JPS5992911A - Preparation of crystalline aluminosilicate - Google Patents

Abstract

PURPOSE:To prepare a crystalline aluminosilicate having excellent fluidity, etc., and suitable as a builder of detergent, etc., by mixing a concentrated aqueous solution of sodium aluminate with an aqueous solution of sodium silicate at a specific ratio, and subjecting the mixture to hydrothermal crystallization. CONSTITUTION:A concentrated aqueous solution of sodium aluminate having a concentration of 30-70wt% is mixed with a concentrated aqueous solution of sodium silicate having a concentration of 35-50wt% to obtain a mixed solution having a composition of SiO2/Al2O3>=2, Na2O/Al2O3>2, (SiO2+Na2O)/Al2O3<= 4.5 and H2O/Al2O3=15-30 (molar ratios). The mixture is made to react with each other at about 50-90 deg.C for about 10-180min to crystallize the aluminosilicate and to obtain the objective crystalline aluminosilicate. The resultant slurry can be added as it is to the slurry base of a powdery detergent, or compounded with a detergent component after drying and pulverization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing crystalline aluminosilicates. More specifically, the present invention relates to a method for producing a concentrated slurry of crystalline aluminosilicate having excellent performance as a detergent builder.

Cleaning agents based on anionic surfactants such as soap and LAS%AO8 create salts that dissolve in water with the divalent metal cations contained in hard water, resulting in problems such as reduced cleaning power and the formation of scale. It is known to cause In order to prevent this and enhance the cleaning effect, various phosphates are used as so-called bilgo ingredients. This phosphate has the ability to chelate and sequester divalent cations, but on the other hand, as a source of eutrophication to environmental waters, its use is becoming limited, especially in sealed waters.

Therefore, methods using various chelating agents and aluminosilicate as substitutes for the function of phosphate have been proposed and disclosed (see, for example, Japanese Patent Application Laid-open No. 12381/1981). Regarding aluminosilicate, Its cation exchange ability has been well known for a long time, and its synthesis method is also well known, as seen in, for example, Japanese Patent No. 217383. Also, regarding its use as a cleaning agent,
It is disclosed in '-1119 and is basically known.

However, the methods proposed so far do not consider the aluminosilicate manufacturing process and the detergent manufacturing process in an integrated manner, so they are by no means satisfactory from the perspective of manufacturing aluminosilicate-containing powder detergents. It's hard to say. In some cases, the gas cessation has been redundant and redundant, and in other cases, the performance properties of the final detergent have been extremely poor.

Therefore, the present inventors conducted extensive research in order to develop an ideal process from the viewpoint of producing a powder cleaning agent.

The ultimate simplified aluminosilicate manufacturing process, which can be directly linked to the powder cleaning agent manufacturing process, is to add one alumina source and silica source into the cleaning agent slurry base, and then add the ion-exchangeable aluminosilicate therein. However, there are some difficulties with this process. One is that the added alumina source is used to create the anionic activator and salt of the detergent. In addition, aluminosilicate gel, which is simply a mixture of alumina source and silica source at normal temperature, does not have ion exchange ability, so heating is required for crystallization, but heating of a system diluted with a detergent slurry base is - Cooling is not only inefficient, but also the heating and cooling behavior of such a multicomponent system is extremely complex from a phase diagram perspective, making it difficult to control. When the soil is heated, the coexistence of inorganic salts such as mirabilite and soda ash in the detergent slurry base may seriously inhibit the development of ion exchange properties. As mentioned above, the above method is technically and economically inefficient.

The next ideal would be to mix the alumina and silica sources to form an aluminosilicate gel, which would then be crystallized and simultaneously added to the powder slurry base and allowed to dry.

In order to carry out this method, an extremely highly concentrated aluminosilicate slurry is required, but this is a method for producing an aluminosilicate slurry that is highly concentrated, has excellent builder performance, and has excellent powder properties when made into a powder detergent. was previously unknown. Therefore, the present inventors conducted extensive research in order to find a method for producing aluminosilicate that satisfies the above conditions.The inventors first used a sodium aluminate aqueous solution and a sodium silicate aqueous solution each having a high concentration within a specific range, and then mixed them. It has been found that an aluminosilicate slurry with excellent performance can be obtained by adjusting the composition of the mixed solution 'f:l within the specified range (see patent application No. 57-157096), and as a result of further research,
By changing the composition of the above-mentioned mixed solution and selecting it within a different specific range that instantly contacts the specific range found earlier, we can produce aluminium oxide powder that has excellent pulverization properties, excellent fluidity and suspension stability, and has a fine particle size. It was discovered that a silicate slurry could be obtained,
We have arrived at the present invention.

