JPH07187654A - Amorphous aluminosilicate and its production - Google Patents

Abstract

PURPOSE:To obtain an amorphous aluminosilicate improved in oil absorption and ion-exchange capacity by allowing an alkali metal aluminate aq. soln. to react with an alkali metal silicate aq. soln. CONSTITUTION:(A) 10-100wt.% alkali metal aluminate aq. soln. having a molar ratio of M2O (M is an alkali metal)/Al2O3 of 1.0-6.0 and (B) 3-50wt.% alkali metal silicate aq. soln. having the molar ratio of SiO2/M2O of 1.0-4.0 are allowed to react under non-agitation or weak agitation of an agitating element tip speed of 0-1m/s to produce a reaction product. The remaining materials are added to this reaction product to allow to react, and an amorphous aluminosilicate having >=1.0mum and <=0.4mum average fine pore size (mercury forcing method), <=0.4cc/g fine pore volume, >=150ml/100g oil absorption and >=150mgCaCO3 cation-exchange capacity and expressed by the formula (M is an alkali metal, Me is an alkaline earth metal, 0<=x<=0.1, 0.5<=y<=2.0 and 1.5<=z<=6.0 is produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous (amorphous) aluminosilicate and a method for producing the same, and more specifically, it has a pore size of 1.0 μm as determined by mercury porosimetry.
It has a pore volume of m or more and 0.4 μm or less of 0.4 cc / g or less, is inexpensive, has a high oil absorption capacity, a high cation exchange capacity, and is very fast for solid-liquid separation of the reaction slurry. The present invention relates to an amorphous aluminosilicate having a characteristic that it can be easily performed and a method for producing the same.

[0002]

2. Description of the Related Art Amorphous hydrated silica called white carbon has been known so far as a highly oil-absorbing inorganic carrier, and its properties are utilized for rubber. Many uses have been developed, such as fillers and papermaking fillers. Further, as the highly oil-absorbing silica, dry silica called Aerosil is known, and it is used as a filler for rubber and plastics, but this is expensive and is used in the paper manufacturing industry. It is not suitable for use in fields requiring inexpensive raw materials. Also,
The petal-like calcium silicate powder marketed under the trade name "Florite" is 500-600 ml / 100 g
It has a very high oil absorption property, but it is expensive.

The above-mentioned silicic acid and calcium silicate powder have a drawback that they have no cation exchange ability in addition to the above-mentioned drawbacks, and are used for applications requiring a softening action of water, for example, for detergent builders and agricultural chemicals. It is unsuitable for the purpose of preventing scale generation due to carriers or ionic impurities such as Ca and Mg ions. As a substance having a high cation exchange ability, crystalline aluminosilicate called zeolite is well known, and in particular, synthetic zeolite 4A type is actually used in large quantities as a builder for synthetic detergents. However, zeolite itself is 1-10μ
Although they are densely packed crystal particles of m and have many holes of molecular order, the retention of macroscopic voids related to oil absorption capacity is extremely small, and the oil absorption capacity is at most 60 ml / 100 g. However, high dispersibility in water cannot be expected, and it cannot be used for applications requiring high oil absorption.

Amorphous aluminosilicate powder marketed under the trade name of "Zeolex" has the same use as white carbon, but has a low oil absorption and a low cation exchange capacity. Various manufacturing methods of amorphous aluminosilicates such as "Zeolex" have been studied. For example, Japanese Patent Laid-Open No. 52-
No. 58099 discloses that an aqueous solution of alkali metal silicate is added and mixed with an aqueous solution of alkali metal aluminate at a temperature of 70 ° C. or lower, and the reaction system is kept at pH 10.5 or higher to absorb oil of 75 ml / 100 g. Above, cation exchange capacity 200 mg CaCO ₃
Disclosed is a method for producing an amorphous alkali metal aluminosilicate fine powder having a physical property of 1 g / g or more. However, this method cannot produce amorphous aluminosilicates having a high oil absorption of 150 ml / 100 g or more. Further, in JP-A-57-92515, an alkaline aluminate aqueous solution and an alkaline silicate aqueous solution are continuously supplied to a reaction system at a temperature of 60 ° C. or less, and a large particle size
A method for producing an amorphous aluminosilicate having excellent cation exchange ability, which is easy to filter and wash, is disclosed. Further, JP-A-62-70220 discloses a sodium aluminate solution in an alkali solution whose concentration is controlled. And a method for producing an amorphous aluminosilicate by individually dropping sodium silicate solution, but these methods are not intended to increase the oil absorption amount, By this method, it is difficult to obtain a highly oil-absorbing amorphous aluminosilicate.

