JP3308309B2 - Manufacturing method of amorphous aluminosilicate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an amorphous (amorphous) aluminosilicate, and more particularly, to an inexpensive, highly oil-absorbing, highly ion-exchangeable, and reaction slurry. The present invention relates to a method for producing an amorphous aluminosilicate having characteristics that can be performed very quickly and easily when performing solid-liquid separation.

[0002]

2. Description of the Related Art As a highly oil-absorbing inorganic carrier, amorphous hydrated silica called white carbon has been known so far. Many applications have been developed, such as fillers and papermaking fillers. However, since amorphous silica has a negative surface potential, when it is used, for example, as a filler for papermaking, it repels the negative surface potential of pulp, and the yield is unfavorably low. Amorphous silica has a high porosity, a surface hydroxyl group, contains a large amount of adsorbed water, and has a lower refractive index than other general silicas. This is disadvantageous in terms of maintaining the properties and is not preferred.

[0003] As silica having high oil absorption, dry silica called aerosil is known.
It is used as a filler for plastics, etc.
This is expensive and is not suitable for use in fields requiring inexpensive raw materials such as the paper industry. Also, the petal-like calcium silicate powder marketed under the trade name "Florite" exhibits a very high oil absorption of 500-600 ml / 100 g, but it is expensive,
In addition, when used for papermaking, it has disadvantages such as causing pitch trouble.

[0004] The above-mentioned silicic acid and calcium silicate powders have a disadvantage that they have no ion exchange ability in addition to the above-mentioned disadvantages, and are used in applications requiring a water softening action, for example, for detergent builders and agricultural chemicals. It is unsuitable for use for preventing generation of scale due to carriers or ionic impurities such as Ca and Mg ions. As a substance having a high ion exchange capacity, crystalline aluminosilicate called zeolite is well known, and in particular, synthetic zeolite 4A type is
In fact, it is currently used in large quantities as a builder for synthetic detergents. However, zeolite itself is a densely packed crystal particle of 1 to 10 μm, and although it has many holes of molecular order, the retention of macroscopic voids related to oil absorption is extremely small, and its oil absorption is at most. It is about 60 ml / 100 g, cannot be expected to have high dispersibility in oil or water, and cannot be used for applications requiring high oil absorption.

Amorphous aluminosilicate powder marketed under the trade name "Zeolex" has the same uses as white carbon and the like, but has low oil absorption and ion exchange capacity. Regarding the production method of amorphous aluminosilicate such as "Zeolex",
Conventionally, various studies have been made. For example, JP-A-52-5809
No. 9 discloses that an aqueous solution of an alkali metal silicate is added to and mixed with an aqueous solution of an alkali metal silicate at a temperature of 70 ° C. or less, and the reaction system is maintained at a pH of 10.5 or more to absorb 75 ml / 100 g of oil. As described above, a method for producing a fine powder of an amorphous alkali metal aluminosilicate having physical properties of 200 mg CaCO ₃ / g or more in ion exchange capacity is disclosed. However, this method does not make it possible to produce amorphous aluminosilicates with a high oil absorption of more than 200 ml / 100 g. Further, JP-A-55-162418 discloses that an aqueous solution of an alkali aluminate and an aqueous solution of an alkali silicate are continuously supplied to a reaction system at a temperature of 60 ° C. or less, and the particle size is large, and filtration and washing are easy. A method for producing an amorphous aluminosilicate having excellent ion exchange capacity is disclosed. Further, Japanese Patent Application Laid-Open No. 62-70220 describes a method for producing an amorphous aluminosilicate by individually dropping a sodium aluminate solution and a sodium silicate solution into a concentration-controlled alkali solution. However, these are not manufactured for the purpose of increasing the oil absorption, and in fact, it is difficult to obtain a highly oil-absorbing amorphous aluminosilicate by this method.

Japanese Patent Application Laid-Open No. 58-156527 discloses that an alkali metal aluminate solution and an alkali metal silicate solution are added to water at a temperature of 60 ° C. or less, or By adding the salt solution to the alkali metal aluminate solution at a temperature of 60 ° C or less, the amorphous aluminosilicate has an oil absorption of 200 ml / 100 g or more and a cation exchange capacity similar to that of various zeolites. A method for producing a salt 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 speed is extremely slow, and thus the method is not suitable for mass production for industrialization.