That is, the present invention involves mixing an aqueous sodium aluminate solution and an aqueous sodium silicate solution to produce a crystalline aluminosilicate by hydrothermal crystallization. A high concentration solution of 35% to 50% silicic acid is used as the aqueous solution, and the composition of the mixed solution is 5% in molar ratio.
102/kt20. ≧2.0, Na207M20.
> 2.0 and (SiO,,+Na20)/A/
:20. ≦4.5, H,,07M20. -i, 5
~3 [Aluminosilicate sla I in the range of J
The present invention provides a method for producing a crystalline aluminosilicate, which is characterized by producing J-.

In the production method of the present invention, in addition to the concentration of the sodium aluminate aqueous solution and the sodium silicate aqueous solution being within the above range, %2? l! It is particularly important that the composition of the mixed solution be within the above-mentioned molar range.

If the concentration of the above aqueous solution is too small, the concentration of the slurry produced will also be low and the object of the present invention will not be achieved, and if it is too large, the crystal particles of the aluminosilicate slurry produced will become coarse, and it may also be used as a cleaning agent. The physical properties of the powder deteriorate when mixed. Furthermore, 1 silicic acid) l) Rum aqueous solution 1-! , 50 by weight, homogeneous mixing is impossible.

Also, regarding the composition of the mixed solution, the 5in2 class is M.
If the amount is less than 2.0 times mole relative to 2C, the water-soluble aluminum salt minirum salt will remain in the aluminosilicate P and interact with the surfactant, which is a component of the cleaning agent, which is undesirable. It is also undesirable because it reacts with acid soda and forms an insoluble gel, which may adhere to clothes during washing.

In addition, when the amount of Na,,O exceeds 2.0 times the mole of M2C, it tends to slightly deteriorate the powder physical properties and cleaning properties of the cleaning agent, but the amount of 5102 may be adjusted depending on the amount of Na2O. Spatula, (Na2O+5iO2)7M20. If the pressure is controlled within the range of ≦4.5, there will be no tube pressure problem and a cleaning agent that can be used in practical use can be obtained. The amount of Na,,O is At20
Even if the amount is less than 2.0 mol per ゜, the expected physical properties and performance of the cleaning agent are excellent. The amount of Na2O is 2.
The larger the mole, the easier it is to crush, the fluidity,
This is advantageous because it provides excellent suspension stability.

The aqueous solution of sulfur aluminate used in the present invention can be obtained by dissolving sodium aluminate in water, dissolving aluminum hydroxide in a solution of sulfur hydroxide, etc. Since the method of dissolving aluminum in an aqueous sodium hydroxide solution can yield an extremely highly concentrated and supersaturated aqueous solution of sodium aluminate in one hour, it is preferable to use the solution obtained by this method as the starting solution. When a supersaturated water bath solution is used, fine crystals may precipitate in some cases, but this does not pose any particular problem in carrying out the present invention.

As the sodium silicate used in the present invention, those having various Si/Na ratios can be used. Therefore, any of the commercially available diatoms No. 1, 2, and 3 can be used as they are. However, considering the overall molar ratio, No. 2 or No. 3 silica is superior.

In carrying out the present invention, it is necessary to thoroughly mix the two reaction liquids. For that purpose, line mill, gear pump j
It is preferable to use a powerful stirring mixer such as a turbine pump or Ledegge mixer.

In the reaction, a preferred method is to gradually add an aqueous sodium aluminate solution to a sodium silicate solution under strong stirring. It is also preferable to add the two reaction solutions simultaneously to an aluminosilicate slurry prepared in advance.

The reaction temperature is 50-90C1, preferably 60-80C. If it is too low, coarse particles will occur, and if it is too high, crystallization will occur, both of which are undesirable. The best results were obtained when a room temperature sodium silicate aqueous solution and a 50-90C supersaturated sodium aluminate aqueous solution were simultaneously added while maintaining the inside of the reactor at 50-90U. The reaction is carried out batchwise in 10 to 1
80 minutes, preferably 15 to 60 minutes. After the addition is complete, it is advisable to continue stirring for 10 to 60 minutes ('f) to help homogenize the gel.
0['', preferably 15-1 by heating to 80-100C
When held for 20 minutes, preferably from 20 to 60 minutes, crystallization of the aluminosilicate (zeolite 4A, ) occurs during this time to form a slurry. At this time, if the crystallization time is too long or the temperature is too high, zeolite)
4A may be converted into hydroxysodalite without ion exchange properties. .