Further, JP-A-58-156527 discloses that by adding an alkali metal aluminate solution and an alkali metal silicate solution to water at a temperature of 60 ° C. or lower, or by adding an alkali metal silicate. By adding the salt solution to the alkali metal aluminate salt solution at a temperature of 60 ° C or less, the oil absorption is 200 ml / 100 g or more, and the cation exchange capacity has the same physical properties as various zeolites. A method of manufacturing is disclosed. However, in this method, the reaction slurry is subjected to solid-liquid separation by filtration.However, since the crystals are fine particles, the filtration rate is very slow, the pore size is small, and the pore volume of 0.4 μm or less is used. Is 0.5 cc / g or more, the solubility in water becomes poor when a liquid activator is absorbed.

The present invention has a high oil absorption capacity, a high cation exchange capacity, a large pore size, a small pore volume of 0.4 μm or less, and a solid-liquid separation process for extracting fine particles from a reaction slurry. It is an object of the present invention to provide an amorphous aluminosilicate having a very high speed and an excellent production efficiency and a method for producing the same.

[0007]

The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems of the prior art. That is, the present invention, the formula x (MeO) · y (M ₂ O) · Al ₂ O ₃ · z (SiO ₂ ) (wherein M is an alkali metal, Me is an alkaline earth metal, x, y , z is 0 ≦ x ≦ 0.1, 0.5 ≦ y ≦ 2.0, 1.5 ≦
Indicates a number within the range of z ≦ 6.0. ) Is an amorphous aluminosilicate having an average pore size of 1.0 μm or more and a volume of pores of 0.4 μm or less (hereinafter abbreviated as micropore volume) of 0.4 cc / g or less. The present invention provides an amorphous aluminosilicate having an oil absorption capacity of 150 ml / 100 g or more and a cation exchange capacity of 150 mgCaCO ₃ / g or more. Also,
The present invention is a method for producing an amorphous aluminosilicate by reacting an alkali metal aluminate aqueous solution with an alkali metal silicate aqueous solution, wherein one of the alkali metal aluminate aqueous solution and the alkali metal silicate aqueous solution is
Mix 10 to 100% by weight with the other 3 to 50% by weight,
Disclosed is a method for producing an amorphous aluminosilicate having the above characteristics, which comprises preliminarily reacting with a stirring blade tip speed of 0 to 1 m / sec without stirring or under weak stirring and then reacting with the rest of the raw materials. .

The raw materials for producing the amorphous aluminosilicate having the above-mentioned characteristics of the present invention are (a) an aqueous solution of alkali metal aluminate and (b) an aqueous solution of alkali metal silicate, and if necessary, (c) ) Alkali metal salt and / or alkaline earth metal salt, (d) Fine powder and / or porous substance, (e) Water-soluble polymer or water is added to each of the above liquids or reaction systems, and the concentration, pH and molar ratio are added. Adjust. In the present invention, the alkali metal belongs to Group IA of the Periodic Table, and the alkaline earth metal belongs to Group IIA of the Periodic Table, and a mixture of two or more of these can be used. Usually sodium is preferred. Next, used in the present invention (a) an aqueous solution of alkali metal aluminate, (b)
The aqueous solution of alkali metal silicate, (c) alkali metal salt and / or alkaline earth metal salt, (d) fine powder and / or porous material, and (e) water-soluble polymer will be described.

(A) Alkali Aluminate Metal Aqueous Salt Solution Although a commercially available alkali metal aluminate salt aqueous solution may be used, an aluminum source (usually aluminum hydroxide) such as aluminum hydroxide or activated alumina is treated with an alkali hydroxide. Alternatively, a high-concentration and low-alkali aqueous solution of alkali metal aluminate may be prepared first, and then mixed with the required amount of water and alkali hydroxide. In this case, the preparation of the high-concentration solution is stabilized by heating and dissolving the aluminum source with alkali hydroxide and then rapidly cooling, but it is desirable to prepare a necessary amount of a lower alkali solution each time. Regarding the aqueous solution of alkali metal aluminate used in the present invention, it is desirable that the molar ratio of M ₂ O (M is an alkali metal) and Al ₂ O ₃ is in the range of M ₂ O / Al ₂ O ₃ = 1.0 to 6.0. , 1.1 to 3.0 is particularly preferable.

