NZ201754A - Zeolitic boro-aluminosilicates and use as olefin producing catalysts - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £01 754 201754 (.g'-g'i . 1.& ■ s>"S>2. • t • • » Priority * *• % « ■" ■ | I Complete Spoc-ir.cslton rusa: .~ Class* . £&•' ^ ■' . >nU 112 JUL 1985J Pubhoatjori Data. .. .* P.O. Journal No: A 2-1) fe'l li MI EM JGS NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION N.Z. No.

,/V - AUG 1982 "BORO-ALUMINOSILICATES HAVING ZEOLITE STRUCTURE, PROCESS FOR THEIR MANUFACTURE , AND THEIR USE" We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany, of D-62 30 Frankfurt/Main 80, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the ;method by which it is to be performed,to be particularly described in and by the following statement 201754 Zeolites are crystalline aluminosilicates, in which due to a three-dimensional linkage of SiO^ and AlO^ tetrarhedra regular structures with cavities and pores are formed. In hydrated state, these pores and cavities are filled with 5 water, which, on the other hand, can be easily removed without influencing the crystalline structure, or replaced by other molecules. The negative charges of the AlO^ tetrahedra are balanced by cations, which can be replaced by other ions of positive charge. These properties allow the 10 use of the zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).

Zeolites of the X, Y, mordenite, erionite or offre-tite type, for example, are of considerable interest in the industrial practice as catalysts for hydrocarbon conversion 15 reactions such as cracking, hydrocracking or isomerization. Zeolites of the pentasil type (for example Zeolite ZSM-5) become increasingly important as catalysts for the conversion of methanol to hydrocarbons.

Because of the numerous application possibilities as 20 catalysts, there is great interest in novel zeolites having specific catalytical properties.

Very interesting zeolites are for example obtained by incorporating other elements instead of aluminum and/or silicon into the zeolite frame. Thus, zeolites of the 25 pentasil series are known which contain boron, iron, arsenic, antimony, vadium, or chromium in tetrahedral position.

Subject of the present invention are boro-aluminosili-cates having a zeolite structure which 2017 5 4 - 3 - iioh amm am a) have the following composition: Si02 : (0.08 ± 0.05) fAl2C>3 + B20^7 : (0.12 ± 0.10) /Na20 + K2Q7 : (0.10 ± 0.09) R20 expressed as molar ratio of oxides; R being choline 5 /f(CH3)3NCH2CH20H7 + b) have the characteristic X-ray diffraction pattern set forth below in Table 1: Table 1 1 u Interplanar Spacing d Cl J Relative Intensity X/Io 11.5 - 0.2 very strong 9.2 ± 0.2 weak 7.6 ±0.2 medium 6.6 ±0.1 strong .7 ± 0.1 medium .35 ± 0.1 weak 4.98 ± 0.1 11 4.56 ± 0.1 strong 3.32 ± 0.1 11 4.16 ± 0.1 weak 3.81 ± 0.1 strong 3-75 ± 0.1 very strong 3.59 ± 0.1 medium 3.30 ± 0.1 it 3.15 ± 0.1 weak 2.86 ± 0.1 strong 2.67 ±0.1 weak I = intensity of the strongest line or peak.

The intensities of Table 1 are defined as follows: relative intensity 100 I/;Co very strong 80 - 100 strong 50 - 80 medium - 50 weak 0 - 20 The aluminum/boron ratio of the zeolites of the invention is generally A12°3 = 0.40 - 0.99 A1203 B2°3 preferably A12°3 ai2o3 + b2o3 — 0.75 - 0.99 expressed as molar ratio of the oxides.

The novel zeolites of the invention have a structure similar to zeolite T (U.S. Patent No. 2,950,952); - - • • — however, they have a different composition, especially with respect to 25 the boron content.

The zeolites of the invention are prepared by mixing water with silicon, aluminum, boron, sodium, potassium and choline compounds, and heating the mixture in a closed vessel The starting compounds are generally used in the following ratio, expressed as molar ratio of the oxides: Si02 : (0.06 * 0.05) A1203 : (0.06 ± 0.05) B203 (0.2 - 0.15) Na20 : (0.12 ± 0.10) K20 : (0.22 ± 0.2) R20 : (50 ~ 40) H20 preferably in a ratio of 2 017 5 4 - 5 - IIOD OUT QQQ Si02 : (0.05 - 0.03) A12C>3 : (0.05 - 0.03) BgOji (0.2 i 0.1) Na20 : (0.09 - 0.05) K20 : (0.22 - 0.2) R20 : (50 ± 40) H20; R being choline.

As compounds, there are used for example silica gel, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, boron trioxide, boric acid, borax, sodium hydroxide, 10 sodium sulfate, potassium hydroxide, potassium sulfate, choline hydroxide, choline chloride. Other silicon, aluminum, boron, potassium, sodium and choline compounds are also suitable for the manufacture of the zeolites according to the invention.

The mixture of the compounds chosen and water is ge nerally heated for 48 to 2,000, preferably 48 to 1,000, hours at a temperature of from 80 to 160°C, peferably 90 to 150°C, in a closed vessel.

The crystalline zeolites which are formed are isola-20 ted in usual manner, for example by filtration, washed and dried. They" can be converted according to known methods to catalytically active forms, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).

After conversion to the catalytically active form, the zeolites of the invention are distinguished by a high selectivity and reduced deposition of coke in the conversion of methanol to lower olefins. It is surprising that zeolites having the characteristics according to the invention can 30 be obtained by means of the indicated method.

