JPH10259015A - Production of crystalline inorganic builder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicate-based builder having highperformance by mixing silica sand with water, an Nacontaining compound, a K-containing compound and a Cacontaining compound and/or an Mg-containing compound, subjecting the obtained mixture to hydrothermal treatment and baking the product. SOLUTION: Silica sand having a maximum particle diameter of <=5,000 μm and an SiO2 content of >=90 wt.% is mixed with an Nacontaining compound such as NaOH, a K-containing compound such as KOH and water and further a Ca containing compound such as CaCO3 and an Mg-containing compound such as MgO to obtain a mixture having a water content of 24-50 wt.%. The mixture is subjected to hydrothermal treatment under 5-15 kg/cm<2> G at 150-200 deg.C for 1-24hr, dried, baked at 300-1,500 deg.C for 0.1-24 hr and pulverized to obtain anhydrous inorganic builder. The objective crystalline product expressed by the formula xM2 O.ySiO2 .zMeO (y/x is 1.0-4.0; z/y is <=1.0; M is Na or K; K/Na is 0.01-2.0; Me is Ca or Mg) can be produced by suspending the above anhydrous inorganic builder in water and drying the produced hydrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a silicate-based crystalline inorganic builder useful as an ion exchanger and an alkali agent.

[0002]

2. Description of the Related Art Silicate builders are used as detergent builders because they have an alkaline buffering capacity.
Particularly, the crystallized product has a high cation exchange capacity and is therefore frequently used as a detergent builder.

As a method for producing such a silicate builder, for example, a method using water glass as a starting material is disclosed in Japanese Patent Laid-Open No. 5-68888. This method is a method of producing crystalline sodium silicate having a layer structure by spray-drying a water glass solution to form amorphous sodium silicate, and then heating while returning a part in a burning zone. However, it is necessary to dry a large amount of water from the water glass, which is not a preferable method in terms of energy saving.

As a method for solving this problem, a method of directly firing a vitrified material is disclosed in Japanese Patent Application Laid-Open No. 6-72008. This method, water glass obtained by cooling a melt of sand and soda crushed, by heating the ground water glass, is a method for producing a crystalline sodium silicate, Na ₂ O-SiO ₂ of 2
Because it is a component, it is difficult to control the crystal system, and its properties as an ion exchanger for detergents are insufficient. Also, because a large amount of heat energy is used during vitrification,
This is not the preferred method.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily producing a high-performance silicate builder using inexpensive silica sand as a raw material in order to solve the above-mentioned problems. .

[0006]

Means for Solving the Problems To solve these problems, the present inventors studied the composition and production method using inexpensive silica sand as a raw material, and as a result, completed the production method of the present invention. Reached.

That is, the gist of the present invention is to provide (1) an anhydrous formula x
M ₂ O.ySiO ₂ .zMeO (where y / x = 1.0
~ 4.0, z / y is 1.0 or less, M is Na and K, K /
Na = 0.01 to 2.0, and Me is Ca and / or Mg. The method for producing a crystalline inorganic builder having a composition represented by the following formula: (a) water, a Na-containing compound, a K-containing compound, and a Ca-containing compound and / or M
adding a g-containing compound to obtain a mixture; (b) hydrothermally treating the mixture obtained in step (a);
A method for producing a crystalline inorganic builder, characterized by firing, (2) anhydrous xM ₂ O.ySiO ₂ (where y /
x = 1.0-4.0, M is Na and K, K / Na = 0.
01 to 2.0. In the method for producing a crystalline inorganic builder having the composition represented by the formula (a), water, a Na-containing compound and a K-containing compound are added to silica sand to obtain a mixture, and (b) the mixture is obtained in step (a). (C) a method for producing a crystalline inorganic builder, wherein the mixture is hydrothermally treated and calcined; (3) a Na-containing compound and K
The containing compounds are hydroxides and carbonates of Na and K, respectively.
(4) The method according to the above (1) or (2), which is a compound selected from the group consisting of nitrates and sulfates.
The method according to any one of the above (1) to (3), wherein the compound-containing compound and the K-containing compound are used as an aqueous solution of a Na-containing compound and an aqueous solution of a K-containing compound, respectively, and the concentrations of the aqueous solutions are each 20 to 70% by weight. (5) The hydrothermal treatment conditions described above in (1), wherein the conditions are 5 to 15 kg / cm ² G.
To (4), the water content of the mixture obtained in (6) step (a) is from 24 to
The production method according to any one of the above (1) to (5), which is 50% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a crystalline inorganic builder according to the present invention is directed to a method for producing a crystalline inorganic builder having a specific composition, wherein (a) water, a Na-containing compound and a K-containing compound are added to silica sand. If necessary, a Ca-containing compound and / or a Mg-containing compound are further added to obtain a mixture. (B) The mixture obtained in the step (a) is subjected to hydrothermal treatment, and (c) calcination. Things.