(B) Alkali Metal Silicate Aqueous Solution As the aqueous alkali metal silicate solution, a commercially available product can be used, but the molar ratio of SiO ₂ and M ₂ O is SiO ₂ / M ₂ O = 1.0 to 4.0.
It is desirable to use those in the range of. The concentration of the aqueous solution is preferably 25 wt% or less in terms of SiO ₂ concentration.

(C) Alkali metal salt and / or alkaline earth metal salt As an alkali metal and an alkaline earth metal, periodic table IA
Group II, Group IIA, potassium, sodium, lithium, magnesium, calcium, barium, etc., and these salts include K ₂ CO ₃ , KCl, K ₂ SO.
₄ , CH ₃ COOK, Na ₂ CO ₃ , NaCl, Na ₂ SO ₄ , CH ₃ COONa, CaCl ₂ ,
_{Ca (NO 3) 2, (} CH 3 COO) 2 Ca · H 2 O, Li 2 SO 4 · H 2 O, LiCl, BaC
l _2, but MgCl _2, MgSO _4, and the like, not limited to these, and may be used two or more of these mixtures.

(D) Fine Powder and / or Porous Substance The fine powder and / or porous substance may be organic or inorganic, and may be added in a dry state or a wet state. Examples of the inorganic substance include amorphous silica, calcium silicate, diatomaceous earth, clay and amorphous aluminosilicate, and examples of the organic substance include various ion exchange resins, polymers of acrylic acid and derivatives thereof, but are not limited thereto. Not used, but also used in a mixture.

(E) Water-soluble polymer Examples of the water-soluble polymer include, but are not limited to, starch, dextrin, carboxymethyl cellulose, cyclodextrin, gelatin, alginic acid, polyvinyl alcohol, acrylic acid polymer, polyethylene glycol and the like. Alternatively, these salts, derivatives and mixtures can be used alone or in combination.

Hereinafter, one example of preferred embodiments of the method of the present invention will be described in detail, but the present invention is not limited thereto. First, water is put in a reaction tank, an alkali metal salt and / or an alkaline earth metal salt is added, mixed and dissolved, and an aqueous solution containing an alkali metal salt and / or an alkaline earth metal salt (hereinafter referred to as an alkaline salt aqueous solution) is added. ) Is prepared. Mix (a) the aqueous solution of alkali metal aluminate and keep it at a temperature of 15 to 60 ° C, and (b) under strong stirring, add 3 to 50% by weight of the total amount of the alkali metal silicate solution used for the reaction. After mixing and performing a preliminary reaction for 0.5 to 120 minutes under weak stirring, the remaining aqueous solution of alkali metal silicate is reacted dropwise under strong stirring. The dropping reaction is 5 to 90 minutes, and 10 to 30 minutes is particularly preferable. After the reaction, by aging for 1 minute or longer, preferably 30 minutes or longer at a temperature between 20 and 100 ° C., an amorphous aluminosilicate having a strong higher order structure can be obtained after filtration and drying.

The reaction temperature for both the preliminary reaction and the dropping reaction is 15 to 60.
The range of ° C is desirable. Particularly, a temperature in the range of 30 to 50 ° C is desirable. When the reaction temperature exceeds 60 ° C, the oil absorption capacity of the obtained amorphous aluminosilicate becomes low. Below 15 ° C, there is no significant improvement in performance, so it is not a good energy measure. When aging at 20 to 100 ° C, not so much stirring is required. This aging is preferably carried out while keeping the reaction system as it is, but may be carried out after partially concentrating by filtration or decantation.