The following Examples illustrate the invention without limiting it in its scope. All X-ray diffraction data as indicated were obtained by means of a computer-controlled powder diffractometer D-500 of the Siemens company. The 35 radiation was the K-<^ doublet of copper. 201754 Example 1 9.0 g of sodium aluminate (54 weight % of Al^O^, 41 weight % of Na20) , 0.83 8 of boron trioxide, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide, and 45.6 g 5 of choline chloride are dissolved in 150 g of water. 117 g of 40 weight % colloidal silica gel are added to this solution, and the suspension so formed is homogenized and heated for 8 days at 150°C. The product obtained is filtered off, washed with water and dried at 120°C. 10 Chemical analysis yields the following composition, expressed as molar ratio of oxides: Si02 : 0.075 Al^ : 0.003 : 0.048 Na20 : 0.023 K20 : 0.060 R20, 15 R = choline.

The result of X-ray diffraction is listed in Table 2. 2 01 7 - 7 - rnir m/r< "7 Table 2 Interplanar Spacing Relative Intensity d Clj I7Io 11.51 100 9.14 4 7.54 24 6.60 43 6.37 8 .73 22 .35 3 4.98 6 4.56 58 4.32 60 4.16 9 3.81 60 3-75 93 3.59 81 3-30 31 3-15 33 2.92 6 2.86 89 2.67 6 2.49 9 2.29 3 2.21 4 2.11 1.89 17 Example 2 2.27 g of borax, 1.43 g of aluminum hydroxide (75 weight % of Al^O^), 1.18 g of sodium hydroxide, 1.06 g of potassium hydroxide, and 9-12 g of choline chloride are 35 dissolved in 30 g water. 23-4 g of 40 weight % colloidal silica gel are introduced into this solution, the suspension so formed is homogenized and heated for 1,200 hours at 2 017 5 4 105°C under its own vapor pressure. After the usual work-up, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained: Si02 : 0.073 A1203 : 0.010 B203 : 0.043 Na20 : 0.029 K20 : 0.055 R20, R = choline.

The X-ray diffraction pattern corresponds to that of Table 1.

Example 3 As in Example 2, a suspension is prepared from 5.6 g of sodium aluminate, 4.1 g of boron trioxide, 7.2 g of sodium hydroxide, 5.3 g of potassium hydroxide, 45.6 g of choline 15 chloride, 117 g of 40 weight % colloidal silica gel and 150 g of water. This suspension is heated for 1,200 hours at 100°C. After usual work-up, a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained: Si02 : 0.050 A1203 : 0.038 B2C>3 : 0.034 Na20 : 0.027 K20 : 0.058 R20, R = choline.

The product has the X-ray diffraction pattern of Table 1. 201754

Claims (7)

1. WHAT WE CLAIM IS: Boro-aluminosilicates having a zeolite structure which a) have the following composition: SiO 2 : (0.08 t 0.05) /A1203 + B^^ (0.12 ± 0.10) /Na20 + K2Q7 : (0.10 ± 0.09) R20 expressed as a molar ratio of the oxides; R being choline Z"(CH3)3nch2CH2OH7 + b) have the characteristic X-ray diffraction pattern set forth below in Table 1: 10 Table 1 15 20 30 Interplanar Spacing d C%J Relative Intensity I/]to 11.5 - 0.2 very strong 9.2 - 0.2 weak 7.6 - 0.2 medium 6.6 i 0.1 strong 5.7 i 0.1 medium 5.35 - 0.1 weak 4.98 - 0.1 it 4.56 - 0.1 strong 3.32 t o.1 m 4.16 - 0.1 weak 3.81 t o.1 strong 3-75 ± 0.1 very strong 3.59 ± 0.1 medium 3-30 - 0.1 n 3.15 - 0.1 weak 2.86 - 0.1 strong 2.67 - 0.1 weak = intensity of the strongest line or peak. 201754 - 10 -
2. 2. Boro-aluminosilicates as claimed in Claim 1, wherein the aluminum/boron ratio is ai2O3 = 0.40 - 0.99 Al^O^ + B203 expressed as a molar ratio of the oxides.
3. 3. Boro-aluminosilicates as claimed in Claim 1, wherein the 10 aluminum/boron ratio is 15 ai2O3 0.75 - 0.99 Al2°3 + B203 expressed as a molar ratio of the oxides. 20
4. 4. A process for the manufacture of boro-aluminosilicates as claimed in one of Claims 1 to 3, which comprises preparing a mixture of silicon, aluminum, boron, sodium, potassium and choline compounds and water which is composed as follows, expressed as a molar ratio of the oxides 25 Si02 : (0.06 i 0.05) A1203 : (0.06 - 0.05) B203 : (0.2 - 0.15) Na20 : (0.12 ± 0.10) KgO : (0.22 - 0.2) R20 : (50 - 40) H20 R being choline, and heating this mixture in a closed vessel
5. 5. The process as claimed in Claim 4, wherein the mixture 30 to be heated is composed as follows, expressed as a molar ratio of the oxides. 35 Si02 : (0.05 i 0.03) Al^ : (0.05 - 0.03) B2°3: (0.2 - 0.1) Na20 : (0.09-0.05) K20 : (0.22 - 0.2) R50 : (50 - 40) H50; :\c to g \»N OQ 40 R being choline.
6. 6. Use of boro-aluminosilicates as claimed in one of Claims 1 to 3 as catalysts in the manufacture of C2-C^-olefins from methanol. - 11 - 201754
7. 7. A boro-aluminosilicate according to claim 1 substantially as herein described. HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: $fc>