The present invention provides a method for producing an amorphous aluminosilicate having a high oil absorption capacity, a high ion exchange capacity, and a very high filtration rate in a solid-liquid separation step of extracting fine particles from a reaction slurry, and having excellent production efficiency. It is intended to provide.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the problems of the prior art as described above, and as a result, have found that alkali metal salts and / or alkaline earth metal salts have been developed. By reacting the aqueous alkali metal aluminate solution and the aqueous alkali metal silicate solution in the presence,
The inventors have found that the above objects can be achieved and completed the present invention.
That is, the present invention provides an aqueous solution of an alkali metal aluminate and an aqueous solution of an alkali metal silicate in the presence of an alkali metal salt and / or an alkaline earth metal salt to form a slurry and perform solid-liquid separation. It is intended to provide a method for producing a characteristic amorphous aluminosilicate,
More preferably, the alkali metal salt and / or the alkaline earth metal salt is present in an amount of 0.05 to 25% by weight based on the reaction system, the reaction temperature is 15 to 60 ° C, and the reaction is aged at a temperature of 15 to 100 ° C. And a method for producing an amorphous aluminosilicate characterized by the following.

Further, the present invention provides an inorganic acid, an organic acid,
One or more acid agents selected from acidic salts are added and the reaction system is allowed to react at a pH of 8 to 14, and a solvent which is water-soluble and has a solubility parameter of 7.5 to 20 is reacted. It is intended to provide a method for producing an amorphous aluminosilicate which enables a high-concentration reaction by adding 0.5 to 50% by weight to the system and reacting the same. Furthermore, the present invention reduces the amount of unreacted raw materials by neutralizing the obtained reaction slurry to pH 5 to 13 with one or more acid agents selected from inorganic acids, organic acids, and acid salts, and Less unreacted raw materials elute from the product,
An object of the present invention is to provide a method for producing an amorphous aluminosilicate which is excellent in detergency when it is incorporated into an activator, and generates very little insoluble matter.

The raw materials for producing the amorphous aluminosilicate of the present invention having the characteristics of high oil absorption, high ion exchange capacity and very high filtration rate are (a) an aqueous solution of an alkali metal aluminate, and (b) Aqueous solution of an alkali metal silicate, (c) an alkali metal salt and / or an alkaline earth metal salt, (d) an inorganic acid, an organic acid, an acid salt, and (e) a solvent. Is added to each of the above-mentioned solutions or reaction systems to adjust the concentration, pH, and molar ratio. In the present invention, an alkali metal belongs to Group IA of the periodic table, and an 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, (a) an aqueous solution of an alkali metal aluminate, (b) an aqueous solution of an alkali metal silicate, (c) an alkali metal salt and / or
Or, an alkaline earth metal salt, (d) an inorganic acid, an organic acid, an acidic salt, and (e) a solvent will be described.

(A) Aqueous solution of alkali metal aluminate A commercially available aqueous solution of alkali metal aluminate may be used, but an aluminum source (usually aluminum hydroxide) such as aluminum hydroxide or activated alumina may be used. May be used to prepare a high-concentration and low-alkali alkali metal aluminate aqueous solution first, followed by mixing with a required amount of water or 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 quenching, but it is desirable to prepare a necessary amount of a lower alkali solution each time. With respect to the aqueous alkali metal aluminate solution used in the present invention, the molar ratio of M ₂ O (M is an alkali metal) to Al ₂ O ₃ is desirably in the range of M ₂ O / Al ₂ O ₃ = 1.0 to 6.0. , 1.1 to 3.0.

[0012] (b) an alkali metal salt aqueous alkali metal silicate solution silicate may be commercially available, but the molar ratio of SiO ₂ and M ₂ O is _{SiO 2 / M 2 O = 1.0} ~4.0
It is desirable to use those in the range. The concentration of the aqueous solution is desirably 25% by weight or less in terms of SiO ₂ concentration.

(C) Alkali metal salts and / or alkaline earth metal salts The alkali metals and alkaline earth metals include the periodic table IA.
Group, group IIA, potassium, sodium, lithium, magnesium, calcium, barium and the like, and as salts thereof, K ₂ CO ₃ , KCl, K ₂ SO ₄ , CH ₃ COOK, NaHC
O ₃ , 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, BaCl ₂ , MgC
l ₂ , MgSO _{4 and the} like, but are not limited thereto, and a mixture of two or more of these may be used.