The method for mixing the aqueous solution of alkali metal aluminate and the aqueous solution of alkali metal silicate before the preliminary reaction is preferably performed in a short time. As a mixer, a vibro mixer (manufactured by Refuse Industry Co., Ltd.) is used. ) And the like are preferable, and the residence time in continuous mixing is preferably 60 seconds or less. If it exceeds 60 seconds, abnormal reaction progresses and good results cannot be obtained. Upon mixing, it is important to mix the two liquids of the raw materials momentarily after contact. By the way, the strength of stirring with the vibro mixer is 15
~ 50 round trips / second is desirable. Further, the linear velocity of the mixture is preferably 1 m / sec or more when it is carried out in a Venturi type tubular reactor. When the linear velocity is less than 1 m / sec, the dispersion is insufficient, and a high-concentration reaction product is locally produced at the contact portion of the two liquids, which is inconvenient. It is rational to adjust the temperature during mixing to the reaction temperature.

In the preliminary reaction of the present invention, the mixing ratio of (a) the aqueous solution of alkali metal aluminate and (b) the aqueous solution of alkali metal silicate is 10 to 100% by weight of one and 3 to 50% by weight of the other. The mixing ratio is not particularly limited as long as it is mixed, but a more efficient mixing ratio is preferably 10 to 100% by weight of (a) and 3 to 50% by weight of (b).
It is particularly desirable to mix 70% by weight or more of (a) with 3 to 20% by weight of (b). (a) against 10 to 100% by weight of (b)
When 3 to 50% by weight is mixed, the effect can be exhibited by setting the reaction solid content concentration to be low. (a) and
When the mixing ratio of (b) is out of the above range, especially (a)
If it is less than 10% by weight, the effect of increasing the pore size is small,
If (b) is less than 3% by weight, the same problem occurs. Furthermore (b)
When the amount exceeds 50% by weight, the catalytic action is too high and the oil absorption capacity tends to decrease, and the micropore volume tends to increase.

The preliminary reaction after mixing is carried out with or without stirring. The stirring intensity when performing the preliminary reaction in the stirring tank is 0 to 1 m / sec at the stirring blade tip speed, and preferably 0 to 0.
It is 5 m / sec. If it exceeds 1 m / sec, performance deterioration such as oil absorption capacity, pore diameter, and micropore volume is observed. Reaction time is 30
It takes more than 2 seconds, and if it is less than 30 seconds, the preliminary reaction becomes insufficient, and the pore size is small, so that the desired performance cannot be obtained. Long-term reaction causes less performance deterioration, but lowers production efficiency.

In the dropping reaction, it is preferable to drop the residual raw material into the preliminary reaction product. The reverse is also possible, but it is not efficient because it is necessary to lower the reaction solid content concentration. The stirring power in the dropping reaction is preferably 1 Kwh or more per ton of the reaction product, and more preferably 2 Kwh or more. 1
If it is less than Kwh, the dispersion becomes insufficient and the performance tends to deteriorate, such as a decrease in oil absorption capacity. The dropping reaction time is 5 to 90 minutes,
10 to 30 minutes is particularly desirable. If it is less than 5 minutes, the pore size becomes small, and if it is 90 minutes or more, the oil absorbing ability is lowered.

The concentration of the reaction system is preferably 1.5 to 20% by weight, more preferably 2 to 10% by weight, as the sum of the solid content concentrations of the alkali metal aluminate salt aqueous solution and the alkali metal silicate aqueous solution.
% By weight. If it is less than 1.5% by weight, production efficiency will be
If it exceeds 5% by weight, the viscosity of the reaction system increases and the product performance deteriorates due to poor dispersion.

In the method of the present invention, it is preferable to add a fine powder and / or a porous substance to the reaction system, and the addition amount is based on the solid content of the aqueous alkali metal aluminate salt solution and the aqueous alkali metal silicate solution. It is preferably 0.001 to 50% by weight. If it is less than 0.001% by weight, the effect of improving the pore size is small, and if it exceeds 50% by weight, the production efficiency decreases.
Regarding the timing of addition, it may be added to the reaction raw material or may be added during the reaction. Further, the fine powder or porous substance can be added in a dry state or a slurry state.

In the method of the present invention, it is preferable to add the water-soluble polymer in the steps after the preliminary reaction.
The water-soluble polymer may be added after the preliminary reaction, in the middle of the reaction step, the aging step, or the drying step. If it is added before the preliminary reaction, the pore size becomes small, which is not preferable. The addition amount is based on the solid content of the alkali metal aluminate aqueous solution and the alkali metal silicate aqueous solution,
0.01 to 60% by weight is preferable. If the addition amount is less than 0.01% by weight, the effect of increasing the cohesive force of the product is small, and if it exceeds 60% by weight, the effect of increasing the cohesive force is strong, but the pore size tends to be small. Depending on the polymer, it may be added in the form of solid, powder or solution.

