JPS5926915A - Preparation of crystalline aluminosilicate - Google Patents

Abstract

PURPOSE:To prepare high-purity crystalline aluminosilicate having uniform particle size, in high reproducibility, by reacting a silica source with an alumina source and an alkali metal source in an aqueous solution in the presence of a specific amine. CONSTITUTION:A silica source such as silica powder, colloidal silica, etc. is mixed with an alumina source such as alumina powder, aluminum sulfate, etc. at a molar ratio (SiO2:Al2O3) of 20:1-300:1, and the mixture is added together with an alkali metal source such as NaOH, KOH, NaCl, KCl, etc. to water. The amounts of the alkali metal source and water are 0.01-10mol and 5-500mol per 1mol of the silica, respectively. 0.1-5mol (based on 1mol of SiO2) of an amine having three primary amino groups in the molecule, e.g. 1,3,6-triaminomethylhexane, is added to the aqueous mixture and the components are made to react with each other at 100-200 deg.C for 5-100hr under atmospheric pressure. A crystalline aluminosilicate having uniform particle size and excellent as a catalyst can be prepared in high purity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing crystalline aluminosilicates. More specifically, the present invention relates to a method for producing crystalline aluminone silicade of high purity, uniform particle size, and with good reproducibility, which is useful as a catalyst in the production of various compounds.

Crystalline aluminone licade is a substance generally called zeolite, and has a rigid three-dimensional structure in which S104 and AlO4 are cross-bonded via oxygen atoms. The ratio of the aluminum atom to silicon atom phase to the oxygen atom is 1:2, and the electron valence of the aluminum-containing tetrahedron is kept in equilibrium by containing various cations within the crystal. It's dripping.

This crystalline aluminosilicate is available as a natural product or a synthetic product, and is used as an adsorbent, a catalyst, etc. Recently, zeolites (Mobil Oil, ZSN-5, etc.) obtained by adding VC tetraalkylammonium ions to a mixture of silica feed material, alumina feed material, alkali metal feed material and water have been developed to remove hydrocarbons from methanol. It is particularly effective as a catalyst in the production and production of baraxylene from toluene, and is attracting particular attention.

However, the above production method has the disadvantage that the tetraalkylammonium ion supplying substance used is expensive and the size of the obtained crystal particles is non-uniform.
This is not necessarily satisfactory as an industrial method.

To overcome these drawbacks, methods using alkylamines, aminoalcohols, alkyldiamines, and organic sulfur compounds have been proposed, but they still have problems in terms of reproducibility, product purity, and production rate. However, almost no effect was observed on the formation of crystal grains.

In view of these circumstances, the present inventors have conducted intensive research to develop a method for producing the crystalline aluminosilicate having catalytic action with high purity, uniform particle size, and good reproducibility. It was discovered that the objective could be achieved by coexisting a certain type of amine in the reaction system, and based on this knowledge, the present invention was completed.

That is, the present invention provides a method for producing crystalline aluminosilicate by reacting a silica supply material, an alumina supply material, and an alkali metal supply material in an aqueous solution, using an amine having three primary amino groups in one molecule. The present invention provides a method for producing crystalline aluminosilicate characterized by the coexistence of crystalline aluminosilicate.

The alumina supply material used in the method of the present invention is not limited in percentage as long as it is commonly used in the production of conventional crystalline aluminosilicate-1. For example, alumina powder,
Aluminum sulfate, sodium aluminate, etc. are used.

The silica supply material used in the present invention is not particularly limited as long as it is commonly used in the production of conventional crystalline aluminosilicate, such as silica powder, silicic acid, colloidal silica, and sodium silicate. An aqueous solution is used.

The ratio of these silica feedstocks and alumina feedstocks to obtain high silica crystalline aluminosilicate is as follows:
The molar ratio of 5i02 and Al2O3 is 10=units to 1o
oo: 1, preferably in the range of 20:1 to 300:l, but molar ratios outside this range can also be used.

'eK, Vc1 Alkaline metal supply substances include hydroxides such as sodium hydroxide and potassium hydroxide, halides such as potassium chloride and potassium chloride, silica supply substances and alumina supply substances such as sodium silicate and sodium aluminate. An alkali metal supplying substance commonly used in the production of conventional crystalline aluminosilicate 1. The amount of this alkali metal supply substance used is 0.01 to 10 per mole of 5i021.
It is in the molar range.

