JPH01148706A - Crystalline metallosilicate and its production - Google Patents

Abstract

PURPOSE:To obtain metallosilicate improved in adsorbing and catalytic properties, by keeping a reaction mixture prepd. form org. cation source, silicon source, aluminum source, iron source, boron source, alkali-ion source and water at a specified temp. CONSTITUTION:The reaction mixture having the compsn. of formula II expressed with a molar ratio of oxides of silicon, aluminum, iron and boron is prepd. by mixing one or more kinds of source (M') among the org. cation source (R), silicon source, aluminum source, boron source, alkali metal ion source, alkaline earth metal ion source and ammonium ion source, and water. Then, the reaction mixture is kept at 100-250 deg.C to obtain the porous crystalline metallosilicate of formula I. In the formula II above-mentioned, T2O3 is Al2O3 + Fe2O3 + B2O3 and n' is valence of M'. And in the formula I, 0<=a<=1.0, a+b<=1, x>=8, M is cation and (n) is valence of M.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a crystalline metallosilicate porous body containing silicon and boron, or these and iron or aluminum, and a method for producing the same. This novel metallosilicate of the present invention is hereinafter collectively referred to as Go5FBS-6. Zeolites are generally aluminosilicates, consisting of Al0 bonded by sharing oxygen atoms with each other.
The TSFBS-6 of the present invention has a three-dimensional skeleton structure of J, and SiO4 tetrahedron.
Or metallosilicate porous bodies with uniform pores replaced with FeO* and BO4 tetrahedra. These metallosilicate porous materials have adsorption properties and catalytic performance that cannot be obtained with conventional zeolites, so they can be used as molecular sieves,
It is useful as an adsorbent or a catalyst component for hydrocarbon conversion reactions. <Prior art> A crystalline silicate porous body containing iron or boron in its skeleton that has been known so far is disclosed in JP-A-61-778.
No. 18 and JP-A-62-113716 disclose a crystalline silicate porous body having the structure of zeolite ZSM-5. Further, Japanese Patent No. 59-88313 discloses an iron aluminosilicate zeolite having an X-ray diffraction pattern similar to the TSFBS-6 of the present invention. This zeolite contains iron and aluminum in its skeleton, but does not contain boron. <Problems to be Solved by the Invention> With zeolite, that is, aluminosilicate, there is a limit to the control of adsorption characteristics and catalytic performance by controlling the Si/At ratio. The present inventors have discovered that by having a zeolite-type structure and containing different atoms in the crystal lattice, it has pore size, solid acid properties, evil adsorption properties, and catalytic performance that cannot be obtained with conventional zeolites. As a result of extensive research aimed at synthesizing metallosilicates, the present invention was achieved. Means for Resolving Problems> The novel substance of the present invention contains silicon in its crystal lattice. Contains iron, boron, or these and aluminum, i.e.
