JPH1111933A - Production of amorphous aluminosilicate powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an amorphous aluminosilicate powder excellent in alkaline earth metal ion capturing ability and oil absorbing ability by synthesizing an amorphous aluminosilicate slurry, substituting an org. solvent for the water contained in the slurry and drying the slurry at a specified temp. SOLUTION: An amorphous aluminosilicate slurry is synthesized, an aliphatic and/or arom. orb. solvent preferably having <=50 dyn/cm surface tension is substd. for the water contained in the slurry and the slurry is dried at <=150 deg.C to obtain the objective amorphous aluminosilicate powder having higher alkaline earth metal ion capturing ability and higher oil absorbing ability than powder obtd. by drying the synthesized slurry as it is. The amorphous aluminosilicate slurry is obtd. by mixing and reacting an aq. alkali metal silicate soln. with an aq. alkali metal aluminate soln. It is preferably obtd. by mixing an aq. alkali metal silicate soln. in which the molar ratio of R2 O to SiO2 (R is the alkali metal) is 0.25-4.0 with an aq. alkali metal aluminate soln. in which the molar ratio of R2 O to Al2 O3 (R is the alkali metal) is 1.0-3.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a detergent, especially an alkaline earth metal ion-capturing ability and oil absorption suitable as a detergent builder to be incorporated into a detergent for clothes, a detergent for dishes, a detergent for face washing or an industrial detergent. Aluminosilicate, which is highly amorphous and can be used as an alkaline earth metal ion scavenger, and which is substantially amorphous as measured by an X-ray diffractometer (hereinafter throughout this specification, this is referred to simply as "amorphous" Aluminosilicate ") powder.

[0002]

2. Description of the Related Art NaA zeolite, which is currently used as a detergent builder, has a large ability to trap alkaline earth metal ions, so that a slurry mixed with an anionic surfactant is spray-dried to obtain a granular detergent. It is blended. However, this NaA-type zeolite is
Since the oil absorption is about 40 g / 100 g, when kneaded with a nonionic surfactant and blended in a detergent, a material having a large oil absorption, such as white carbon, having no alkaline earth metal ion trapping ability. Was not a granular detergent without the addition of.

For this reason, there is a disadvantage that it is difficult to make the detergent compact. As a means for solving the above problems, amorphous aluminosilicate is being used,
Until now, amorphous aluminosilicates have been dried and pulverized in a water-containing state, and the ability of this amorphous aluminosilicate to capture alkaline earth metal ions and absorb oil has been determined by blending it with a detergent. For use as a metal ion scavenger, its performance is not always satisfactory, and there has been a demand for the production and development of an amorphous aluminosilicate having both excellent performances.

[0004]

SUMMARY OF THE INVENTION The present inventors have surprisingly devised a drying means in the course of conducting research to solve this problem, so that the ability to capture alkaline earth metal ions and the ability to absorb oil have been improved. The present inventors have found that an excellent product can be obtained as compared with the product obtained by the method of the present invention, and have made the present invention. Accordingly, an object of the present invention is to provide a method for producing an amorphous aluminosilicate having excellent characteristics with respect to both of these properties.

[0005]

SUMMARY OF THE INVENTION The present invention is to provide an amorphous aluminosilicate having the above-mentioned excellent properties. First, after synthesizing a slurry of the amorphous aluminosilicate, the water content is reduced. After replacing with an organic solvent, 150
Second, a method for producing an amorphous aluminosilicate powder which is dried at a temperature of not more than 50 ° C. is as follows.
A method for producing an amorphous aluminosilicate powder, which is an aliphatic and / or aromatic liquid of yn / cm or less, is described below. Provided is a method for producing a porous aluminosilicate powder.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above-mentioned problems, the present inventors have intensively studied the effects of the powdery amorphous aluminosilicate slurry on the alkaline earth metal capturing ability and the oil absorbing ability during drying. Was piled up. As a result, the moisture content is preferably replaced with an aliphatic and / or aromatic organic solvent having a surface tension of 50 dyn / cm or less, followed by drying at a temperature of 150 ° C. or less. It has been found that both of the alkaline earth metal trapping ability and the oil absorbing ability are higher than those of the prior art.