In the above reaction, to reduce the viscosity of the reaction mixture,
Suitable dispersants, e.g. molecules 1-ij 5 U U to 10
000 polyacrylic acid polymers, copolymers, etc. may also be used. The slurry after crystallization can be added to the slurry base of the powder cleaning agent as it is or after neutralization if necessary. In addition to carbon dioxide gas for neutralization,
An anionic activator compound (87'111) (for example, a bed-based oroalkylbenzene sulfone), which is a detergent component, can be used. Carbon dioxide gas may be directly blown into the reaction tank, or may be mixed in a static mixer while being circulated. Furthermore, after partially filling the core with carbon dioxide gas, it is also possible to complete the core 1) with an S agent.

Alternatively, the slurry may be dried and powdered and then blended with the cleaning agent components.

By using the method of the present invention, an aluminosilicate having excellent builder performance and good powder physical properties can be obtained directly as a concentrated slurry for use in the production of a detergent slurry.

Size of crystal grains obtained by the method of the present invention.

The proportion of coarse particles is small and the particles become fine (200mθsh
It has excellent fluidity and suspension stability, and there is little risk of it adhering to clothing when it is used as a detergent for washing clothes. Of course, if necessary, it can be easily ground even more finely using a mill.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the examples, the calcium ion exchange capacity is the value after 10 minutes. 〇Example 1 Reagents, sodium hydroxide (moisture 4.3%) in a round bottom flask 147. Or 112.7f'
After heating to 50C, add aluminum hydroxide 196.8F with a moisture content of 4.7% and an average particle size of 50 μm.
The temperature was raised while stirring. After holding at the boiling point temperature for 20 minutes while refluxing and confirming the dissolution of the total solution, 50C
Lower the temperature to a uniform, thick, viscous aluminic acid)
A supersaturated solution of Jum was obtained. 1 of another three rose parables
into a flat bottom flask, No. 3 sodium silicate (Na2O9
-42%, Si, 022B, 99%, moisture 61.
59%) 1502 in advance and 5% in an oil bath.
After raising the temperature to DC, the entire amount of the supersaturated solution of sulfur and lithium aluminate and 350 g of No. 3 sodium silicate were added simultaneously at a constant rate for 60 minutes using a microtube pump. During this time, stirring was continued at 500 rpm using an rfJ9AN U-shaped stainless steel stirrer with a length of 9 mm. The temperature of the sodium aluminate added was 50 tl', and the temperature of No. 3 sodium silicate was room temperature.

The resulting sodium aluminosilicate becomes hard temporarily, but
As the stirring continued, the slurry became fluid. After 60 minutes of temperature rise, stirring was stopped, and the container was rapidly cooled in water at room temperature. The composition of the mixed solution is the same as Mozeolite 4A, p, a-=
In the diffraction line of 2.98 degrees (hkt=410, 322), the relative intensity with respect to the standard crystal (Lined θ4A) was calculated to be 92%. The ion exchange capacity of this product was 274.5 (G0aOOMe anhydrous zeolite 2), which was comparable to 271.6 of commercially available zeolite for detergents.

Classification using a water sieve revealed that 6.2% of particles were 200 mθsh On.

The resulting slurry was heated to pH 10.9 with carbon dioxide gas (a cleaning agent with good water washability) was obtained.

Example 2 In the same manner as in Example 1, sodium hydroxide (moisture 4.3
%) 137.5F is dissolved in water 124.8F, and aluminum hydroxide (moisture 47%) 195. E
l' was added to obtain a supersaturated solution of sodium aluminosilicate. Add this to No. 3 sodium silicate (Na2O9, 42%)
, 5iO22B, 99chi, moisture 61.59%) 15
In the same manner as in Example 1, the mixture was added together with 346.72 ml of sodium silicate into a 1 t flask that had been placed in advance, and a thick white slurry could be obtained by aging, heating, and cooling. The composition of this mixed solution is Ha, O:
At20. :B102:I(20=2.U1:1
: 2. [J 1 : 0 which was 25.07 The X-ray pattern of the obtained crystal matched that of zeolite 4A. When the crystallinity was checked in the same manner as in Example 1, it was 95.4%.
Met. The ion exchange part was 277 (g0a00u/y anhydrous zeolite), which was comparable to commercially available zeolite.

When the obtained slurry was neutralized in the same manner as in Example 1 and mixed into a detergent powder dough, a good detergent could be obtained.