Expressed in molar ratio of oxides, (1±0,3) M2/nO・aFe2O3IIbB2O3・(1-a-b)AI2Oa・xS 1o2 (in the formula, a, b
is 0≦a<1. O<b≦1 and a+b
≦1, X is a number of 8 or more, M represents at least one cation, and n represents the valence of M. A porous crystalline metallosilicate having a chemical composition of the anhydride group i as shown in FIG. The cation M is not particularly limited, but may be an organic cation, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a hydrogen ion, or a mixture of these cations. Table 1 Powder X-ray diffraction pattern spacing d(A') Peak intensity 13.70±
0.50 M 9.10±0.30 M~■S 6.61±0.15 M~S 4.53±0.07W-M 4.00±0.07 M~S 3.48±0. 05 M~■S 3.39±0.05 W~M (In the table, W, M, S, and VS are each weak. Medium 9 represents strong and very strong.) The crystallinity of the present invention is shown below. metallosilicate) T-SFBS-
The manufacturing method of No. 6 will be explained. Silicon source; Iron source; Boron source; Aluminum source; Organic cation source; Any one or more of alkali metal ions, alkaline earth metal ions, and ammonium ion sources: and water are mixed to produce silicon, aluminum, iron, and boron. is expressed as the molar ratio of oxides and has the following composition: 5102/T2O3 10-100 B2O3/T2O30,01-1. O Fe? 03/T2O30~0.99 0H-/H2O0,010~0.019M″2/II・
O/SiO+O~1.0H2O/Si○230~100 R/(SiO2+T2O3) O~1.0 (however,
T2O3 is (A 12O3+ Fe2O3+B 2O
3), R represents an organic cation, M' represents one or more of alkali metal ions, alkaline earth metal ions, and ammonium ions, and n' represents the valence of M'. ) is prepared, and the reaction mixture is divided into 100
After crystallization while maintaining the temperature between .degree. C. and 250.degree. C., TSFBS-6 can be obtained by collection, washing, and drying operations. The silicon source, iron source, boron source, aluminum source, organic cation source, alkali metal ion, alkaline earth metal ion, or ammonium ion source is not particularly limited. For example, as a source of alkali metal ions, alkaline earth metal ions, or ammonium ions, hydroxides of the ions or neutral salts thereof can be used. As the silicon source, water glass, colloidal silica, amorphous silica, fumed silica, etc., which are conventionally used in zeolite production, can be used. Iron source is iron sulfate. Iron nitrate, iron chloride, iron ammonium sulfate, iron hydroxide, etc. can be used. Boric acid or borates can be used as the boron source. As an aluminum source, alumina sol is traditionally used in zeolite production. Pseudoboehmite, sodium aluminate, aluminum hydroxide, aluminum oxide, aluminum sulfate, etc. are used. The organic cation source used is one containing nitrogen or phosphorus. Preferably, it is supplied by introducing a hydroxide or halide of tetraethylammonium or benzyltrimethylammonium. If the reaction mixture is heterogeneous, impurities may be generated as by-products, so these raw materials are added under stirring, and the intermediate mixture until all of the raw materials are added and the final reaction mixture after the supply is substantially free. It is preferable to stir until the mixture becomes homogeneous. The final reaction mixture thus obtained is crystallized in a sealed pressure vessel made of stainless steel lined with an inert plastic material, such as polytetrafluoroethylene, to prevent contamination with impurities. Crystallization is preferably carried out under natural pressure for about 10 minutes until crystals of TSFBS-6 form.
This is done by maintaining a temperature of 0°C to about 250°C. Generally, it is sufficient to leave it at this temperature for about 2 hours to about 200 hours. The product is recovered by conventional separation methods such as filtration or centrifugation. TSFBS-6 thus obtained contains the organic matter used as a mineralizer in its pores. This organic matter can be removed if necessary, but is not removed by treatments such as ion exchange, but by calcination at boat fishing calcination temperatures, ie, temperatures of 400 to 650°C. The X-ray diffraction pattern of TSFBS-6 is not substantially changed by this calcination. CuK-α radiation was used for X-ray diffraction of the product. As is known to those skilled in the art, the determination of the parameter 2θ is subject to human and mechanical errors, which can impose an error of approximately 0.4 @ on each recorded value of 2θ. Also,