Further, in the method of the present invention, it is preferable to add an alkali metal salt and / or an alkaline earth metal salt to the reaction system because a slurry having a filtration rate of 800 kg / m ² · Hr or more can be obtained. The amount of the alkali metal salt and / or the alkaline earth metal salt added is preferably 0.05 to 25% by weight, more preferably 1 to 10% by weight, and particularly preferably 2 to 8% by weight, based on the reaction raw material. When the addition amount is lower than the above range, the filtration rate is slow, and when it is too high, the washing efficiency of the filter cake is lowered. As an aqueous alkaline salt solution,
A neutralized solution of the filtrate obtained by filtering the reaction slurry, or a filtrate of the neutralized solution, and further, a filtrate obtained by neutralizing the reaction slurry and then filtering the excess alkaline water generated from the reaction system. Can be used.

The reaction slurry thus obtained is subjected to solid-liquid separation, for example, filtration to obtain a wet cake as it is, or after washing with water, it is dried if necessary to obtain a fine powder of amorphous aluminosilicate.

By the method of the present invention, inexpensive amorphous aluminosilicate can be stably produced with high production efficiency. Furthermore, in terms of performance, it has physical properties such as an average pore diameter of 1.0 μm or more and a fine pore volume of 0.4 cc / g or less as determined by mercury porosimetry, and has unprecedented high oil absorption capacity and high cation exchange capacity. .

When the amorphous aluminosilicate obtained in the present invention is used as a filler for papermaking, it is effective because it retains the opacity of the paper after printing. Further, the detergent having excellent detergency can be obtained by mixing the amorphous aluminosilicate obtained in the present invention with a surfactant. In addition, rubber, plastic filler,
It can be used as a carrier for agricultural chemicals.

[0027]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The methods for measuring physical properties and the methods for preparing raw materials in Examples and Comparative Examples are shown below.

(1) Oil absorption capacity After drying the sample, a coffee mill (MK-Made by Matsushita Electric Co., Ltd.)
It was pulverized with (51M) for 30 seconds and measured by the oil absorption measurement method of JIS K 6220. (2) Loss on ignition Ignite at 800 ° C for 1 hour in advance, put a few grams of the sample into a magnetic crucible that has reached a constant weight in a desiccator, and weigh accurately.
Then, the material was ignited at 800 ° C. for 1 hour in an electric furnace, and the weight which reached a constant weight was precisely weighed in a desiccator to determine the ignition loss in% by weight.

(3) Cation exchange capacity: 0.1 g of a sample was accurately weighed in terms of anhydride calculated from loss on ignition, and 100 ml of calcium chloride solution (500 ppm in CaCO ₃ )
Add to the inside, stir for 15 minutes at 25 ℃, suction filter with two sheets of Toyo Filter Paper No. 5C stacked, and take 50 ml of the filtrate to remove Ca in the filtrate.
EDTA titration was performed, and the calcium ion exchange capacity of the sample was determined from the value and used as the cation exchange capacity. Incidentally, the calcium ion exchange capacity is evaluated to be rather high when the washing of the powder is insufficient. In other words, if excess alkali ions remain, they react with CO ₂ gas in the air to form a carbonate, which apparently has a high calcium ion exchange capacity. Therefore, the measurement sample must be thoroughly washed.

(4) Filtration rate Using a nutsche and a suction bottle, the sample was filtered under reduced pressure under the following conditions to obtain the filtration rate.・ Filtration temperature 25 ℃ -27 ℃ ・ Decompression degree 350torr ・ Filter material (filter paper) No.5C manufactured by Toyo Roshi Kaisha, Ltd. ・ Sample weight The amount that cake thickness becomes 15-17mm Adjust the vacuum degree of the filter to 350torr. Put the sample into the nutche and filter it. From the time of sample introduction to the time when the slurry or liquid disappears on the nutche and the time when gas is mixed in the filtrate, the filtration time is 1 hour per 1 m ^{2 of} filtration area. From the start of filtration The average amount of filtrate until the end was determined as the filtration rate (unit: kg / m ² · Hr).