In the method of the present invention, the reaction between the silica supplying material, the alumina supplying material and the alkali metal supplying material is carried out at 3 times per molecule.
It is necessary to carry out the reaction in the presence of an amine having at least 3 primary amine groups, and this amine preferably has 3 or more carbon atoms, preferably 7 or more carbon atoms. Particularly preferred is [1,3,6-)lyaminomethylhexane represented by the formula (in the formula, xIY and Z are each an integer of 0 or 1 or more, x
+y+z is 5 to 6) oxypropylene amine, and lysine-β-aminoethyl ester represented by the formula %[).

These triamines may be used alone or in combination of two or more.

The summer dose of triamine in the method of the present invention is 51021
The range is from 0.01 to 10 mol per mole, preferably from 0.1 to 5 mol.

In the present invention, it is necessary to carry out the reaction in an aqueous solution.

The amount of water at this time is usually in the range of 5 to 500 moles per mole of 5i021.

The reaction conditions in the present invention are not particularly limited as long as they are the conditions used for the production of ordinary crystalline aluminosilicate, but usually 50 to 300"c1, preferably 1
It is carried out at a temperature of 00 to 200°C and under normal or autogenous pressure. The reaction time is usually 1 to 500 hours, preferably 5 to 100 hours, although it depends on the temperature and pressure.

The reaction in the present invention can be carried out either batchwise or continuously, with a difference in temperature, and can also be carried out with stirring as desired.

The crystalline aluminosilicate produced by the method of the present invention can be prepared with any necessary cations, such as protons, proton precursors, and elements IA, II of the Periodic Table of Elements.
Ion exchange can be performed with one or more cations of metals belonging to A, Iln, rvA, ILB, group II, and rare earth metals.

The crystalline aluminosilicate produced by method I of the present invention is used as a catalyst or an adsorbent in a dry state, in a state in which the product is calcined at 300° C. or higher, or in an ion-exchanged state. As a catalyst, for example, production of hydrocarbons from methanol, alkylation reaction, reaction to obtain alkylbenzene or dialkylbenzene from benzene or alkylbenzene, cracking reaction, polymerization reaction,
Disproportionation reactions, e.g. toluene J: reactions to obtain lixylene and benzene; isomerization reactions, e.g. reactions to obtain xylene from ethylbenzene; dehydration reactions, e.g. reactions to obtain olefins from alcohols; It is used in reactions to obtain The crushed adsorbent is used, for example, for adsorption separation of isomers of aromatic compounds.

In this method using tetrapropylammonium salts, various alkyl monoamines, alkyl diamines, polyargylene polyamines, amino alcohols, etc. in 1, the particle size of the crystalline aluminosilicate produced becomes non-uniform, and However, when the triamine of the present invention is used, the crystalline aluminosilicate produced has an extremely uniform particle size. and also
It has the advantage of containing almost no impurities such as gel-like substances or α-quartz. Furthermore, whereas the prior art method described above requires a relatively long period of time, e.g. is for a very short time,
For example, crystalline aluminosilicate with high crystallinity can be obtained even after 5 hours.

These advantages are of great importance in industrial implementation.

Next, the invention will be explained in more detail with reference to Examples.

Example 1 In 60 g of water, A12(SO4)3ts H2Oo,s,
? 1゜3.6-) Add 5 g of methylhexane to make a homogeneous solution. This solution was converted into Q brand silicate solution (NJO=8.9wt%, 5i02=28
．． 9wt%.

H20 = 62.2 wt%) 20 g was added dropwise from a VC stirrer. Furthermore, 20% H2SO4 was added dropwise to the bath solution to adjust the pH to 11.5 to obtain a homogeneous gel. This was placed in a Teflon test tube and heated to 180°C at 20°C in a pressure-resistant container.
Let it stand for a while.

The obtained product is 17! After washing and filtering with water, 120°
It was dried at C for 5 hours and subjected to X-ray diffraction analysis.

The X-ray diffraction pattern is shown in Table 1. This diffraction pattern almost matched that of ZSM-5.