(D) Inorganic acid, organic acid, acid salt Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, carbonic acid (CO ₂ ), and phosphoric acid. Examples of the organic acid include formic acid, acetic acid, butyric acid, and caproic acid. , Acrylic acid, oxalic acid, succinic acid, adipic acid,
Benzoic acid, citric acid and the like. The acidic salt is a salt of the inorganic acid or the organic acid, for example, sodium phosphate, sodium citrate, incompletely neutralized salts such as sodium succinate, but are not limited thereto. One of these may be used, or a mixture of two or more thereof may be used.

(E) Solvent The solvent is water-soluble and has solubility parameters (CM Hansen, J. Paint Tech., 39,
104 (1967), abbreviated as SP value) is 7.5 to 20, methanol, ethanol, propanol, isopropanol, acetone, ethyl methyl ketone, ethyl acetate, ethylene glycol, glycerin, propylene Examples include, but are not limited to, glycols and triethanolamine, and one or a mixture of two or more of these can be used.

In the production of an amorphous aluminosilicate having good solid-liquid separation properties according to the present invention, the composition of the above-mentioned alkali metal aluminate, alkali metal silicate, alkali metal salt and / or alkaline earth metal salt is used. Although the ratio is not particularly limited, for example, in the case of amorphous aluminosilicate for detergent, the following composition ratio is preferable. x (MeO) · y (M 2 O) · Al 2 O 3 · z (SiO 2) · w (H 2 O) (Me in the formula represents an alkaline earth metal, M represents an alkali metal, x , Y, z, w represent the number of moles of each component within the range of the following numerical values: 0 ≦ x ≦ 0.1 0.2 ≦ y ≦ 2.0 0.5 ≦ z ≦ 6.0 w: any positive number including 0) or less Preferred embodiments of the method of the present invention will be described in detail below.

First, water is poured into a reaction vessel, 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 alkali salt). Aqueous solution) is prepared. An aqueous solution of an alkali metal aluminate salt (a) is mixed with the mixture, and the mixture is kept at 15 to 60 ° C., and the aqueous solution of an alkali metal silicate salt of (b) is added dropwise over 3 to 120 minutes with stirring to cause a reaction. In this reaction, it is preferable to carry out the reaction under strong stirring, specifically, with stirring power of 0.2 KW / M ³ or more in order to make the growth of particles uniform. After the reaction, at a temperature between 15 and 100 ° C,
By aging for at least 30 minutes, preferably at least 30 minutes, an amorphous aluminosilicate having a strong higher-order structure can be obtained.

One or more acid agents selected from inorganic acids, organic acids, and acid salts are added to the aqueous alkali salt solution or supplied to the reaction system in accordance with the dropwise addition of the aqueous alkali metal silicate solution. Can be managed. For the solvent, the same addition method as that for the acid agent is used. After aging, the reaction slurry is neutralized, for example, by blowing CO ₂ gas under normal pressure or under pressure.

The order of adding the raw materials may be as follows, but is not particularly limited. 1) A method in which an aqueous solution of an alkali metal aluminate is dissolved in an aqueous solution of an alkali salt, and the aqueous solution of an alkali metal silicate is added dropwise thereto. 2) A method of simultaneously dropping an aqueous solution of an alkali metal aluminate and an aqueous solution of an alkali metal silicate into an aqueous solution of an alkali salt. 3) A method in which an aqueous solution of an alkali metal silicate is dissolved in an aqueous solution of an alkali salt, and the aqueous solution of an alkali metal aluminate is added dropwise thereto. 4) A method in which an alkali metal salt and / or an alkaline earth metal salt are added to and dissolved in an aqueous solution of an alkali metal aluminate diluted with water, and then the aqueous solution of an alkali metal silicate is dropped. 5) A method of adding an alkali metal salt and / or an alkaline earth metal salt to an aqueous solution of an alkali metal silicate diluted with water, dissolving the solution, and then dropwise adding the aqueous solution of an alkali metal aluminate. In these various reaction formulations and addition orders, the addition of (d) an inorganic acid, an organic acid, an acid salt, and (e) a solvent may be added as needed in accordance with the raw material to be added, and may be added to other raw materials before the addition. You may mix them.