(5) Pore size and micropore volume After drying the sample, a coffee mill (MK-Matsushita Electric Co., Ltd.)
What was pulverized with (51M) for 30 seconds was measured with a pore sizer 9320 (mercury porosimeter, manufactured by Shimadzu Corporation) to obtain an average pore diameter. The micropore volume is 0.4 μm from the measurement chart.
The following volumes were determined.

<Preparation of raw materials> In a 1000 cc 4-neck flask,
Add 243 g of Al (OH) _{3 and} 307 g of 48% NaOH aqueous solution and stir it.
It was heated to 110 ° C. and dissolved for 30 minutes to prepare a sodium aluminate aqueous solution. As an aqueous solution of alkali metal silicate,
Commercially available No. 3 water glass (silica) was used (SiO ₂ concentration 29
%).

Example 1 11.05 g of No. 3 water glass (equivalent to 8% by weight of the total amount) diluted with twice the amount of water was dissolved in 488.7 g of ion-exchanged water. 26.35 g of sodium aluminate aqueous solution (100 wt% of the total amount) was added to 52.7
g of ion-exchanged water, and these diluted solutions were supplied to a mixer (Vibro Mixer VS-LABO, manufactured by Refuse Industry Co., Ltd.) at a rate of 41.6 g / min and 6.58 g / min, respectively. The stirring speed was 50 reciprocations / second and the residence time was set to 5 seconds.
Put 419.7 g of the obtained mixed solution into four 1000 cc stainless steel reaction tanks with baffles (diameter 100 mmφ, length 150 mm round bottom type, with stirring turbine blades (diameter 70 mmφ)) and stir without stirring. After preliminarily reacting for 5 minutes, vigorous stirring (stirring power 2.3 Kwh /
92 g of No. 3 water glass (corresponding to 92% by weight of the total amount) diluted with twice the amount of water was added dropwise under 15 minutes. Furthermore, aging was performed for 30 minutes. The mixing, preliminary reaction, dropping reaction and aging temperature were all carried out at 40 ° C. Filter the filter paper (manufactured by Toyo Roshi Kaisha Ltd. N
The cake obtained by filtration under reduced pressure and washing with water was dried at 105 ° C., 300 torr for 10 hours to obtain amorphous aluminosilicate. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

Example 2 Preliminary reaction and dropping reaction were carried out under the same conditions as in Example 1 except that 2.52 g of the dry amorphous aluminosilicate obtained in Example 1 was added to the reaction raw material and reacted. Got a silicate. The composition of this thing,
Table 1 shows the values of oil absorption capacity, cation exchange capacity, filtration rate, pore diameter, and fine pore volume.

Example 3 A 1% solution of carboxymethyl cellulose (manufactured by Nippon Paper Industries Co., Ltd., APP-4, hereinafter abbreviated as CMC) was used as a pre-reactant.
Preliminary reaction and dropping reaction were performed under the same conditions as in Example 1 except that 50 g was added to obtain amorphous aluminosilicate. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

Example 4 11.05 g of No. 3 water glass diluted with twice the amount of water was dissolved in 488.7 g of 6% Na ₂ CO ₃ aqueous solution to prepare an aqueous solution of sodium aluminate 2
6.35 g was dissolved in 52.7 g of 6% Na ₂ CO ₃ aqueous solution and mixed in the same manner as in Example 1. Preliminary reaction depends on stirring conditions
The same procedure as in Example 1 was carried out except that the reaction was carried out at 0.5 m / sec for 5 minutes. Subsequent steps are performed in the same manner as in Example 1,
A powder product of amorphous aluminosilicate was obtained. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

Example 5 Preliminary reaction and dropping reaction were carried out under the same conditions as in Example 4 except that 2.52 g (dry basis) of the wet state amorphous aluminosilicate obtained in Example 1 was added to the reaction raw material and reacted. Then, an amorphous aluminosilicate was obtained. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

Comparative Example 1 The same 1000 cc reaction tank with baffle as in Example 1 was charged with 306 g of water.
Then, 12.76 g of a sodium aluminate aqueous solution was dissolved therein. No. 3 water glass diluted with 2 times water to this solution 4
3.44 g was reacted dropwise at 40 ° C. under strong stirring for 20 minutes. It was aged at the same temperature for 30 minutes, and then post-treated in the same manner as in Example 1 to obtain amorphous aluminosilicate powder. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

Comparative Example 2 An amorphous aluminosilicate was obtained by carrying out the preliminary reaction and the dropping reaction in the same manner as in Example 1 except that the stirring condition of the preliminary reaction was 2.6 m / sec. Table 1 shows the composition, oil absorption capacity, cation exchange capacity, filtration rate, pore size, and micropore volume of this product.