[0007] That is, the amorphous aluminosilicate powder obtained by drying the synthetic slurry as it is has low alkaline earth metal trapping ability and low oil absorption ability, but is dried after replacing the contained water with the above organic solvent. As a result, it has been found that an amorphous aluminosilicate powder having a high alkaline earth metal trapping ability and a high oil absorbing ability can be easily obtained, which has led to the present invention. The obtained aluminosilicate is
No agglomeration occurs, and no agglomeration is caused as in the case of drying in a water-containing state.

Hereinafter, the method for producing an amorphous aluminosilicate of the present invention will be described in more detail. The amorphous aluminosilicate of the present invention is preferably produced by mixing and reacting an aqueous solution of an alkali metal silicate and an aqueous solution of an alkali metal aluminate. As the alkali metal silicate, sodium silicate or potassium silicate can be used. As the alkali metal aluminate, sodium aluminate, potassium aluminate and the like can be used.

The aqueous solution of an alkali metal silicate or the aqueous solution of an alkali metal aluminate may be mixed with an aqueous solution of an alkali metal hydroxide, if necessary. Further, an aqueous solution of an alkali metal hydroxide may be mixed when the aqueous solution of an alkali metal silicate and the aqueous solution of an alkali metal aluminate are mixed. Sodium hydroxide, potassium hydroxide and the like can be used as the aqueous alkali metal hydroxide solution.

The method of mixing the aqueous solution of the alkali metal silicate and the aqueous solution of the alkali metal aluminate is not particularly limited.
One aqueous solution of an alkali metal salt may be added to a vessel filled with one aqueous solution of an alkali metal salt, or both aqueous solutions of an alkali metal salt may be simultaneously added to a reaction vessel.
The addition is preferably performed while stirring so that the respective aqueous alkali metal salts can be sufficiently mixed.

More specifically, the molar ratio of R ₂ O / SiO ₂ is 0.1.
And alkali-metal silicate salt solution of from 25 to 4.0, R ₂ O
/ Al ₂ O ₃ molar ratio is preferably mixed with an aqueous solution of an alkali metal aluminate having a molar ratio of 1.0 to 3.0 (here,
R is a general term for one or more elements selected from alkali metals). In that case the mixing composition, the alkali metal salt solution silicate and an alkali metal aluminates solution, SiO ₂ minutes Al ₂ O ₃ minutes R ₂ O content and the SiO in a molar ratio of _2: Al ₂ O _3:
It is preferable that R ₂ O = 5 to 30: 2 to 10:60 to 93 (where R is a general term of one or more elements selected from alkali metals).

[0013] The slurry-like amorphous aluminosilicate obtained as a result of this mixing is first subjected to filtration and washing with water to remove the mother liquor from the precipitated precipitate. After that, the filter cake generated here is filtered and washed again with an organic solvent,
The water adhering to the cake is replaced by an organic solvent. In this case, the replacement with the organic solvent is preferably at least 50% by weight, particularly at least 60% by weight of the contained water.
The organic solvent used here must be capable of replacing water on the surface of the amorphous aluminosilicate powder. Further, in order to suppress condensation on the surface of the amorphous aluminosilicate powder when dried later, the surface tension is preferably small, and is preferably substantially 50 dyn / cm or less, and is substantially 30 dyn / cm or less. Is more preferable.

That is, an organic solvent satisfying these conditions,
That is, any aliphatic and / or aromatic organic solvent having a surface tension of 50 dyn / cm or less can be used. Among those that are used well,
There are lower alcohols such as methanol, ethanol, isopropyl alcohol and butyl alcohol, and benzene and acetone. Water may be contained in the organic solvent. However, when the content of water is large, the efficiency of substitution with the organic solvent becomes small.
% By weight, more preferably 5% by weight or less.

The slurry of the amorphous aluminosilicate substituted with the organic solvent is 150 ° C. or lower, preferably 10 ° C.
Dry below 0 ° C. If the temperature is high, characteristics such as the ability to capture Ca ions are undesirably reduced. Various methods can be applied as means for drying, but spray drying, fluidized drying, mixed drying, standing drying or vacuum drying is preferable. In particular, when vacuum drying is used, 60
It is preferable because drying at a temperature of not more than ℃ is easy and the used organic solvent can be easily recovered. The collected organic solvent can be reused. When spray drying is used, the drying time is short and the temperature can be increased, but the temperature is preferably 150 ° C. or lower.