That is, in the present invention, in the production of a crystalline inorganic silicate in which potassium and, if necessary, an alkaline earth metal are positively introduced, the conditions for preparing the raw material before firing are specified. This is a production method in which a crystalline silicate can be easily obtained. The details will be described below.

[0010] The crystalline silicate in the present invention means a substance having the following composition. First embodiment: anhydrous xM ₂ O.ySiO ₂ .zMeO (where y / x = 1.0 to 4.0, z / y is 1.0 or less, M is Na and K, K / Na = 0.01-2.0, M
e is Ca and / or Mg. ), Or the second aspect: in waterless xM ₂ O · ySiO ₂ (wherein, y / x = 1.0~4.0, M is Na and K, K
/Na=0.01 to 2.0. )

The silica sand used in the present invention is Si sand.
The O ₂ content is desirably 90% by weight or more, preferably 95% by weight or more, and more preferably 97% by weight or more. Specific examples of these silica sands include, for example, Australian pearl sand and fluttery sand;
Indonesian Sarawak sand or silica sand crushed from silica stone is used.

The shape and size of the silica sand are not particularly limited, but those having a maximum particle size of 5000 μm or less are preferred from the viewpoint of reactivity.

The Na-containing compound and K-containing compound used in the present invention are used.
As the compound, sodium or potassium hydroxide
Substances, carbonates, nitrates, sulfates and the like.
Is NaOH, KOH, Na_TwoCO_Three, K_TwoCO_Three, N
aNO_Three, KNO_Three, Na_TwoSO _Four, K_TwoSO_FourEtc. are for
Can be. Na-containing compounds and K-containing compounds to be added
The amount is determined by the composition of the crystalline silicate.

In the present invention, water may be added alone, water may be substantially added by using a Na-containing compound or a K-containing compound as an aqueous solution, or both may be used in combination. You may. When the Na-containing compound and the K-containing compound are used as aqueous solutions, those prepared as separate aqueous solutions may be used, or those prepared as aqueous solutions containing both may be used. N
When the a-containing compound and the K-containing compound are used as respective aqueous solutions, the concentration of the aqueous solution is determined by the amount of Na present
Concentration of the containing compound and the K-containing compound in terms of anhydride,
20 to 70% by weight, and the amount of water added as an aqueous solution is preferably 24 to 50% by weight, particularly preferably 36 to 48% by weight, based on the total weight of the raw materials.
It is preferable that the concentration and the amount of the aqueous solution of the containing compound and the K-containing compound are adjusted. When an aqueous solution containing a Na-containing compound and a K-containing compound is used, the concentration of the aqueous solution is 2%.
0 to 70% by weight. When water is separately added, the water content of the whole raw material is preferably 24 to 50% by weight, particularly preferably 36 to 48% by weight based on the total weight.
Adjust so that

That is, the water content in the mixture obtained in step (a) is preferably from 24 to 50% by weight, particularly preferably from 36 to 48% by weight. If the amount of water is larger than this range, a large amount of energy is required at the time of firing, and if the amount of water is smaller than this range, the effect of hydrothermal treatment is small, crystallization at the time of firing becomes difficult, water resistance and ion The exchange characteristics tend to decrease.

The Ca-containing compound and the Mg-containing compound used for producing the crystalline silicate according to the first aspect of the present invention include calcium or magnesium oxides, hydroxides, carbonates, chlorides, nitrates, sulfates and the like. And specifically, CaCO ₃ , MgCO ₃ , Ca (OH) ₂ ,
Mg (OH) ₂ , MgO, CaCl ₂ .nH ₂ O, Mg
Cl ₂ .nH ₂ O, Ca (NO ₃ ) ₂ .nH ₂ O, Mg
(NO ₃ ) ₂ .nH ₂ O, CaSO ₄ .nH ₂ O, MgS
O ₄ .nH ₂ O (these are usually n = 0 to 20) and the like are used. The amount of the Ca-containing compound and the Mg-containing compound to be added is determined by the composition of the crystalline silicate as in the case of the Na-containing compound and the K-containing compound. In the present invention, it is preferable from the viewpoint of reactivity to perform a hydrothermal treatment after the addition of the Ca-containing compound and the Mg-containing compound.