A neutralized solution of the filtrate obtained by filtering the reaction slurry as an aqueous solution of an alkali salt, or a filtrate of the neutralized solution, or a filtrate obtained by neutralizing the reaction slurry and then filtering the reaction solution. Excess alkali water generated from the system can be used. The concentration of the alkali metal salt and / or alkaline earth metal salt contained in the aqueous alkali salt solution is 0.1 to 3
0% by weight is preferred, and the alkali metal salt and / or the alkaline earth metal salt are added to the reaction system (here, the reaction system is the total amount of the reaction solution at the end of the reaction) in an amount of 0.05 to 25% by weight, desirably. 0.5-20% by weight, more preferably 2-15% by weight
Good to exist. When the amount of the alkali metal salt and / or the alkaline earth metal salt is less than 0.05% by weight, the filtration rate is slow, and when it is more than 25% by weight, the washing efficiency of the solid in solid-liquid separation is reduced. .

In the present invention, the higher the reaction temperature, the higher the ion exchangeability. But,
If it is too high, the oil absorption capacity of the obtained amorphous aluminosilicate will be low. In order to obtain both high ion exchange property and high oil absorption property, the reaction temperature must be
A temperature in the range of 15 to 60 ° C is desirable, and a temperature in the range of 30 to 50 ° C is particularly desirable. In the case of aging at 15 to 100 ° C, not so strong stirring is required. This aging is desirably performed while keeping the reaction solution as it is, but may be performed after partial concentration or concentration by decantation or the like.

The concentration of the reaction system is preferably such that the sum of the solid contents of the aqueous alkali metal aluminate solution and the aqueous alkali metal silicate solution is 1.5 to 30% by weight, more preferably 2 to 20% by weight, based on the reaction system. %. Further, in the present invention, one or more acid agents selected from inorganic acids, organic acids and acid salts are added to the reaction system, and the pH of the system is controlled to 8 to 14 to improve the performance (oil absorption capacity). High product is obtained. Desirably, controlling the pH between 9.5 and 13.5 will enhance the effect. In the present invention, by adding a water-soluble solvent having a solubility parameter of 7.5 to 20 to the reaction system, the reaction rate can be controlled and the oil absorbing ability can be increased. Particularly, in a high-concentration reaction, a good product cannot be obtained unless the above-mentioned solvent is added. The amount of the solvent to be added is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, based on the reaction system.

In the present invention, unreacted raw materials can be reduced by neutralizing the obtained reaction slurry to pH 5 to 13 with at least one acid agent selected from inorganic acids, organic acids and acid salts. Can be done. In the case of a weak acid such as carbonic acid, a method of directly adding the reaction slurry is used as a neutralization method of the reaction slurry.However, in the case of a strong acid such as hydrochloric acid and sulfuric acid, the reaction slurry is sufficiently diluted or used indirectly. As a neutralization method, a mild liquid in which a neutralized liquid obtained by adding an acid to a liquid part (filtrate) separated by a solid-liquid separator and a solid content (cake) obtained by solid-liquid separation are mixed again. Neutralization is preferred. The neutralization degree is 5 to 13 at the pH of the neutralized product, preferably 9 to 12.5.
It is. If the pH is less than 5, the product itself is susceptible to decomposition by acid, and if it exceeds 13, the neutralizing effect cannot be obtained.

The raw materials used in the present invention, (a) an aqueous solution of an alkali metal aluminate and (b) an aqueous solution of an alkali metal silicate can be used as prepared. May be. A wet cake is obtained by subjecting the reaction slurry obtained as described above to solid-liquid separation, for example, filtration, centrifugation and the like. The cake is washed as it is or after being washed with water, and then dried to obtain a fine powder of amorphous aluminosilicate. On the other hand, the filtrate
It can be recycled as it is or by adjusting the salt concentration and alkali concentration by neutralizing with an acid. Further, the reaction slurry can be neutralized and filtered.

According to the method of the present invention, an inexpensive amorphous aluminosilicate having extremely high production efficiency can be stably produced. Further, in terms of performance, it has unprecedented high oil absorption and high ion exchange ability. When the amorphous aluminosilicate obtained by the present invention is used as a filler for papermaking, it is effective because the opaque retention of the paper after printing is excellent. Also, by mixing the amorphous aluminosilicate obtained in the present invention with a surfactant, a detergent having excellent detergency can be obtained. Furthermore, it can be used as a filler for rubber and plastic, a carrier for agricultural chemicals, and the like. The feature of the production method of the present invention described above is that an alkali metal salt and / or an alkaline earth metal salt is used, whereby a high oil absorption capacity (a value measured by the following measurement method is 200 ml / 100 g or more) and high calcium ion exchange capacity (200meq / 100 g or more measured by the following measurement method), and the filtration rate is high.
It has very fast physical properties such as 850 kg / m ² · Hr or more. Further, the mother liquor obtained by neutralizing the reaction slurry with carbon dioxide gas and removing excess alkali can be recycled as it is.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The methods for measuring the measured values and the methods for preparing the raw materials in the examples and comparative examples are shown below. (1) Oil Absorption A sample was crushed in a mortar and measured by the oil absorption measurement method of JIS K 6220. (2) Loss on ignition Ignition is carried out in advance at 800 ° C for 1 hour, and several g of a sample is put into a magnetic crucible which has reached a constant weight in a desiccator, and precisely weighed.
Then, the mixture was ignited in an electric furnace at 800 ° C. for 1 hour, and the weight reached constant weight was precisely weighed in a desiccator to determine the ignition loss in weight%.