The recorded values of 2θ and peak intensity may vary depending on the composition of the substance's skeleton, the type of cations, the degree of heat treatment, etc. This error, of course, introduces uncertainty into the d-spacing and relative intensity values calculated from each recorded value. However, this uncertainty is not sufficient to prevent the novel materials of the present invention from being distinguished from prior art materials. <Effects of the Invention> The above organic cation-containing TSFBS-8 can be decomposed and removed by firing at 400 to 650°C in an air stream as necessary, and then treated with, for example, ammonium hydroxide, ammonium sulfate, or ammonium nitrate. After converting into ammonia form by ion exchange with ammonium salt such as 4
Ammonia can be removed by firing at 00 to 650°C to obtain J-active hydrogen type TSFBS-6. The acid strength and acid amount of TSFBS-6 of the present invention continuously change depending on the difference in its composition. Even in conventional aluminosilicate, Si in the crystal
It was possible to control the acid strength and acid amount by changing the 02/A 12O3 molar ratio. However, generally the acid strength of aluminosilicate is S i
02/A I has a positive correlation with the 2O3 molar ratio,
Since the amount of acid has a negative correlation with the S i 02 /A 12O3 molar ratio, it was not possible to control the acid strength while maintaining the amount of acid. Furthermore, aluminosilicate is S
It is known that hydrophilicity decreases as the i02/A12O3 molar ratio increases. However, the TSFBS-6 of the present invention has a high acid strength and acid content that cannot be achieved with conventional aluminosilicates. It is possible to control each independently and maintain its hydrophilicity,
For example, by controlling the acid strength and acid amount in a hydrocarbon conversion reaction, the selectivity of the reaction can be favorably influenced. T'SFBS-8 can be used as a catalyst component for hydrocarbon conversion reactions, etc. by supporting desired metal ions through conventional ion exchange, impregnation, etc. TSFBS-6 also exhibits unique performance as an adsorbent. The interplanar spacing in the X-ray powder diffraction pattern of TSFBS-6 changes continuously depending on the difference in its components. Boron and iron form the skeleton of TSFBS-6. Regarding the bond distance between each of aluminum and silicon and oxygen, there is a relationship of B-0<5i-0<Al-0<Fe-0. Therefore, by increasing the content of boron, which has a shorter bond distance with oxygen than aluminum or silicon, among the elements constituting TSFBS-6, a smaller pore diameter can be obtained. Further, by increasing the content of iron, which has a longer bond distance with oxygen than aluminum or silicon, a larger pore diameter can be obtained. Therefore, the TSFBS-
By controlling the composition of the skeleton, No. 6 enables a wide range of pore diameter control that could not be obtained with conventional aluminosilicates, and can favorably affect the selectivity of adsorbed molecules. <Examples> In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited to the following Examples. Example 1 Aluminum chloride (AlCl2.6H2O) 5°36g
, ferric nitrate (Fe(NO3)3.9H2O) 9.04
Solution A was prepared by dissolving 0.691 g of boric acid in 148.7 g of water. Water glass (S 1o2 = 29.3 wt%, Na2O = 9
．． 35wt%, Al2O3=0. 016wt
%. H2O=61.334wt%) 143.3g and water 48
．． Add sodium hydroxide (98%
Solution B was prepared by dissolving 12.6 g of NaOH). 58.8g of tetraethylammonium bromide to 273.6g
g of A in water under stirring. Both solutions B were added dropwise to prepare a reaction mixture having the following composition. SiO2/T2O3=25 B2O3/T2O3=0.2 Fe2O3/T2O3=0.4 0H-/H2O=0.012 NazO/Si○2 =0.28H2O/SiO
2=45 TEA+/(S io2+T2O5)=0.38 (However, T2O3 is (A I 2O3+F e2O3
+B2O3), and TEA+ represents traethylammonium ion. same as below. ) The reaction mixture was sealed in an autoclave and heated to 165 DEG C. under natural pressure with constant stirring and maintained at this temperature for 69 hours to obtain a crystalline product. After filtering and washing with water, 1
It was dried at 10°C. Chemical analysis revealed that this product had the molar composition shown in Table 7. Moreover, this was a metallosilicate of the present invention having an X-ray diffraction pattern shown in Table 2. Table 2 L] 13.62 47 10.54 26 9.09 100 6.61 50 6.41 18 6.08 13 5.81 21 5, 03 5 4, 53 484.15
