg CaO / g AS

Example A6

Precipitation conditions:

As example AI, but using 50 g ABS composition of the dried precipitate:

1.3 Na20 • AI203 • 2.7 SiÓ2 • 3.9 H20 33.4% ABS '

Concentration of the suspension:

11.7% solids of the above composition

105 mg CaO / g AS

Example A7

Precipitation conditions:

As example AI, but using 1 g of TPS in the form of a solution containing 20 g / l. Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 • 6.4 H20 1.7% TPS concentration of the suspension:

9.5% solids of the above composition

108 mg / g ai

Example A8

Precipitation conditions:

As example AI, but using 1 g MS in the form of a solution containing 20 g / 1. Composition of the dried precipitation product:

1.1 Na20 • A1203 • 2.7 Si02 • 4.1 H20 0.1% MS

Concentration of the suspension:

8.9% solids of the above composition

104 mg CaO / g AS

Example A9

Precipitation conditions:

As example AI, but using 1 g of FAS in the form of a solution containing 20 g / 1. Composition of the dried precipitation product:

1.2 Na20 • A1203 • 2.9 Si02 • 6.4 H20 0.1% FAS

Concentration of the suspension:

9.3% solids of the above composition calcium binding capacity:

111 mg CaO / g AS

Example AIO

Precipitation conditions:

As example AI, but using 1 g

Fa-ÄO-S in the form of a solution containing 20 g / l. Composition of the dried precipitate:

1.2 NazO • A1203 • 2.9 Si02 ■ 6.1 H20 0.1% FA-ÄO-S

5 Concentration of the suspension:

9.3% solids of the above composition calcium binding capacity:

120 mg CaO / g AS

io Example Al 1

Precipitation conditions:

As example AI, but using 1 g of OS in the form of a solution containing 10 g / 1. Composition of the dried precipitate: 15 1.2 Na20 • A1203 • 2.8 Si02 • 6.7 H20 0.1% OS concentration of the suspension :

9.4% solids of the above composition

20 108 mg CaO / g AS

Example A12

Precipitation conditions:

As example AI, but using 1 g of 25 FA-ÄO-CMÄ

Composition of the dried precipitation product: 1.2 Na20 • A1203 • 2.9 Si02 • 5.3 H20 0.2% FA-ÄO-CMÄ Concentration of the suspension:

so 9.1% solids of the above composition calcium binding capacity:

98 mg CaO / g AS

Comparative experiments on examples A1-A12 35 precipitation conditions:

As example AI, but without the addition of surfactants. Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 • 5.3 H20 0.00% surfactant 40 Suspension concentration:

9.1% solids of the above composition calcium binding capacity:

90 mg CaO / g AS

A comparison of the 45 products produced according to Example A1-A12 with the product of the comparative experiment shows a significantly higher sedimentation rate in the latter, so that the products according to the invention can be stored longer without settling. In addition, the products according to the invention show a higher cation exchange rate than those produced without the addition of surfactants, i.e. bring the products with solutions of calcium salts e.g. with hard water, the exchange equilibrium is established faster.

55 Example A13

Precipitation conditions:

0.1 g ABS as a 20% technical solution and 9.05 g of a 25% aqueous solution of Na20 • 8 Si02 dissolved in 400 ml deionized water is mixed with a solution of 5.50 g 60 sodium aluminate (41% Na20; 54% A1203) in 80 ml of water

Composition of the dried precipitate:

1.2 Na20 ■ A1203 ■ 2.7 Si02 • 6.4 H20 0.7% ABS

65 Concentration of the suspension:

approx. 2% solids of the above composition

105 mg CaO / g AS

7

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Example Al4

Precipitation conditions:

4 g ABS as a 20% technical solution is dissolved in 10 ml deionized water and mixed with 361.6 g 25% Na20 • 8 Si02. 109.6 g of solid sodium aluminate (41% Na20, 54% A1203) were added to this solution 5 in portions with vigorous stirring.

Composition of the dried precipitate:

1.2 Na20 • A1203 • 2.7 Si02 • 5.1 H20 2.0% ABS ok

Concentration of the suspension:

37.2% solids of the above composition

98 mg CaO / g AS

15

Example AI 5

Precipitation conditions:

1.0 g ABS as a 20% technical solution and 32.6 g sodium aluminate (41% Na20, 54% A1203) dissolved in 300 ml deionized water, is dissolved with 70.0 g 25% 20 Na20 • 8 S02 in 100 ml of water added Composition of the dried precipitate:

1.1 Na20 • A1203 • 1.6 Si02 • 4.8 1.6% ABS

Concentration of the suspension: 25

9.2% solids of the above composition

115 mg CaO / g AS

Example A16 30

Precipitation conditions:

1.0 g of ABS as a 20% technical solution and 18.8 g of sodium aluminate (41% Na20, 54% A1203) dissolved in 300 ml of deionized water is dissolved in with a solution of 124.5 g of 25% Na20 ■ 8 S02 100 ml of water added 35

Composition of the dried precipitate:

1.5 Na20 • A1203 • 3.8 Si02 • 5.2 H20 1.7% ABS concentration of the suspension:

9.9% solid of composition 40 above

Calcium binding capacity:

116 mg CaO / g AS

Example A17

Precipitation conditions:

0.1 g ABS as a 50% technical paste and 148 g of a 45 35% aqueous solution of Na20 • 3.46 Si02 dissolved in 637 g deionized water are mixed with a solution of 54.8 g sodium aluminate (41% Na20, 54% A1203) in 160 g of water

Composition of the dried precipitate: 50

1.25 Na20 ■ A1203 • 2.75 Si02 -4 H20 0.032% ABS concentration of the suspension:

approx. 10% solids of the above composition calcium binding capacity: 55

100 mg CaO / g AS

In order to be able to determine the low surfactant content of the precipitation product according to Example A17 with sufficient accuracy, the amount of substance obtained in 3 batches was extracted with alcohol and the solution obtained was titrated as described above after concentration.

Example class

Precipitation conditions:

0.5 g CTMA as a 25% technical solution and 90.4 g 65 25% Na20 • 8 Si02 dissolved in 300 ml deionized water, is dissolved with a solution of 27.4 g sodium aluminate (41% Na2Q; 54% A1203) added in 80 ml of water

Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.9 Si02 • 6.4 H20 0.9% CTMA concentration of the suspension:

9.4% solids of the above composition

109 mg CaO / g AS

Example K2

Precipitation conditions:

As example Kl, but using 1.0 g CTMA

Composition of the dried precipitate:

1.2 Na20 • A1203 • 2.8 Si02 • 6.8 H20 1.9% CTMA

Concentration of the suspension:

9.6% solids of the above composition

113 mg CaO / g AS

Example K3

Precipitation conditions:

As example Kl, but using 2.5 g CTMA

Composition of the dried precipitate:

1.1 Na20 • A1203 • 3.1 Si02 • 5.5 H20 4.6% CTMA

Concentration of the suspension:

9.5% solids of the above composition

121 mg CaO / gAS

Example K4

Precipitation conditions:

As example Kl, but using 5 g CTMA

Composition of the dried precipitate:

1.3 Na20 • A1203 • 3.2 Si02 • 5.4 H20 6.3% CTMA

Concentration of the suspension:

9.9% solids of the above composition

114 mg CaO / gAS

Example K5

Precipitation conditions:

As example Kl, but using 10 g CTMA

Composition of the dried precipitate:

1.2 Na20 • A1203 • 2.9 Si02 • 4.8 H20 15.3% CTMA

Concentration of the suspension:

10.8% solids of the above composition

128 mg CaO / g AS

Example K6

Precipitation conditions:

As example Kl, but using 50 g CTMA

Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 • 5.7 H20 14.3% CTMA concentration of the suspension:

10.4% solids of the above composition

122 mg CaO / AS

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8th

Example K7

Precipitation conditions:

As example Kl, but using 1 g LTMA composition of the dried precipitation product: 1.3 NaaO • A1203 ■ 2.9 Si02 • 5.3 H20 1.4% LTMA concentration of the suspension:

9.2% solids of the above composition

115 mg CaO / g AS

Example K8

Precipitation conditions:

As example Kl, but using 1 g LPYC composition of the dried precipitate:

1.1 Na20 • A1203 • 2.8 Si02 • 6.5 H20 1.2% LPYC

Concentration of the suspension:

9.5% solids of the above composition

107 mg CaO / g AS

Comparative experiment to the examples K1-K8 precipitation conditions:

As example Kl, but without the addition of surfactants. Composition of the dried precipitation product:

1.2 Na20 • A1203 • 2.8 Si02 • 5.3 H20 0.00% surfactant

Concentration of the suspension:

9.1% solids of the above composition

90 mg CaO / AS

A comparison of the suspension prepared according to Example K1-K8 with the suspension of the comparative test shows a much higher sedimentation rate in the latter, so that the suspensions according to the invention can be stored longer without settling.