(3) Ion exchange capacity The sample was precisely weighed in 0.1 g in terms of anhydride calculated from the loss on ignition, added to 100 ml of a calcium chloride solution (500 ppm in terms of CaCO ₃ ), and stirred at 25 ° C. for 15 minutes. , Two layers of Toyo filter paper No.5C were filtered by suction, 50 ml of the filtrate was taken and Ca in the filtrate was ED.
TA titration was performed, and the Ca ion exchange capacity of the sample was determined from the value.
The unit of ion exchange capacity was the amount of calcium exchange per 100 g of sample (in terms of anhydride) expressed in milliequivalents. Incidentally, the calcium ion exchange capacity is evaluated to be rather high when the washing of the powder is insufficient. In other words, when excess alkali ions remain, they react with CO ₂ gas in the air to form carbonates, which apparently show high Ca ion exchange capacity. Therefore, the measurement sample must be sufficiently washed.

(4) Filtration Speed Using a nutsche and a suction bottle, the sample was filtered under reduced pressure under the following conditions to obtain a filtration speed.・ Filtration temperature 25 ℃ ～ 27 ℃ ・ Decompression degree 350torr ・ Filter material (filter paper) No.5C made by Toyo Roshi Co., Ltd. ・ Sample weight Amount to make cake thickness 15-17mm Adjust the decompression degree of the filter to 350torr. filtered the sample is placed Nutsche, slurry or on Nutsche from sample entry point, there is no liquid, to the point where the gas in the filtrate is mixed as a filtration time, obtained by filtration area 1 m ² per hour, from the start of filtration The average filtrate volume until completion was determined as the filtration rate (unit: kg / m ² · Hr).

(5) Method for measuring the amount of insoluble matter A test sample and a nonionic surfactant are mixed in equal amounts,
After storing for 0.8 days, 0.83 g was sampled, added to tap water at 40 ° C, and stirred with a magnetic stirrer for 10 minutes.
Filter through a 200-mesh wire gauze, and determine the filtration residual ratio (%) after drying.

(6) Method for measuring Si elution amount 10 g of a test sample was dispersed in 100 ml of a 2% aqueous NaOH solution, stirred at 25 ° C. for 16 hours, and colorimetrically measured (SiO _{2 in} the filtrate after filtration). Is obtained from Oil Chemistry, Vol. 25, p. 156, 1976).

(7) Method of measuring Al elution amount 1 g of a test sample was dispersed in 50 ml of ion-exchanged water, stirred for 10 minutes with a magnetic stirrer, filtered through a 0.2 μm filter, and 60 ml of ion-exchanged water was added to 10 ml of the filtrate. In addition, HNO ₃
After adjusting the pH to 2-2.5 with sodium acetate, the pH is adjusted to 3-3.5 with sodium acetate.
And Add 10 ml of 0.01 M EDTA and boil for 15 minutes. After cooling, add 20 ml of ammonium acetate and make up to 150 ml with ion-exchanged water. In addition, xylenol orange 4 ~
Add 5 drops and titrate with 0.01M zinc acetate.

<Preparation of Raw Materials> In a 1000 cc four-necked flask,
243 g of Al (OH) ₃ and 298.7 g of a 48% aqueous NaOH solution were added, and the mixture was heated to 110 ° C. with stirring and dissolved for 30 minutes to prepare a sodium aluminate aqueous solution. As an aqueous solution of an alkali metal silicate, commercially available No. 3 water glass (silica) was used (SiO ₂ concentration
29%).

