JPS6117417A - Crystalline aluminosilicate zeolite and its preparation - Google Patents

Abstract

PURPOSE:To obtain the titled zeolite having X-ray diffraction pattern utterly different from that of existing zeolite, by blending SiO2 with Al2O3, Na<+>, tetramethylammonium and water in a specific ratio, subjecting the blend to hydrothermal treatment, calcining it. CONSTITUTION:An SiO2 source, Al2O3, a sodium ion source, a tetramethylammonium source, and water as raw materials are blended in molar ratios of SiO2/ Al2O3 of 30-400, OH<->/SiO2 of 0.3-0.8, Na<+>/SiO2 of 0.3-0.8, TMA<+>/SiO2 of 0.3-4.0, and H2O/SiO2 of 30-60 to give a blend, which is subjected to hydrothermal treatment at about 100-200 deg.C for about 10-200hr under self-pressure. Then, the reaction product is filtered or centrifuged to separate a solid component, which is washed with water, dried, and calcined in an air atmosphere at about 400-600 deg.C for about 2-50hr, to give crystalline aluminosilicate zeolite having a chemical composition shown by the formula (0<a<2, 30<c<300) exhibited by molar ratios of prepared oxides, showing powder X-ray diffraction pattern exhibited by the table.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention seeks to provide a novel synthetic crystalline aluminosilicate zeolite and a method for producing the same.

Crystalline aluminosilicate zeolites exist in large numbers naturally, and can also be produced artificially. Each crystalline aluminosilicate zeolite forms a certain skeletal structure and has many voids and tunnels within the structure,
Therefore, it has the function of causing adsorption of molecules of a predetermined size, but excluding molecules larger than that, and is also called a molecular sieve. The size and shape of pores due to voids and tunnels are 5in4 and A70 in the skeleton structure.
It is determined by the form in which 4 is bonded covalently with oxygen.

The electronegative nature of aluminum-containing tetrahedra is kept electroneutral by cations, usually alkali metal ions.

Therefore, in general, aluminosilicate zeolite can be expressed in terms of the molar ratio of oxides in a dehydrated state as follows.

・ , ・ ・
・ Force”; Mz/nO-A1203-
xsi02 (M is a cation of valence n) Zeolites occur naturally and are also produced synthetically. In recent years, when synthesizing zeolite, there have been many reports on the use of organic ammonium cations such as tetramethylammonium, tetraprolylammonium, and tetrapropylammonium in addition to using alkali metals such as sodium as cations.

When tetramethylammonium is used, the synthesized zeolite is TMA offretite (M・K, 几u
bin Qer, 0ffen 1,806.154
(1969), .

43M4 (Mobile Oil C0rp, ,1
3rit, Pat, 1,117°568 (1968
)) etc. These zeolites have different X-ray diffraction patterns and are thought to belong to a different class structurally. It is well known that even if the same starting materials are used, different zeolites can be synthesized due to differences in raw material composition ratio, hydrothermal treatment, etc. conditions.

As a result of intensive research, the present inventors completed a novel aluminosilicate zeolite 14, which has a completely different X-ray diffraction pattern from existing ones, by hydrothermally treating an aqueous gel containing tetramethylammonium.

The crystalline aluminosilicate zeolite of the present invention (hereinafter referred to as C
I (referred to as C-2) will be explained in detail.

The chemical composition of the synthetic form of CHC-2 of the present invention is expressed as a dehydrated oxide molar ratio of aNa20. b(TMA)20・Al2O3・cS1o
2 (here TMA is tetramethylammonium)
However, 0(a('2.0 0(1)(10,0 30(C(300).

Furthermore, the lattice spacing determined by X-ray diffraction is shown in Table 1. Note that these XS diffraction patterns were obtained using standard X-ray techniques by irradiating copper with alpha rays, and the height of the peak representing reflection is at 2 of Black's angle, which corresponds to the lattice spacing d. times, recorded on the recorder as a function of 2θ. The relative intensity 100I/Io is a relative value to the highest peak height ■0.