In the production method of the present invention, a mixture is obtained by adding water, a Na-containing compound, a K-containing compound and, if necessary, a Ca-containing compound and / or a Mg-containing compound to the above-mentioned silica sand. After that, the hydrothermal treatment, then firing, but firing in this way after the hydrothermal treatment,
This is for increasing the reactivity and promoting crystallization.

Here, the hydrothermal treatment is performed in an alkaline aqueous solution.
This is an operation to dissolve silica sand under pressure, and the hydrothermal treatment condition is 5 to 15 kg / cm ² G, preferably 7 to 12 kg.
/ Cm ² G, more preferably 8 to 10 kg / cm ² G
It is desirable that The processing temperature is 150 to 200 ° C., preferably 160 to 190 ° C., and more preferably 170 to 200 ° C.
To 180 ° C, and the treatment time is not particularly limited, but is preferably 1 to 24 hours. In addition, the hydrothermally treated product may be dried before firing if necessary.
It can be performed by a known method such as spray drying and reduced pressure drying.

As the calcination method in the present invention, a generally known method is used, and usually 300 to 1500 ° C., preferably 500 to 1300 ° C., more preferably, using the calcination raw material obtained by the hydrothermal treatment as described above. Is 520-9
A method of firing at a temperature in the range of 00 ° C. to crystallize. In this case, if the heating temperature is lower than 300 ° C., the crystallization is insufficient and the water resistance is poor. Heating time is usually 0.1 ~
24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

After firing, the powder is crushed as required to adjust the particle size to a predetermined value. As the crusher, for example, a ball mill, a roller mill, or the like is used.

The crystalline inorganic builder of the present invention can be easily converted into a hydrate by a known method. For example, the inorganic builder obtained as described above is suspended in ion-exchanged water. Hydrated, dried and powdered.

The crystalline inorganic builder obtained by the production method of the present invention as described above has a first aspect: anhydrous xM ₂ O.ySiO ₂ .zMeO (where y / x = 1.0-4. 0, z / y is 1.0 or less, M is Na and K, K / Na = 0.01 to 2.0, M
e is Ca and / or Mg. ), Or the second aspect: in waterless xM ₂ O · ySiO ₂ (wherein, y / x = 1.0~4.0, M is Na and K, K
/Na=0.01 to 2.0. ). In the present invention, particularly, in the above formula, the first
In the embodiment, y / x = 1.5 to 2.5, K / Na = 0.0
2 to 1.0, z / y is 1.0 or less, preferably 0.0
From 0.5 to 1.0, and in the second embodiment, y / x
= 1.5-2.5 and K / Na = 0.02-1.0 are preferable from the viewpoint of structural stability in water. The composition in the present invention in which K is positively introduced not only enhances the ion exchange performance, but also acts on the silica network more favorably in water than Na, so that even when silica sand is used, the hydrothermal treatment can be performed. The amount of undissolved matter is small, and the formation of a crystalline silicate precursor is facilitated by a relatively low-temperature hydrothermal treatment. Therefore, according to the production method of the present invention, the filtration step can be omitted, which is industrially particularly useful.
If undissolved matter remains, it is difficult to produce crystals having excellent ion exchange properties by firing.

Since these crystalline inorganic builders have excellent ion exchange ability, ion exchange rate, alkali ability, water resistance, etc., they are useful as ion exchangers and alkali agents. Accordingly, the present invention provides a detergent composition containing the crystalline inorganic builder. Further, there is provided a detergent for clothing containing the detergent composition.

[0024]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, Examples 1 to
12 corresponds to the first mode, and Examples 13 to 21 correspond to the second mode.

The ion exchange characteristics in Examples and the like were as follows. 0.04 g of a sample pulverized to 325 mesh (average particle size: 10 ± 2 μm: measured by a laser diffraction particle size distribution analyzer, LA-500 manufactured by Horiba, Ltd.) was purified. Weigh and add calcium chloride solution (concentration is 100 ppm as CaCO ₃ ) 10
After stirring at 10 ° C. for 1 minute, filtration was performed using a membrane filter having a pore size of 0.2 μm, and the amount of Ca in 10 ml of the filtrate was measured by EDTA titration (CaCO ₃ / g · min). ).