Example 1 306 g of water and 12.3 of Na ₂ CO _{3 were} placed in a reaction vessel having a baffle plate of 1000 cc.
g, and stirred and dissolved at room temperature, and 12.76 g of an aqueous sodium aluminate solution was dissolved therein. To this solution, 43.44 g of No. 3 water glass diluted with twice the amount of water was added dropwise at room temperature for 20 minutes with stirring. After the reaction, heat to 50 ° C and ripen for 30 minutes,
Thereafter, the mixture was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha Co., Ltd.) and washed with water. The obtained cake is 105 ℃, 300tor
r, dried for 10 hours. The composition, oil absorption capacity, ion exchange capacity, and filtration rate are shown in Table 1.

Example 2 The filtrate generated in Example 1 was neutralized to pH 11 with carbon dioxide gas.
The mixture was filtered with the filter paper used in Example 1. Na ₂ CO _{3 in} this filtrate
Was contained at 1%. 306 g of this filtrate was put into a 1000 cc reaction tank equipped with baffles, and an aqueous solution of sodium aluminate was added thereto.
43.44 g of No. 3 water glass diluted with 2.76 g and twice the amount of water was dropped simultaneously at room temperature and stirred for 20 minutes to react. After the reaction, 50
After heating to 30 ° C. for aging for 30 minutes, carbon dioxide gas was blown in to neutralize excess alkali (pH 11). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). A part of the filter cake was washed with water 1000 times, filtered and dried (105 ° C., 300 torr, 10 hours), and the remainder was dried under the same conditions. Table 1 shows the values of the composition, oil absorption capacity, ion exchange capacity, and filtration rate.

Example 3 The filtrate generated in Example 2 (Na ₂ CO ₃ concentration 1.9)
%) 306 g, calcium chloride 8 g and No. 3 water glass 14.4
8 g is placed in a 1000 cc reaction vessel with baffle plate.
41.72 g of aqueous sodium aluminate solution diluted with 2.27 times water
At 40 ° C. for 20 minutes with stirring. After the reaction, the mixture was heated to 50 ° C. and aged for 30 minutes. Thereafter, 10% sulfuric acid was gradually added dropwise to neutralize excess alkali (pH 10). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). Wash a part of the filter cake with 1000 times water,
After filtration and drying (105 ° C., 300 torr, 10 hours), the remainder was dried under the same conditions. Table 1 shows the values of the composition, oil absorption capacity, ion exchange capacity, and filtration rate.

Comparative Example 1 306 g of water was placed in a 1000 cc reaction vessel equipped with baffles, and 12.76 g of an aqueous sodium aluminate solution was dissolved therein. To this solution, 43.44 g of No. 3 water glass diluted with twice the amount of water was added at room temperature.
A drop reaction was performed in 20 minutes with stirring. After the reaction, heat to 50 ° C
After aging for 30 minutes, this reaction slurry was filtered and washed under reduced pressure using filter paper (No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.). The filter cake was dried at 105 ° C., 300 torr and 10 hours. The composition, oil absorption capacity, ion exchange capacity, and filtration rate are shown in Table 1.

COMPARATIVE EXAMPLE 2 306 g of water was placed in a 1000 cc reaction vessel equipped with baffles, and 43.44 g of No. 3 water glass obtained by diluting 12.76 g of an aqueous sodium aluminate solution with twice as much water was stirred at room temperature for 20 minutes under stirring. To react dropwise. Immediately after the reaction, filter paper (Toyo Filter Paper Co., Ltd. No.5C)
, And filtered and washed under reduced pressure. This filter cake 1
It was dried at 05 ° C, 300 torr and 10 hours. The composition, oil absorption capacity, ion exchange capacity, and filtration rate are shown in Table 1.

[0038]

[Table 1]

As is clear from Table 1, in Examples 1 to 3, alkali salts were added to the reaction system.
The filtration speed is fast and the performance is good. However, in both Comparative Examples 1 and 2, the alkali metal salt and / or the alkaline earth metal salt were not added, so that the filtration rate was extremely low.

Example 4 Sodium carbonate was dissolved in ion-exchanged water to prepare a 6% strength aqueous solution. 132 g of this aqueous solution and 38.28 g of sodium aluminate aqueous solution were put into a 1000 cc reaction tank equipped with a baffle plate. 201.4 g of No. 3 water glass diluted with twice the amount of water at 40 ° C
A drop reaction was carried out in 20 minutes under strong stirring. During the dropping reaction, the reaction rate was optimized by blowing CO ₂ gas to control the pH of the reaction system. The pH change during the reaction is shown in Table 2. After the reaction,
After heating to 50 ° C. for aging for 30 minutes, CO ₂ gas was blown in to neutralize excess alkali (pH 11). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). A part of the filter cake was washed with water 1000 times, dried by filtration (105 ° C., 300 torr, 10 hours), and the remainder was dried under the same conditions. Each composition, oil absorption capacity,
Table 2 shows the values of ion exchange capacity, filtration rate, Si elution amount, Al elution amount, and insoluble matter amount.