74, 00
753, 84
213.48 81
3, 40 553, 22
743, 21
633.11
112, 95 9
2, 90 252.71
7 Example 2 Example 1 except that aluminum chloride was not used.
A reaction mixture having the following molar composition was prepared in a similar manner. SiO2/T2O3=25 B2O3/T2O3=0.6 Fe2O3/T2O3=0.4 ○ H-/H2O=0. 0 1 2 Na2O/Si ○2 =0. 37H
2O/5iOz =60TEA+/(S
i ○2+T2O3)=0. 38 The reaction mixture was sealed in an autoclave, heated to 165° C. under natural pressure with constant stirring, and maintained at this temperature for 69 hours to obtain a crystalline product. After filtering and washing with water, 11
It was dried at 0°C. Chemical analysis revealed that this product had the molar composition shown in Table 7. Moreover, this was a metallosilicate of the present invention having an X-ray diffraction pattern shown in Table 3. Table 3 Beans-Ll->-・ 13.70 30 10.03 7 9.03 100 6.60 27 6.38 ? 6. 07
65.81
14 5, 04 24, 53
33 4, 27 24.15
9 3, 99 353.83
21 3, 76 53, 63
63, 4B
343.38 25 3, 22 403, 2O
283.10
22, 94 42.8
9 12 2, 70 3 Example 3 A reaction mixture having the following molar composition was prepared in the same manner as in Example 1, except that aluminum chloride was not used. 5i02/T2O3=25 B2O3/T2O3=0.2 Fe2O3/T2O3=0.8 0H-/H2O=0.012 Na2O/S Zo2 =0.28H2O/SiO
2=45 TEA”/(S i02+T?oa)=0.38 This reaction mixture was sealed in an autoclave, heated to 165° C. under natural pressure with constant stirring, and maintained at this temperature for 68 hours to obtain a crystalline product. After filtering and washing with water,
It was dried at 0°C. Chemical analysis revealed that this product had the molar composition shown in Table 7. Moreover, this was a metallosilicate of the present invention having an X-ray diffraction pattern shown in Table 4 and FIG. Table 4 Wataru-Ll) - 13.80 39 10.32 5 9.18 60 6.62 66 6, 42 9 6.08 12 5.83 14 5, 0? 4 4.54 50 4, 25 5 4.17 12 4.00 80 3.85 29 3, 77 9 3.64 10 3.48 Zo. 3.39 52 3.23 79 3.219 41 3.11 92.95
112, 90
302.71
8 (However, 2, S indicates that it was observed as a shoulder. The same applies hereinafter.) Example 4 Example 1 except that aluminum chloride was not used.
A reaction mixture having the following molar composition was prepared in a similar manner. S i 02/T2O3= 15 B2O3/T2O3=0.2 Fe2O3/T2O5=0.8 0H-/H2O=0.012 Na2O/S Zo2=0.27H2O/SiO
2=45 T E A”/(S i 02+ 72O3)=0.
38 The reaction mixture was sealed in an autoclave, heated to 165° C. under natural pressure with constant stirring, and maintained at this temperature for 68 hours to obtain a crystalline product. After filtering and washing with water, 11
Dry at 0'C. Chemical analysis revealed that this product had the molar Mi composition shown in Table 7. Moreover, this was a metallosilicate of the present invention having an X-ray diffraction pattern shown in Table 5. Table 5 疋IJ,＞-柾l''1

[Yu 3'' - 13,6634] 0.28 4 9.10 100 6.60 31 6.41 9 6, 07 8 5.80 14 5, 05 3 4.53 32 4.15 93, 99
373.83
12 3, 76 43, 63
53, 48
383, 39 253,
23 45 3, 2O929 3,104 2,945 2,9012 2,704 Example 5 Example 1 except that aluminum chloride was not used
A reaction mixture having the following molar composition was prepared in a similar manner. SiO+/T2O3=40 B2O3/T2O3=0, 2 Fe2O3/T2O3=0.8 0H-/H2O=0. 0 1 6 Na 2 O/S io 2 =0. 35H
2O/SiO2=45 T EA”/ (S i 02+ T2O3)=
0. 39 The reaction mixture was sealed in an autoclave, heated to 165° C. under natural pressure with constant stirring, and maintained at this temperature for 68 hours to obtain a crystalline product. After filtering and washing with water, 11
It was dried at 0°C. Chemical analysis revealed that this product had the molar composition shown in Table 7. Moreover, this was a metallosilicate of the present invention having an X-ray diffraction pattern shown in Table 6. Table 6 Stop-ml old 1] ± 13.62 19 10.05 2 9.04 100 6.60 12 6, 39 3 8, 0? 36, 79
1 1 5, 04 1 4.53 2O 4.15 7 4.00 15 3, 83 6 3, 83 3 3.48 15 3.39 12 3.22 36 3.2O321 3,102 2,942 2,906 2,713 Table 7 Molar composition of product tTEA2OφmNa2O- aF e2O3-bB2O3- (1-ab)Al2O3・yS 1o2

[Brief explanation of the drawing]

Figure 1 shows metallosilicate powder X obtained in Example 3.