The amorphous aluminosilicate according to the present invention comprises X
When measured with a line diffractometer, no crystalline substance is detected, or even if it is detected, the content is preferably 5% by weight or less.
Such amorphous aluminosilicates are suitable as alkaline earth metal ion scavengers, especially as detergent builders to be incorporated into clothing detergents, dishwashing detergents, face wash detergents or industrial detergents.

[0016]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples 1 and 2 and Comparative Examples 1 and 2, but the present invention is not limited thereto. In addition, the measured value was measured by the following method. [Ca ion trapping ability by Method A] Sample 1.
0 g was weighed and a calcium chloride solution (CaO concentration was 30
0 wt ppm) in 1000 ml, and further added 1N sodium hydroxide solution to adjust the pH to 10.0 to 10.5.
Then, the mixture was stirred at 25 ° C. for 10 minutes. Ten minutes later,
Filtration was performed using filter paper of No. 5 type C (defined in JIS P3801; the same applies hereinafter). Take 20 ml of the filtrate, measure the amount of Ca in the filtrate by EDTA titration, and determine the amount of Ca ions remaining in the filtrate, that is, not captured (uncaptured) from the value. By subtracting the amount of uncaptured Ca ions from the amount of Ca ions present, the amount of Ca ions captured per gram of anhydride in the sample was determined.

[Ca ion trapping ability by method B] 0.10 g of a sample in terms of anhydride was weighed out, and a calcium chloride solution (C
(aO concentration is 30 wt ppm), and pH was adjusted to 10.0 by adding 1N sodium hydroxide solution.
After adjusting to 0 to 10.5, the mixture was stirred at 25 ° C. for 10 minutes. After 10 minutes, the mixture was filtered using a filter paper of No. 5 type C (defined in JIS P3801; the same applies hereinafter). The filtrate 1
After taking 0 ml and diluting 10 times with pure water, the Ca concentration in the filtrate was measured by atomic absorption spectrometry, and from the value,
The amount of uncaptured Ca ions remaining in the filtrate was determined, and then the amount of uncaptured Ca ions was subtracted from the amount of Ca ions originally present, whereby the amount of Ca per 1 g of anhydride in the sample was determined.
The amount of trapped ions was determined.

[Oil Absorption] In a 300 ml beaker, weigh 25 g of the dried sample powder, and mix well with 1 g of linseed oil.
Was added. From the initial dry powdery state to a lump (lump) gum-like state (time point), that is, a glossy and smooth paste, the weight was measured as the adsorption limit, and the oil absorption per 100 g of the sample The amount was determined. If linseed oil is added any more, the viscosity sharply decreases.

Example 1 A commercially available aqueous solution of sodium silicate No. 3 (Na ₂ O: 9.49% by weight, SiO ₂ : 29.3)
336.0 g) was placed in a 1000 ml beaker and stirred for 48% aqueous sodium hydroxide solution.
By adding 0 g, 372.0 g of an aqueous sodium orthosilicate solution (Na ₂ O / SiO ₂ molar ratio 0.48) was prepared (hereinafter referred to as “solution A”). Commercially available sodium aluminate solution (Na ₂ O: 20.46% by weight, Al ₂ O ₃ : 20.
32 _{wt%, Na 2 O / Al 2} O 3 molar ratio 1.66) 45
6.0 g was placed in a 3000 ml beaker, and 720.0 g of a 48% aqueous sodium hydroxide solution was added thereto with stirring to give a sodium aluminate aqueous solution (Na ₂ O / Al ₂ O _3).
(Molar ratio: 7.79) (hereinafter referred to as “solution B”).

Solution B is stirred vigorously with a homomixer (700
(0 rpm), solution A was added slowly over 20 minutes. The molar ratio of each oxide component in the mixed solution is S
iO ₂ : Al ₂ O ₃ : Na ₂ O = 15.8: 8.7: 75.
5, and the SiO ₂ / Al ₂ O ₃ molar ratio was 1.81. After completion of the addition, stirring was continued for 30 minutes to cause a reaction to precipitate a precipitate. The temperature of the reaction solution during and after the addition is 25
４０40 ° C. After the stirring was completed, the reaction product was filtered through a type 5 C filter paper and washed with 7500 g of pure water. The obtained cake is further subjected to 1200 g of 99.5 wt% ethanol (surface tension: 22.0 dyn / cm, 25 ° C.).
And the water content in the cake was replaced with 99.5% by weight of ethanol. Thereafter, vacuum drying was performed at 40 degrees to obtain aluminosilicate powder.