Furthermore, the chemical composition of CHC-2 of the present invention after firing is aNa20-AlzO3-cSio expressed as a dehydrated oxide molar ratio.
a〈 ・20 30〈C〈300.

Further, the lattice spacing determined by X-ray diffraction is shown in Table 2.

As described above, the crystalline aluminosilicate zeolite of the present invention, CI-I C-2, has an XS diffraction pattern completely different from that of existing zeolites in both the synthesized form and the post-calcination form, and is a novel crystalline aluminosilicate. It is zeolite.

Table 1 + 4.45 0. IS 2.94 ambition 0.0
5 VW+ + 4.300. I S 2.870.05 W+ 4.08 0. IS 2.83!060
5 V'W+''-4,030,I VS 2.780.05 W 10 4.
00 0. IS 2.76 0.0
5 W 1113.95 0.07 S 2.69 0
．． 05 W388±0.07 VS
2.63±0.05 VW+ 3.85 0.07 M z, so support o, o
s vw 13.70 0.07 W 2.44 0.0
5 VW (However, VW 20-5, W: 5-201M
=20~4o1S:40~60,vS:60~100)
Table 2 (VW: O~5, W:5~20, M:20~
40, S: 40-60, VS: 60-100) Next, the method for producing the crystalline aluminosilicate zeolite of the present invention will be described.

In the present invention, the molar ratio of 5102 source, Al2O3 source, Na source, tetramethylammonium source and water is as follows: SiO□ZA1203-30 ~4000H/5in2
0.3~0.8 NA /5in203~08 TMA/S 102 0.3~4.01120/
The crystalline aluminosilicate zeolite of the present invention is characterized in that a mixture of SiO□3° to 6° is hydrothermally treated at 100 to 200°C, preferably 130 to 180°C, under autogenous pressure for 10 to 200 hours. The present invention relates to a manufacturing method.

The method for producing the crystalline aluminosilicate zeolite of the present invention will be specifically described. In the water droplet, 5102 source, A
/ho3 source, l'Ja source, tetramethylammonium source, and water are mixed in a predetermined ratio, and this mixture is treated under hydrothermal conditions to obtain zeolite, and the obtained solid product is washed with water, dried, and calcined. By doing so, the crystalline aluminosilicate zeolite of the present invention can be produced.

As the 5102 source, water glass, silica sol, phosphoric acid gel, and phosphoric acid can be used, and water glass and silica sol are preferably used.

As the Al2O3 source, aluminum sulfate, aluminum nitrate, aluminum chloride, sodium aluminate, alumina sol, alumina, metal aluminum, etc. can be used, but aluminum nitrate and sodium aluminate are preferable.

As a sodium source, in addition to sodium hydroxide, etc.
102 sources and A120A sources, such as sodium oxide and sodium aluminate contained in water glass, can also be used.

As the tetramethylammonium source, tetramethylammonium bromide, tetramethylammonium iodide, etc. can be used.

When mixing the above-mentioned 5102 source, Al2O3 source, etc. in a predetermined ratio, the mixing order and mixing method are not particularly limited.

This mixture is then hydrothermally treated under conditions that produce zeolite. i.e. 100-2001nT]
The mixture is hydrothermally treated at 130 to 180° C. for 10 to 200 hours in a closed container under autogenous pressure with stirring.

After the hydrothermal treatment, the reaction product is stale, and solid components are separated by centrifugation, excess ionic substances are removed by washing with water, and then dried at 100℃ and heated to 400 to 600℃ in an air atmosphere.
By calcining at 0°C for 2 to 50 hours, the crystalline aluminosilicate zeolite of the present invention, CI-I C-2, is obtained.

In general, zeolite can be used as an adsorbent or as a catalyst in the production of petrochemical products, but the crystalline aluminosilicate zeolite of the present invention, CI (C = 2), also has ion exchange ability, and can be used as an adsorbent or catalyst. Can be used as a catalyst.