It is a figure showing a line diffraction pattern. Patent applicant: Tosoh Corporation

Claims (1)

[Claims] (1) Expressed in molar ratio of oxides, (1±0.3)M_2_/_nO・aFe_2O_3・bB_2O_3・(1-a-b)Al_2O_3・xSiO_2 (in the formula a
, b is a number that satisfies 0≦a<1, 0<b≦1 and a+b≦1, x is a number of 8 or more, M is at least one kind of cation, and n is the valence of M. represents. ) A porous crystalline metallosilicate having a chemical composition on an anhydrous basis, and having a powder X-ray diffraction pattern substantially including the interplanar spacings shown in Table 1 in an unfired state. Table 1 Powder X-ray diffraction pattern Planar spacing d(A): Peak intensity 13.70±0.50: M 9.10±0.30: M~VS 6.61±0.15: M~S 4.53 ±0.07: W~M 4.00±0.07: M~S 3.48±0.05: M~VS 3.39±0.05: W~M (In the table, W, M, S , VS represent weak, medium, strong, and very strong, respectively.) (2) Expressed as the molar ratio of oxides, (1±0.3)M_2_/_nO・aFe_2O_3・bB_2O_3・(1-a -b) Al_2O_3・xSiO_2 (a in the formula
, b is a number that satisfies 0≦a<1, 0<b≦1 and a+b≦1, x is a number of 8 or more, M is at least one kind of cation, and n is the valence of M. represents. ) A method for producing a porous crystalline metallosilicate, which has a chemical composition on an anhydrous basis, and has a powder X-ray diffraction pattern substantially including the interplanar spacings listed in Table 1 in an unfired state. A source of organic cations; a silicon source; an aluminum source; an iron source; a boron source; one or more of alkali metal ions, alkaline earth metal ions, and ammonium ion sources; ,
Iron and boron are expressed in molar ratio of oxides and have the following composition: SiO_2/T_2O_3: 10-100 B_2O_3/T_2O_3: 0.01-1.0Fe_
2O_3/T_2O_3: 0~0.99OH^-/H_
2O: 0.010~0.019M'_2_/_n・O/
SiO_2:0~1.0H_2O/SiO_2:30~
100 R/(SiO_2+T_2O_3): 0 to 1.0 (However, T_2O_3 is (Al_2O_3+Fe_2O_3
+B_2O_3), R represents an organic cation, M' represents one or more of alkali metal ions, alkaline earth metal ions, and ammonium ions, and n' represents the valence of M'. ), and the reaction mixture was heated at 100°C to 25°C.
A method for producing a porous crystalline metallosilicate, the method comprising maintaining the temperature at 0°C. (3) The method for producing a porous crystalline metallosilicate according to claim 2, wherein the organic cation is a tetraethylammonium ion, a benzyltrimethylammonium ion, or a mixture thereof.