Example K9

Precipitation conditions:

0.1 g CTMA as a 25% technical solution and 9.05 g 25% Na20 • 8 Si02 dissolved in 400 ml deionized water is dissolved in a solution of 5.50 g sodium aluminate (41% Na20; 54% A1203) 80 ml of water added Composition of the dried precipitate: 1.1 Na20 • A1203 • 2.7 Si02 ■ 5.6 H20 approx. 2% CTMY concentration of the suspension:

1.8% solids of the above composition

116 mg CaO / AS

Example K10

Precipitation conditions:

4 g of CTMA as a 25% technical solution is dissolved in 10 ml of deionized water and mixed with 361.6 g of 25% NajO • 8 Si02. This solution was mixed in portions with vigorous stirring with 109.6 g of solid sodium aluminate (41% Na20, 54% A1203). Composition of the dried precipitate:. 1.3 Na20 ■ A1203 • 3.3 Si02 • 7.4 H20

1.9% CTMA concentration of the suspension:

38.3% solids of the above composition

98 mg CaO / g AS

Example Kll

Precipitation conditions:

1.0 g of CTMA as a 25% technical solution and 32.6 g of sodium aluminate (41% Na20, 54% A1203) dissolved in 300 ml of deionized water is mixed with a solution of 70.0 g of 25% Na20. 8 S02 in 100 ml of water. Composition of the dried precipitate: 1.0 NazO • A1203 • 1.6 Si02 ■ 5.3 H20 1.5% CTMA io Concentration of the suspension:

9.2% solids of the above composition

115 mg CaO / g AS

15 Example K12

Precipitation conditions:

1.0 g CTMA as a 25% technical solution and 18.8 g sodium aluminate (41% Na20, 54% A1203) dissolved in 300 ml deionized water, is dissolved with a solution of 124.5 g 20 25% Na20 • 8 Si02 in 100 ml of water. Composition of the dried precipitate: 1.5 Na20 • A1203 • 3.8 Si02 ■ 5.2 H20 1.9% CTMA concentration of the suspension:

25 9.7% solids of the above composition

108 mg CaO / g AS

Example K13

30 precipitation conditions:

As example Kl, but using 1.0 g LDBD

Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 • 5.4 H20 35 1.8% LDBD

Concentration of the suspension:

9.7% solids of the above composition

110 mg CaO / g AS

40

Example K14

Precipitation conditions:

As example Kl, but using 1.0 g LBDM

45 Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.7 Si02 • 5.9 H20 1.7% LBDM concentration of the suspension:

9.5% solids of the above composition so calcium binding capacity:

116 mg CaO / gAS

Example K15

Precipitation conditions:

55 As example Kl, but using 1.0 g TDMA

Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 ■ 5.7 H20 1.7% TDMA 60 concentration of the suspension:

9.7% solids of the above composition

114 mg CaO / g AS

65 Example K16

Precipitation conditions:

As example Kl, but using 1.0 g CTMB

9

624 914

Composition of the dried precipitate: 1.1 Na20 • A1203 • 2.9 Si02 • 4.8 H20 1.9% CTMB concentration of the suspension:

9.9% solids of the above composition

108 mg CaO / g AS

Example K17

Precipitation conditions:

As example Kl, but using 5 g of N, N-didodecylamine

Composition of the dried precipitate: 1.37 Na20 • A1203 • 2.7 Si02 • 4.18 H20 + 7.5% N, N-didodecylamine Concentration of the suspension:

approx. 10% solids of the above composition

115 mg CaO / g AS

Example class 8

Precipitation conditions:

As example Kl, but using 5 g of N-do-decyl-N, N-dimethylamine

Composition of the dried precipitate: 1.32 Na20 • A1203 • 2.57 Si02 • 4.52 H20 + 1.6% N-dodecyl-N, N-dimethylamine Concentration of the suspension:

approx. 10% solids of the above composition

115 mg CaO / g AS

Example K19

Precipitation conditions:

As example K1, but using 5 g of octylamine

Composition of the dried precipitation product: 1.01 Na20 • A1203 • 2.39 Si02 • 3.87 H20 + 3.1% octylamine Concentration of the suspension:

approx. 10% solids of the above composition

110 mg CaO / gAS

Example K20

Precipitation conditions:

As example K1, but using 5 g of C12-C18 coconut fatty acid polydehydanolamide containing 5 g of tertiary amino groups (= condensation product of 1 mol of coconut fatty acid and 2 mol of diethanolamine)

Composition of the dried precipitation product: 1.36 Na20 • A1203 • 2.38 Si02 • 3.78 H20 + 3.4% coconut fatty acid polydiethanolamide Concentration of the suspension:

approx. 10% solids of the above composition

120 mg CaO / g AS

Example K21

Precipitation conditions:

50 mg CTMA in the form of a 25% technical solution and 148 g of a 35% aqueous solution of Na20 • 3.46 Si02 dissolved in 637 g deionized water are mixed with a solution of 54.8 g sodium aluminate (41% Na20, 54 % A1203) in 160 g of water. Composition of the dried precipitate: 1.25 Na20 • A1203 • 2.75 SiOz • 4 H20 0.02% DTMA

Concentration of the suspension:

approx. 10% solids of the above composition

100 mg CaO / g AS

In order to be able to determine the low surfactant content of the precipitation product according to Example K21 with sufficient accuracy, the amount of substance obtained in 3 batches was extracted with alcohol and the solution obtained was concentrated after concentration as described above.