Crystalline aluminosilicate zeolite of the present invention, CHC
-2 is used as an adsorbent, tetramethylammonium contained as a synthetic form 400 ~
After removing part or all of it by firing at 600°C for 2 to 50 hours, it can be used in a conventional manner.

When used as a catalyst, it can be used in any form such as a gas-solid catalytic reaction after part or all of the tetramethylammonium has been removed by the above method. Generally, catalytic performance can be altered by ion-exchanging at least a portion of the sodium ions in the synthetic form with other ions.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto unless it exceeds the gist thereof.

Example 1゜160 ammonium sulfate 16-18 hydrate in 116 I water
g, 3.54 g of sodium hydroxide, and 49.3 g of tetramethylammonium bromide.
3040 g of id 5I was gradually added to form a homogeneous mixture. The composition of this mixture is expressed in molar ratio: SiO□/A
#z03= ] O01OH/SiO□=0,4, TM
A/Sin21.6, H20/S i 02= 40
It is.

This mixture was sealed in a magnetically stirred autoclave with an internal volume of 300 ml, and hydrothermal synthesis was carried out at 150° C. for 20 hours while stirring at a rotational speed of soor-pm under autogenous pressure.

After the reaction was completed, solid components were separated from the reaction mixture by centrifugation and thoroughly washed with ion-exchanged water to remove excess ionic substances. This material was dried at 120°C for 5 hours to obtain a white powder.

The X-ray diffraction pattern of this white powder is shown in Table 4 and Figure 1. The chemical composition of this powder is Q, 84 Na2O.4.
7 (TMA)20.Alz03.62Si02.

In addition, the X-ray diffraction pattern of the powder obtained by firing the above white powder at 500°C for 20 hours in an air atmosphere is shown in Tables 5 and 2.
As shown in the figure. The chemical composition of this powder is 0.84 Na2OH
Al1203 H625i02 Teatsu7'i(.

Examples 2 to 5 As shown in Table 3, experiments were conducted in the same manner as in Example 1 except that the raw materials for the hydrothermal reaction were changed and the reaction conditions were changed. All of the materials obtained were white powders whose X-ray diffraction patterns were essentially the same as those shown in Table 4 and No. 1.

Example 2 Example 3 Amount of raw material charged U) Catalo soil dSI-304040 Sodium hydroxide 3.66
3 water
116 11f Raw material charging molar ratio 5102/A1□035o5c OH/5i02 0.4
C+ Na/5102 0.4
CTMA/Sin□1.6
0H20/5in240/iC
Hydrothermal reaction conditions Temperature CC) A (hr) 160/20
] (i.

Product chemical composition 0.39 Na2O0,36
Na2O Example 4 Example 5. 56 2,56 0.64,
．． 6G 3.66 3,40
1.6 12.3 77.01
50 20Or40.4
0.4 1"40・40.4 1.8 0.4 2,50
, 38 Na2O1,7Na20 − -mtakirb + 8-8/rrXhK^M/”1
Usage Example Mix 1 g of the calcined white powder obtained in Example 1 with 5 Q ml of a 1N hydrogen chloride aqueous solution, and add 1 g of the calcined white powder at room temperature.
The mixture was stirred for a period of time to exchange sodium ions with hydrogen ions. Thereafter, it was thoroughly washed, dried at 100°C, and then fired at 500°C for 8 hours. Elemental analysis of the obtained white powder was carried out and the results were completed.
It was Na20.Al2O3.64S10□. This was compressed into tablets at a pressure of 400 and 9/crfL2, and then pulverized, and 4 ml of 10 to 20 mts was filled into a reaction tube with an inner diameter of IQ mm. 4m of liquid methanol
Send it to the vaporizer at a rate of l/hr, where 4! Mll/m
The mixture was mixed with argon gas sent through the inlet (7), introduced into a reaction tube, and reacted at 400°C. Analysis of the product using a gas chromatograph revealed that the methanol conversion rate was 39%, and the product was mainly dimethyl ether.