[0040]

[Table 1]

Note) * 1: CMC content is a value obtained by measuring CMC in the filtrate and subtracting it from the charged amount.

As is clear from Table 1, Comparative Example 1 does not undergo the preliminary reaction and therefore has a large micropore volume. Further, in Comparative Example 2, the stirring speed in the preliminary reaction is too high, and therefore the volume of fine pores is large. On the other hand, in Examples 4 and 5, the alkaline salt aqueous solution was added, so that the filtration rate was much faster than in Examples 1 to 3 and Comparative Examples 1 and 2.

[0043]

According to the method of the present invention, with high production efficiency,
Stable production of inexpensive amorphous aluminosilicate is possible. Further, in terms of performance, it has physical properties such as an average pore diameter of 1 μm or more and a fine pore volume of 0.4 cc / g or less as determined by mercury porosimetry, and has unprecedented high oil absorption capacity and high cation exchange capacity. Further, by blending the surfactant and the amorphous aluminosilicate according to the present invention, a detergent having excellent detergency can be obtained. Furthermore, since it has many of these functions, it can be used as a filler for paper, especially for light weight paper, as well as an adsorbent carrier for gases and fragrances, detergents, toothpaste additives, sebum control agents, pesticide additives, and paint additives. It can be applied to many fields of application such as agents and additives for ceramic binders. Furthermore, since the filtration rate of the reaction slurry is very high, the solid-liquid separation process is simplified and the amorphous aluminosilicate can be efficiently produced.

Claims (5)

[Claims] During claim 1 formula x (MeO) · y (M 2 O) · Al 2 O 3 · z (SiO 2) ( wherein, M is an alkali metal, Me represents an alkaline earth metal, x, y, z is 0 ≦ x ≦ 0.1, 0.5 ≦ y ≦ 2.0, 1.5 ≦
Indicates a number within the range of z ≦ 6.0. ) Is an amorphous aluminosilicate having an average pore size of 1.0 μm or more and a volume of pores of 0.4 μm or less of 0.4 cc / g or less and an oil absorption capacity of 150 ml / 100 g as determined by the mercury intrusion method.
As described above, an amorphous aluminosilicate having a cation exchange capacity of 150 mg CaCO ₃ / g or more. 2. A method for producing an amorphous aluminosilicate by reacting an alkali metal aluminate aqueous solution with an alkali metal silicate aqueous solution, wherein 10 to 100 of one of the alkali metal aluminate aqueous solution and the alkali metal silicate aqueous solution is used. It is characterized in that 3% to 50% by weight of the other is mixed with 1% by weight, and the mixture is preliminarily reacted with or without stirring with a stirring blade tip speed of 0 to 1 m / sec, and then reacted with the rest of the raw materials. Amorphous aluminosilicate manufacturing method. 3. The solid content of the alkali metal aluminate aqueous solution and the alkali metal silicate aqueous solution is 0.001 to 50.
The method for producing an amorphous aluminosilicate according to claim 2, characterized in that a fine powder and / or a porous material (weight%) is added and reacted. 4. The water-soluble polymer is added in an amount of 0.01 to 60% by weight based on the solid content of the alkali metal aluminate aqueous solution and the alkali metal silicate aqueous solution in the steps after the preliminary reaction. Item 4. A method for producing an amorphous aluminosilicate according to item 2 or 3. 5. A slurry having a filtration rate of 800 kg / m ² · Hr or more is obtained by adding 0.05 to 25% by weight of an alkali metal salt and / or an alkaline earth metal salt to a reaction raw material and reacting them. 5. The method for producing an amorphous aluminosilicate according to any one of claims 2 to 4.