Example ZI

Precipitation conditions:

As example AI, but with the addition of 1 g of a betaine of the formula ch3 ch3

to the sodium silicate solution composition of the precipitate:

1.3 Na20 • A1203 • 2.7 Si02 • 5.6 +

0.05% betaine concentration of the suspension:

9.4% solids with the above composition

103 mg CaO / g AS

Example Z2

Precipitation conditions:

As example ZI, but using 5.0 g betaine

Composition of the dried precipitate:

1.2 Na20 ■ A1203 -.2.8 Si02 • 4.9 H20 +

0.06% betaine

Concentration of the suspension:

9.5% solids of the above composition

105 mg CaO / g AS

Example Z3

Precipitation conditions:

As example ZI, but using 25.0 g betaine

Composition of the dried precipitate:

1.3 Na20 • A1203 • 2.9 Si02 • 5.1 H20 +

0.1% betaine

Concentration of the suspension:

9.3% solids of the above composition

116 mg CaO / g AS

Example Z4

Precipitation conditions:

As example AI, but using 1 g of a betaine of the formula

R - N®- CH "" COO ~

/ \ rrjr

CH. CH

3 2 \ _ /

where R is a cocoalkyl radical (Ci2-Ci6-alkyl, average chain length C, 3.5)

Composition of the dried precipitate: 1.3 Na20 • A1203 • 2.8 Si02 • 5.2 H20 +

0.05% betaine concentration of the suspension:

9.4% solids of the above composition

106 mg CAO / g AS

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

624 914

10th

Example Z5

Precipitation conditions:

As example AI, but using 1 g of a betaine of the formula

CH - CH-OH

+ '2 2

R -N - ClU - COO

Composition of the dried precipitate: 1.3 Na20 • A1203 ■ 2.7 Si02 • 5.4 H20 + 0.05% sulfate betaine Concentration of the suspension:

9.4% solids of the above composition

106 mg CaO / g AS

ch2-ch2-o-ch2ch2oh with R = cocoalkyl

Composition of the dried precipitate: 1.3 Na20 • A1203 • 2.7 Si02 - 5.4 H20 +

0.05% betaine concentration of the suspension:

9.4% solids of the above composition

107 mg CaO / g AS

Example Z6

Precipitation conditions:

As example AI, but using 1 g of a betaine of the formula

.çh2-ch2oh

C12H25 "f

-N - CH2COO

\ / CH2 CH2

Composition of the dried precipitate: 1.3 Na20 • A1203 • 2.8 Si02 • 5.1 H20 +

0.05% betaine concentration of the suspension:

9.5% solids of the above composition

110 mg CaO / gAS

Example Z7

Precipitation conditions:

As example AI, but using 1.0 g of a sulfobetaine of the formula

C12H25 ~} C - CH2-CH2-CH2-S03-

3 CH3

Composition of the dried precipitate: 1.2 Na20 • A1203 • 2.8 Si02 • 5.1 H20 +

0.05% sulfobetaine concentration of the suspension:

9.5% solids of the above composition

107 mg CaO / g AS

Example Z8

Precipitation conditions:

As example AI, but using a sulfate betaine of the formula

C16H33 * CH2-CH0H-CH2-0S03-

CH3 CH3

Example Z9

io Precipitation Conditions:

50 mg of the betaine according to Example ZI as a 30% technical solution and 148 g of a 35% aqueous solution of Na20 • 3.46 Si02 in 637 g deionized water are dissolved with a solution of 54.8 g sodium aluminate (41% 15 Na20, 54% A1203) in 160 g of water

Composition of the dried precipitate: 1.25 Na20 • A1203 • 2.75 Si02 • 4 H20 0.05% betaine Concentration of the suspension:

20 approx. 10% solids of the above composition calcium binding capacity:

100 mg CaO / g AS

In order to be able to determine the betaine contents with sufficient precision in the precipitation products with very low betaine contents, in particular in the precipitation product according to Example 25 Z9, the amount of substance obtained in 3 batches was extracted with alcohol and freed from inorganic constituents via ion exchange columns. The filtrate was evaporated.