Table 4 8.95 18 3.54
328.34 45
3.43 56.57 2
7 3.29 186.24
64 3.25 2
65.64 7 3.1.
0 145.38 8
3.04 54.63
7 2.97 54
．． 45 53 '2.94
54.30 4.7
2.87 184.08
45 2.83 3
4.03 100 2.78
124.00 60
2.76 133.95
60 2.69 103
．． 88 73 2.63
33.85 29
2.50 43.70
18 2.44 4th
5 Table 8.93 37 3.7], 58.34 9
5 3.50 16 6.56 45 3.43 5 6.19 100 3.29 20 5.67 15 3.09 10 5.61 16 3.01 7 5.34 7 2.96 7 4.44 29 2 .88 10 4.30 20 2.85 7 4.11 27 2.80 5 4.03 45 2.75 7 3.94 43 2.67 5 3.84 43 2.49 5 3.80 18 2.31 5

[Brief explanation of drawings]

FIG. 1 is an X-ray diffraction pattern of the synthetic form of the material obtained in Example 1. FIG. 2 is an X-ray diffraction pattern of the material obtained in Example after firing.

Claims (1)

[Claims] (1) Expressed as a molar ratio of oxides, aNa_2O・Al_
A crystalline aluminosilicate zeolite having a chemical composition of 2O_3.cSiO_2 where 0<a<2 30<c<300 and exhibiting the powder X-ray diffraction pattern shown in the following table. Table d value (Å) Relative intensity d value (Å)
Relative intensity (100I/Io) (100I/I
o) 8.93±0.1 M 3.71±0.
07 VW 8.34±0.1 VS 3.50±0.
07 W 6.56±0.1 S 3.43±0.
07 VW 6.19±0.1 VS 3.29±0.
07 M 5.67±0.1 W 3.09±0.
07 W 5.61±0.1 W 3.01±0.
07 W 5.34±0.1 VW 2.96±0.
05 W 4.44±0.1 M 2.88±0.
05 W 4.30±0.1 M 2.85±0.
05 W 4.11±0.1 M 2.80±0.
05 VW 4.03±0.1 S 2.75±0.
05 W 3.94±0.07 S 2.67±0.
05 VW 3.84±0.07 S 2.49±0.
05 VW 3.80±0.07 W 2.31±0.
05 VW (VW: 0-5, W: 5-20, M: 20-40
, 5:40-60, VS:60-100) (2) Using SiO_2 source, Al_2O_3 source, sodium ion source, tetramethylammonium source and water as raw materials, molar ratio SiO_2/Al_2O_3 30-400OH^-/
SiO2 0.3-0.8Na/SiO_2
0.3~0.8TMA/SiO_2
0.3~4.0H_2O/SiO_2 30~
By hydrothermally treating a mixture so as to have a concentration of 60% and firing the obtained crystalline aluminosilicate zeolite, the resulting oxide is expressed as a molar ratio of aNa_2O・Al.
A method for producing crystalline aluminosilicate zeolite having a chemical composition of _2O_3.cSiO_2 where 0<a<2 30<c<300 and exhibiting a powder X-ray diffraction pattern shown in the following table. Table d value (Å) Relative intensity d value (Å)
Relative intensity (100I/Io) (100
I/Io) 8.93±0.1 M 3.71±0.
07 VW 8.34±0.1 VS 3.50±0.
07 W 6.56±0.1 S 3.43±0.
07 VW 6.19±0.1 VS 3.29±0.
07 M 5.67±0.1 W 3.09±0.
07 W 5.61±0.1 W 3.01±0.
07 W 5.34±0.1 VW 2.96±0.
05 W 4.44±0.1 M 2.88±0.
05 W 4.30±0.1 M 2.85±0.
05 W 4.11±0.1 M 2.80±0.
05 VW 4.03±0.1 S 2.75±0.
05 W 3.94±0.07 S 2.67±0.
05 VW 3.84±0.07 S 2.49±0.
05 VW 3.80±0.07 W 2.31±0.
05 VW (VW: 0-5, W: 5-20, M: 20-40
, S: 40-60, VS: 60-100)