For powder X-ray diffraction, Geigerflex manufactured by Rigaku Juiki was used, and for X-rays, cuKd &l whole stool was used.
9 and NaOH20,! Melt 9 and add 1.3.6
-) Add 50.9 i of lyaminomethylhexane to obtain a homogeneous solution. Colloidal silica (5i02
= 30 wt) Put 200g into the blade, stir even more strongly, then add 20w Ii 2S O4 dropwise until the pH is 12.
A homogeneous solution was obtained. This solution was placed in a Teflon-lined v1p volume autoclave and heated and stirred at 150°C for 5 hours.

The patterns are shown in Table 2. This diffraction pattern is ZBl,
It almost matched the diffraction pattern of A and 5. An electron micrograph of this product is also shown in the attached drawing.

From this electron microscope rIj and mirror photograph, it was found that most of the sizes were 5 to 10 μ.

Example 3 In 200 g of water, A'12 (SC14)3 ], 8
H2O8& and NaOH159 are added, and an amine represented by the formula (Diefermin T-403 manufactured by Mitsui Texaco Chemical Co., Ltd.) 50.9 is added to obtain a uniform wet liquid. Colloidal silica (Si02.3 Q w
t%) 150.9 was added dropwise, and 20% H2SO was added dropwise to obtain a homogeneous solution with a pH of 12. This dissolved solution was placed in a Teflon-lined v1g autoclave at 160°C.
Heat and stir for 48 hours.

The X-ray diffraction pattern of the obtained product after pilot filtration and drying at 120° C. for 5 days was almost the same as the diffraction pattern of ZSM-5. Also, the average particle size of this product is 6.
It was μ.

Example 4 Al(NO3), 59 K2O2,9, and 30 g of the amine used in Example 3 were added to 300 g of water to make a homogeneous solution.

This solution was added to the Q brand silicate 7 in a bath solution of 100.9 K.
Drip with a single drop. Furthermore, 6C was obtained in this solution. This gel was placed in an 11-volume Teflon-lined autoclave and stirred at 180° C. for 60 hours.

After washing and filtering the obtained product with water, 120°C for 5 hours:
The X-ray diffraction pattern after drying almost matched the diffraction pattern of ZSM-5.

k Example 5 Water 200,! 9, A12(so4)318 H2O
Dissolve 8jj and 15g of NaOH, and then add lysine-β
-Ryominoe 1 Add 30.9% of thyl ester to obtain a homogeneous solution.

This solution contains colloidal silica (5io2=a o wt
%)y 200g'5710E, Sara [20%
H2E+04 was added dropwise to adjust the pH to 11 to obtain a homogeneous solution. This solution was placed in a 5-length V1 autoclave inside Teflon, and heated and stirred at 150°C for 50 hours.

This product was washed with water, filtered, and then dried at 120°C for 5 hours.
The resulting X-ray diffraction pattern almost matched that of ZBM-5.

Example 6 In water 609, A'12 (eO, a ) x 18 N20
0.5g and lysine-β-aminoethyl ester 5! j
'i Add uniform melting W7. Create. After dropping this m solution into 20g of Q brand silicate aqueous solution,
04i was added and the pH was adjusted to 10.5 to obtain a homogeneous gel. Place this gel in a Teflon test tube and place it in a pressure-resistant container.
It was left standing at 180°C for 48 hours.

The X-ray diffraction pattern of the obtained product after being pilot-filtered and dried at 120° C. for 5 hours almost matched the diffraction pattern of ZSM-5.

Reference Example The product of Example 2 was air-calcined at 500°C for 8 hours, ion exchanged with a saturated ammonium chloride water bath solution for 30 hours, and further air-calcined at 500°C for 4 hours to remove toluene. It was used as a catalyst for the equalization reaction.

A conventional fixed bed flow reactor was used as the reactor, and the reaction conditions were: reaction temperature: 600°C, normal pressure, N2/toluene molar ratio: 3, WH: 8V 2. I went with Qllr.

As a result, the results from 5 to 6 hours after the start of the reaction were as follows.

[Brief explanation of drawings]

The drawing is an enlarged microscopic photograph of crystalline aluminosilicate obtained by the method of the present invention. Patent applicant: Asahi Kasei Industries Co., Ltd. Agent: Akira Agata

Claims (1)

[Claims] 1. When producing crystalline aluminosilicate by reacting a silica supply material, an alumina supply material, and an alkali metal supply material in an aqueous solution, a feature is that an amine having three primary amine groups in one molecule is allowed to coexist. A method for producing crystalline aluminium non-licade.