30th

Comparative experiment to examples Z1-Z9 precipitation conditions:

As example AI, but without the addition of surfactants. Composition of the dried precipitation product: 35 1.2 Na20 • A1203 ■ 2.8 SiOz • 5.3 H20 Concentration of the suspension:

9.1% solids of the above composition

90 mg CAO / g AS 40 A comparison with the suspensions prepared according to Example A1-A7 shows that in the comparative experiment, about 95% of the aluminum silicate settles at 25 ° C. on the bottom of the measuring vessel within 1 hour. The suspensions prepared in the manner according to the invention were still less than 90% sedimented after 24 45 hours.

As can be seen from the examples, the composition of the products according to the invention is in the range of 0.9-1.5 Kat2 / nO • A1203 • 1.3-4 Si02, the water content not being taken into account. As far as anionic and cationic surfactants are concerned, the surfactant content of the products dried in the manner described above is 0.01-35, preferably 0.1-20,% by weight; zwitterionic surfactants were found in the determination method described in amounts of 0.01-0.1% by weight.

55 The procedure described in the examples can also be modified by pouring the two solutions into the reaction vessel at the same time.

Like the products of Examples A1-A12, those of the other examples also showed a higher cation exchange rate than those produced without the addition of surfactants.

The crystallization capacity of the sodium silicates precipitated in the presence of hardness-resistant surfactants is lower than that in the usual way, i.e. in the absence of surfactants, manufactured sodium aluminum silicates. Therefore, the products manufactured according to the information in the examples remain in the X-ray amorphous state for longer or longer.

s

Claims (9)

624 914 1. A process for the preparation of cation-exchanging, water-insoluble, bound water-containing, X-ray amorphous alkali aluminosilicates by reacting aqueous solutions of alkali silicate and alkali aluminate, characterized in that a) the alkali silicate solution and the alkali aluminate solution are combined with one another in the presence of 0.005-10 % By weight, based on the total reaction mixture, of hardness-resistant ionic surfactants from the group of anionic, zwitterionic and cationic surfactants mixed together under normal atmospheric pressure and at room temperature of the solutions, b) that this mixture is constantly stirred for about 30 minutes, during which the aluminosilicate precipitates, c) separating the precipitate present in suspension in the aqueous phase from the aqueous phase, d) that the precipitated product is freed from water by washing from adhering mother liquor, and e) that it is subsequently dried at temperatures of 20-150 ° C., wherein the process steps are coordinated so that the new ionic surfactant is obtained as the process product in amounts of 0.01-50% by weight, based on the mixture of anhydrous alkali alumosilicate and surfactant, and bound alkali alumosilicate containing water, per mol A1203 0.7-1.5 mol Kat2 / nO, Kat = a cation of valence n, and 0.8-6 mol Si02 as well as a calcium binding capacity of 50-200 mg CaO / g anhydrous alkali alumosilicate and a particle size below 30 // . 2. The method according to claim 1, characterized in that one carries out the reaction in the presence of hardness-resistant anionic surfactants, in particular in the presence of anionic surfactants of the sulfate, sulfonate or carboxylate type. 2nd PATENT CLAIMS 3. The method according to claim 1, characterized in that one carries out the reaction in the presence of hardness-resistant cationic surfactants. 4. The method according to claim 1, characterized in that one carries out the reaction in the presence of hardness-resistant zwitterionic surfactants. 5. The method according to claim 1, characterized in that the aluminate, preferably dissolved in water, is mixed with an aqueous silicate solution, the surfactants being in the silicate solution. 6. The method according to any one of claims 1-5, characterized in that the washing is carried out after process step d) with water which contains the same ionic surfactants, and that one produces an alkali alumosilicate which has a calcium binding capacity of 80 to 160 mg CaO / g and preferably has a particle size of at most 8ju. 7. Use of the product produced by the process according to claim 1 for the preparation of an aqueous suspension, characterized in that the process product in a concentration of 2-50 wt .-%, based on that for about 3 hours at 80 ° C and 100 Torr dried product, suspended in water. 8. Use according to claim 7, characterized in that said concentration is 5-35 wt .-%. 9. Use according to claim 7 or 8, characterized in that a still moist process product is suspended in water to achieve the concentration mentioned. Aluminum silicates are known which contain exchangeable cations and which have the ability to bind the hardness formers of the water. Such substances are obtained in a simple manner, for. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in a solid state can be reacted with the other component present as an aqueous solution. The desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water. Such aluminum silicates can also be produced from Al (OH) 3, A1203 io or Si02 by reaction with alkali silicate solutions.