Example 5 The filtrate generated in Example 4 (alkaline salt concentration 6.9%, pH 1
132 g of a liquid whose pH was adjusted to 10 by blowing CO ₂ gas into 1.2)
And 38.28 g of an aqueous solution of sodium aluminate were placed in a 1000 cc reaction vessel equipped with baffles, and 201.4 g of No. 3 water glass diluted with twice the amount of water was added dropwise to this solution under strong stirring at 40 ° C. for 20 minutes. The pH change during the reaction is shown in Table 2. After the reaction, 30
After aging for ₂ minutes, CO ₂ gas was blown in to neutralize excess alkali (pH 11). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). A part of the filter cake is washed with water 1000 times and filtered and dried (105 ° C,
300 torr, 10 hours), and the remainder was dried under the same conditions. Table 2 shows the values of each composition, oil absorption capacity, ion exchange capacity, filtration rate, Si elution amount, Al elution amount, and insoluble matter amount.

Example 6 55 g of a 6% aqueous solution of sodium carbonate prepared in Example 4, 51.04 g of an aqueous solution of sodium aluminate and 25 g of ethanol were added to 10 g of
The reaction solution was placed in a 00 cc reaction vessel equipped with a baffle plate, and 268.5 g of No. 3 water glass diluted with twice the amount of water was added dropwise to the solution under vigorous stirring at 40 ° C. for 20 minutes. After the reaction, aged at 40 ° C for 30 minutes,
CO ₂ gas was blown in to neutralize excess alkali (pH 11).
This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). A part of the filter cake is washed with water 1000 times and dried by filtration (105 ° C, 300torr, 10 hours)
The remainder was dried as it was under the same conditions. Table 2 shows the values of each composition, oil absorption capacity, ion exchange capacity, filtration rate, Si elution amount, Al elution amount, and insoluble matter amount.

Example 7 55 g of a 6% aqueous solution of sodium carbonate prepared in Example 4, 51.04 g of an aqueous solution of sodium aluminate and 25 g of ethanol were added to 10 g of
The reaction solution was placed in a 00 cc reaction vessel equipped with a baffle plate, and 268.5 g of No. 3 water glass diluted with twice the amount of water was added dropwise to this solution under vigorous stirring at 40 ° C. for 20 minutes. During the dropping reaction, the reaction rate was optimized by blowing CO ₂ gas to control the pH of the reaction system. The pH change during the reaction is shown in Table 2. After the reaction, the mixture was aged at 40 ° C for 5 minutes, and then citric acid was added dropwise to adjust the pH of the reaction slurry.
11.5. This neutralized slurry is filtered with filter paper (Toyo Roshi Kaisha, Ltd.)
No. 5C), and filtered under reduced pressure. A part of the filter cake is washed with water 1000 times and filtered and dried (105 ° C, 300torr).
r, 10 hours) and the remainder was dried under the same conditions. Table 2 shows the values of each composition, oil absorption capacity, ion exchange capacity, filtration rate, Si elution amount, Al elution amount, and insoluble matter amount.

Comparative Example 3 51.04 g of an aqueous sodium aluminate solution was added to 55 g of ion-exchanged water.
Into a reaction vessel with a baffle plate of 1000 cc, and 268.5 g of No. 3 water glass diluted with twice the amount of water was added to this solution under strong stirring at 40 ° C.
A drop reaction was performed in 20 minutes. After the reaction, the mixture was heated to 50 ° C. and aged for 30 minutes, and the reaction slurry was filtered with a filter paper (No. 5 manufactured by Toyo Roshi Kaisha, Ltd.).
After filtering under reduced pressure using C), the filter cake is washed with water 10 times and dried by filtration (105 ° C, 300 torr, 10 hours).
did. Table 2 shows the values of each composition, oil absorption capacity, ion exchange capacity, filtration rate, Si elution amount, Al elution amount, and insoluble matter amount.