Furthermore, in the classification of the obtained slurry using a water sieve,
200 Mesh on particles were observed in 46% Example 3 Sodium hydroxide (4.3% moisture) 188.5 F water 154.1's Aluminum hydroxide (88% moisture)
206.7f, No. 5 sodium silicate (kJa209.
42%, Ri, 022 B, 99%, moisture 6159
A white viscous slurry was obtained in exactly the same manner as in Example 1 except that 500F (%) was used. The mixed gel composition at this time has a molar ratio of CN a, 0: At?O,: si
O2: H20=2.50: 1:2.00:
It was 2 Otsu and 3. The ion exchange capacity of this product is 276.4
(gcaao, /Ii' anhydrous zeolite).

The powder detergent obtained by mixing 20% of the anionic detergent into the fabric after carbon dioxide neutralization in the same manner as in Example 1 showed good powder physical properties and detergency.

Example 4 The same raw materials as in Example 6 were used, and the amount used was 151. OS', water 57.6521
Using aluminum hydroxide 190.5s' and No. 3 sodium silicate 500F, a white viscous slurry was obtained in Examples 1 and 4. In addition, the mixed gel composition at this time is IJa20'1~ノ,Q,°G02''112U=2 in molar ratio.
．． The ratio was 31:1:2.17:24.0. The ion exchange capacity of this product is 257 (odor'c a c
03/' dry solid content), and after the middle step 11 in the same manner as in Example 1, it was mixed into detergent dough to make a powder detergent. (l
It was done.

Example 5 The raw material 1 conditions used were the same as in Example 6, and the amounts used were sodium hydroxide 11B, 7r, and aluminum hydroxide 179.
7? , water 94.2 S', No. 3 sodium silicate 50
At 0 V, gelation and crystallization were performed to obtain a white viscous slurry. In addition, the mixed gel composition at this time is Na in molar ratio.
2O:Al2O:5102:H20=2.08:1:
It was 2^0:26.7. When this was neutralized in the same manner as in Example 1 and mixed into detergent fabric to make a powdered detergent, a product with satisfactory powder physical properties and detergency was obtained.

△ Rium 23 Otsu 12, Water 2,! + 0.32, aluminum hydroxide 245.7F, No. 3 sodium silicate 500
2 was mixed into a gel and crystallized to obtain a concentrated slurry of crystalline sodium aluminosilicate. In addition, the mixed gel composition at this time (at a molar ratio of Na20'fi-1-
20,:61102:H,,0=2.40:1:
1.61: 25.6 and 0 This detergent was neutralized in the same manner as in Example 1, and then mixed with 20% detergent fabric and dried. The detergent had extremely poor washability.

Comparative Example 2 Using the same raw materials as Example 3 and under the same conditions as Example 1, sodium hydroxide 219.4F, water 121911, aluminum hydroxide 205.7R, No. 3 sodium silicate 500
2 was mixed into a gel and crystallized to obtain a concentrated slurry of crystalline sodium aluminosilicate. The mixed gel composition at this time was Na2O:A40. in molar ratio. :SiO2
:Ii,,O=2.82:1:2.01:26
．． It was 3. A powder detergent obtained by neutralizing carbon dioxide gas and mixing 20% of this product into a phosphorus-free anionic detergent fabric as in Example 1 had poor powder fluidity and insufficient cleaning properties. Ta.

Comparative Example 3 Sodium hydroxide 1 using the same raw materials and under the same conditions as Comparative Example 2
19. Of, aluminum hydroxide, 17o22, water 10
5.8? , No. 3 silicate sl/liu 1% 5002 were mixed, gelled, and crystallized to obtain a concentrated slurry of crystalline sodium aluminosilicate. At this time, the mixed gel composition t has a molar ratio of 1.4 a20:A720. ;Si
O2:H20=2.27:1:2.43:2
It was 8.3. A powdered cleaning agent obtained by neutralizing this in the same manner as in Example 1, mixing 20% of it in phosphorus-free cleaning agent fabric, and drying it had poor powder physical properties and unsatisfactory anti-layer properties. Ta.

Applicant's agent: Furutani ψ5

Claims (1)

[Claims] 1. When producing a crystalline aluminosilicate by mixing an aqueous sodium aluminate solution and an aqueous sodium silicate solution and performing hydrothermal crystallization, the sodium aluminate aqueous solution has a high content of 30 to 70% by weight. A concentrated solution is used, and a high concentration solution of 35 to 5% by weight is used as an aqueous sodium silicate solution, and the composition of the mixed solution is S i 02/At in molar ratio.
20. ≧2.0, Na2O/At20. > 2.
0. and (Si02+Na,,O)/M20. @ 4.
5. A method for producing a crystalline aluminosilicate, which comprises producing an aluminosilicate streak so that H20/M, 03=15 to 30. 2. The method for producing a crystalline aluminosilicate according to claim 1, wherein the aqueous sodium aluminate solution is a supersaturated solution.