The undissolved material after the hydrothermal treatment was filtered using a No. 5c filter paper and measured by the weight of the filtration residue.

Example 1 Silica sand (Fluttery sand from Australia, SiO
₂ Purity 99.8% by weight, average particle size 150 μm)
6g, NaOH aqueous solution (concentration of 48% by weight) 283.2
g, 135.9 g of KOH aqueous solution (concentration of 48% by weight), C
_{a (OH) 2 5.74g, Mg} (OH) were mixed ₂ 0.90 g, in a nickel crucible, 4 9.5 kg / cm ² G
Hydrothermal treatment for hours. There was no undissolved material.

This treated material is filtered in a nickel crucible without filtration.
It baked at 600 degreeC for 5 hours using the electric furnace. After firing, 3
The inorganic builder powder 1 was obtained by pulverizing the powder to 25 mesh or less and pulverizing the powder.

The ion exchange properties of the obtained inorganic builder are shown in Table 2 together with the production conditions. This powder showed crystallinity according to the X-ray diffraction pattern and also had excellent ion exchange properties.

Examples 2 to 21 The same procedures as in Example 1 were carried out except that the raw materials shown in Table 1 were used to prepare the compositions, hydrothermal treatment conditions and firing temperatures shown in Table 2. Thus, inorganic builder powders 2 to 21 were obtained. Table 2 shows the ion exchange characteristics of the obtained inorganic builder powder. In each case, it shows crystallinity,
The ion exchange properties were excellent.

Comparative Example 1 244.2 g of silica sand and 339.2 g of an aqueous NaOH solution (concentration of 48% by weight) were mixed, and a comparative powder 1 was obtained in the same manner as in Example 1. Also, some undissolved matter remained after the hydrothermal treatment.

Although the obtained comparative powder showed crystallinity,
Its ion exchange properties were inferior to the examples as shown in Table 2.

Comparative Examples 2 to 5 The same procedures as in Comparative Example 1 were carried out except that the raw materials shown in Table 1 were used, and the compositions, hydrothermal treatment conditions, and firing temperature were set as shown in Table 2. Thus, comparative powders 2 to 5 were obtained. In each case, the ion exchange characteristics of the obtained comparative powder were inferior to those of the examples as shown in Table 2.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

According to the method for producing a crystalline inorganic builder of the present invention, a high-performance silicate builder can be easily produced using silica sand which is easy to handle as a raw material.

Continuation of front page (72) Inventor Masaharu Takeno 1334 Minato, Wakayama-shi Kao Corporation Research Laboratory

Claims (6)

[Claims] 1. Anhydrous xM ₂ O.ySiO ₂ .zMeO
(Where y / x = 1.0 to 4.0, z / y is 1.0 or less, M is Na and K, K / Na = 0.01 to 2.0, M
e is Ca and / or Mg. In the method for producing a crystalline inorganic builder having a composition represented by (a), (a)
Water, Na-containing compound, K-containing compound, and C
a) obtaining a mixture by adding an a-containing compound and / or a Mg-containing compound; (b) hydrothermally treating the mixture obtained in the step (a); and (c) calcining the mixture. . 2. Anhydrous xM ₂ O.ySiO ₂ (wherein y
/X=1.0-4.0, M is Na and K, K / Na =
It is 0.01 to 2.0. In the method for producing a crystalline inorganic builder having a composition represented by the formula (a), water, a Na-containing compound and a K-containing compound are added to silica sand to obtain a mixture, and (b) the mixture is obtained in step (a). A method for producing a crystalline inorganic builder, comprising subjecting the mixture to a hydrothermal treatment and calcining (c). 3. The Na-containing compound and the K-containing compound are compounds selected from the group consisting of hydroxides, carbonates, nitrates and sulfates of Na and K, respectively.
The manufacturing method as described. 4. A Na-containing compound and a K-containing compound are used as an aqueous solution of a Na-containing compound and an aqueous solution of a K-containing compound, respectively.
The production method according to any one of claims 1 to 3, wherein the content is% by weight. 5. The hydrothermal treatment condition is 5 to 15 kg / cm ^2.
5. The method according to claim 1, wherein G is G. 6. The method according to claim 1, wherein the water content of the mixture obtained in step (a) is 24 to 50% by weight.