[0045]

[Table 2]

As is clear from Table 2, Examples 4 and 5
The reaction pH was controlled by adding an acid to the reaction system, which enabled high-concentration reactions, high oil absorption capacity, high ion exchange capacity, and high-quality aluminosilicate with low elution amounts of Si and Al and small amounts of insolubles. Was done. In Examples 6 and 7, a solvent was added to the reaction system, and in Example 7, the reaction was controlled by adding an acid. Thus, a high-concentration reaction was possible, and the oil absorption capacity and ion exchange capacity were high, and the elution of Si and Al was performed. A high-quality aluminosilicate having a small amount and a small amount of insoluble matter was obtained.
However, Comparative Example 3 was a reaction of a high concentration system, and did not include addition of an alkali metal salt and / or an alkaline earth metal salt.
The quality was poor because the reaction was not controlled by solvent or acid.

[0047]

The amorphous aluminosilicate obtained by the method of the present invention has an unprecedented high oil absorption capacity and a high ion exchange capacity. Further, since the filtration speed of the reaction slurry is very high, the solid-liquid separation step is simplified, and an inexpensive amorphous aluminosilicate with good production efficiency can be produced. Further, at the time of the reaction, one or more acid agents selected from inorganic acids, organic acids, and acid salts are added, and the reaction is carried out by controlling the pH of the reaction system to 8 to 14. Solubility parameter
By adding 0.5 to 50% by weight of a solvent having a ratio of 7.5 to 20 to the reaction system and causing the reaction, a high-concentration reaction becomes possible and an amorphous aluminosilicate having a high oil absorption ability can be produced. In addition, the obtained reaction slurry is neutralized to pH 5 to 13 with one or more acid agents selected from inorganic acids, organic acids, and acid salts to reduce unreacted raw materials and to reduce unreacted materials from products. When the reaction raw material is less eluted and is mixed with the activator, it is possible to obtain an amorphous aluminosilicate having a small amount of aluminum eluted and excellent in detergency, a small amount of silicon eluted and very little generation of insoluble substances.

Since the amorphous aluminosilicate obtained by the present invention has many of these functions, it can be used as a filler for paper, especially for lightweight paper, an adsorbent for gas and fragrance, a detergent, an additive for dentifrice, and a sebum control agent. It can be applied to many fields of application, such as additives for agricultural chemicals, additives for paints, and additives for ceramic binders.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-162418 (JP, A) JP-A-57-61613 (JP, A) JP-A-58-156527 (JP, A) JP-A 52-162 58099 (JP, A) JP-A-62-191419 (JP, A) JP-A-62-70220 (JP, A) JP-A-62-191417 (JP, A) JP-A-61-25653 (JP, A) JP-A-57-92515 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 33/20-39/54

Claims (8)

(57) [Claims] An alkali metal salt ( alkaline aluminate)
An aqueous solution of an alkali metal aluminate and an aqueous solution of an alkali metal silicate are reacted in the presence of a lithium metal salt and an alkali metal silicate) and / or an alkaline earth metal salt to form a slurry and solid-liquid separation A method for producing an amorphous aluminosilicate. 2. The method for producing an amorphous aluminosilicate according to claim 1, wherein the alkali metal salt and / or the alkaline earth metal salt is present in an amount of 0.05 to 25% by weight based on the reaction system. 3. The reaction temperature is 15 to 60 ° C., and the reaction temperature is 15 to 60 ° C.
The method for producing an amorphous aluminosilicate according to claim 1, wherein the aging is performed at a temperature of 100 ° C. 4. During the reaction, one or more acid agents selected from inorganic acids, organic acids and acid salts are added to adjust the pH of the reaction system to 8 to 14.
The method for producing an amorphous aluminosilicate according to claim 1, wherein: 5. The amorphous alumino according to claim 1, wherein a solvent having a solubility parameter of 7.5 to 20 is added to the reaction system in an amount of 0.5 to 50% by weight based on the reaction system. Manufacturing method of silicate. 6. The obtained reaction slurry is prepared by using at least one acid agent selected from inorganic acids, organic acids and acid salts at pH 5 to 5.
The method for producing an amorphous aluminosilicate according to claim 1, wherein the amorphous aluminosilicate is neutralized to 13. 7. The method for producing an amorphous aluminosilicate according to any one of claims 1 to 6, which has a filterability of a filtration rate of 850 kg / m ² · Hr or more. 8. The amorphous aluminosilicate has an oil absorption capacity of 200 ml / 100 g or more and a calcium ion exchange capacity of 20 ml / 100 g or more.
The method for producing an amorphous aluminosilicate according to any one of claims 1 to 7, wherein the amount is 0 meq / 100 g or more.