The weight of the aluminosilicate powder was 195.0 g in terms of anhydride. As a result of chemical analysis, Na ₂ O: Al ₂ O ₃ : SiO ₂ = 1.
63: 1.00: 2.81. Further, it was confirmed by X-ray diffraction that it was amorphous. BET surface area (unit: m ² / g), amount of captured Ca ions by method A and method B (unit: mgCaO / g), oil absorption (unit: g / 10)
0g) is shown in Table 1.

Example 2 The organic solvent used to replace the water contained in the cake was 99.5 wt% isopropyl alcohol (surface tension: 20.9 dyn / cm, 25 ° C.)
Aluminosilicate powder was obtained in the same manner as in Example 1, except that The weight of this aluminosilicate powder was 192.0 g in terms of anhydride. Chemical analysis showed that the oxide molar ratio was Na ₂ O: Al ₂ O ₃ : SiO ₂ =
1.63: 1.00: 2.81, which was equivalent to the amorphous aluminosilicate powder obtained in Example 1. Also,
X-ray diffraction confirmed that the film was amorphous. BET surface area (unit: m ² / g), amount of captured Ca ions by method A and method B (unit: mgCaO / g), oil absorption (unit: g)
/ 100 g) are shown in Table 1.

Comparative Example 1 An aluminosilicate powder was obtained by performing the same operation as in Example 1 except that the water content in the cake was not replaced with an organic solvent and vacuum drying was performed at 40 ° C. as it was. The weight of this aluminosilicate powder was 199.0 g in terms of anhydride. Chemical analysis revealed that the molar ratio of oxides was Na ₂ O: Al ₂ O ₃ : SiO ₂ = 1.68: 1.
00: 2.72. It was confirmed by X-ray diffraction that it was amorphous. BET surface area (unit: m ² /
g), the amount of captured Ca ions by the method A and the method B (unit:
mgCaO / g) and oil absorption (unit: g / 100 g) are shown in Table 1.

Comparative Example 2 Example 1 except that the water content in the cake was replaced with a mixed solution of ethanol and water containing 90.0% by weight of ethanol and then vacuum dried at 40 ° C.
The same operation as described above was performed to obtain an aluminosilicate powder. The weight of this aluminosilicate powder was 201.5.0 g in terms of anhydride. Chemical analysis showed that the molar ratio of oxides was Na ₂ O: Al ₂ O ₃ : SiO ₂ = 1.70:
1.00: 2.71. It was confirmed by X-ray diffraction that it was amorphous. BET surface area (unit: m ² /
g), the amount of captured Ca ions by the method A and the method B (unit:
mgCaO / g) and oil absorption (unit: g / 100 g) are shown in Table 1.

[0025]

[Table 1]

According to this table, after replacing the water content in the cake of the amorphous aluminosilicate with the organic solvent, 1
It can be more clearly understood that by drying at 50 ° C. or lower, an amorphous aluminosilicate having high alkaline earth metal ion trapping ability and high oil absorbing ability can be obtained.

[0027]

Industrial Applicability According to the present invention, an aluminosilicate powder having both high alkaline earth metal ion trapping ability and high oil absorption ability and excellent characteristics can be produced, and the obtained aluminosilicate powder is currently used as a detergent builder. Compared with the used NaA type zeolite, the alkaline earth metal ion trapping ability is almost the same, the oil absorbing ability is large, the surfactant impregnation is excellent, the detergent for clothes, dishwashing detergent, face wash It can be used as an alkaline earth metal ion scavenger suitable as a detergent builder to be added to a detergent or industrial detergent.

Claims (3)

[Claims] 1. A method for producing an amorphous aluminosilicate powder, comprising synthesizing a slurry of an amorphous aluminosilicate, replacing the water content with an organic solvent, and then drying at a temperature of 150 ° C. or lower. 2. An organic solvent having a surface tension of 50 dyn / c.
The method for producing an amorphous aluminosilicate powder according to claim 1, which is an aliphatic and / or aromatic liquid of m or less. 3. The method for producing an amorphous aluminosilicate powder according to claim 1, wherein water in the organic solvent is 10% by weight or less.