NZ206144A - Titanium,zirconium and/or hafnium containing zeolites - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £06144 Priority Date(s): t$r. J J.; £{<? Complete Specification Filed: .5. ; J J r.?3 Class: ff?.\.EZ&Jd&s.

Publicetion Date: P.^9.1®??...

' P.O. Journal, No: . .V?.?.? NO DRAWINGS NEW ZEALAND Patents Act, 1953 COMPLETE SPECIFICATION "Titanium—, zirconium— and/or hafnium—containing zeolites, a process for their preparation, 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 heoreby 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: - ^ 06 f 44 N.Z.No. 206144 iimi OQi'r o<r Zeolites is the name given to, in particular, crystalline a luminosi licates in which regular structures with cavities and pores are formed by a threedimensiona I linking of SiO^ and AlO^ tetrahedra. In the hyd-5 rated state these pores and cavities are full of water. The water can be removed, or be replaced by other molecules, without affecting the crystal structure. The negative charges of AIO4 tetrahedra are compensated by cations. These cations can be replaced, if desired, by 10 other cations. The properties described permit the use of these zeolites as ion exchange materials, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Sieves, 1974).

For example, zeolites of the X, Y, mordenite, erionite and offretite types are of considerable technical 15 interest for catalyzing conversion reactions of hydrocarbons, such as cracking, hydrocracking or isomerizations. Zeolites of the pentasil type (for example, zeolite ZSM-5) are becoming increasingly important as catalysts for converting methanol to hydrocarbons.

Because of the numerous possibilities of using them as catalysts, there is great interes-t in new zeolites having specific catalytical properties. For example, very interesting zeolites are obtained by incorporating elements other than aluminum and/or silicon into the zeolite skele-25 ton. For instance, zeolites of the pentasil ser^ alia, have been disclosed as containing boron !/«£ 206144- iron, arsenic, antimony, vanadium, chromium or gallium on tetrahedron sites. Moreover, titanosilicates (U.S. Patent 3,329,481) and zirconosilicates (U.S. Patent 3,329,480) with a zeolite structure have been disclosed. 3,329,480) with a zeolite structure have been disclosed. 10 Furthermore, the following have already been des cribed: boron-containing zeolites, gallium- and/or indium-containing zeolites, titanium-containing zeolites as well as zirconium- and/or hafnium-containing zeolites* The invention relates to titanium-, zirconium- and/ or hafnium-containing zeolites which a) contain silicon, aluminum, sodium, potassium, an organic ammonium compound and at least one element from the group consisting of titanium, zirconium and hafnium in the following ratio: <Si02 + M02) : (0.02 - 0.30)Al203 : (0.05 - 0.30) (Na20 + K20) : (0.01 - 0.30)R20, expressed in molar ratios of the oxides, wheire M is equal to titanium, zirconium and/or hafnium, R denotes ammonium radicals of the general formulae (H0CH2CH2)4N, (H0CH2CH2)3R1N or (HOCH2CH2)2R 1R2N, and the radicals R1 and R2 can be identical or different and /y'9 2 06144 denote alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and b) have, in the X-ray diffraction diagram, the charac teristic signals listed in Table 1: Table 1 Lattice distances Relative intensity d(8> I/I0 11.5 + 0.3 strong to very strong 9.2 + 0.2 weak 7.6 + 0.2 weak to medium 6.6 + 0.1 medium to strong 6.3 + 0.1 weak .7 + 0.1 weak .35 + 0.1 weak 4.56 + 0.1 weak to medium 4.32 + 0.1 strong 4.16 + 0.1 weak 3.81 + 0.1 medium to strong 3.75 + 0.1 strong to very strong 3.59 + 0.1 strong to very strong 3.3D + 0.1 medium 3.15 + 0.1 medium 2.86 + 0.1 strong to very strong 2.80 + 0.1 weak to medium 2.67 + 0.1 weak to medium 2.49 + 0.1 weak to medium In the Table, I0 denotes the intensity of the strongest signal.

The intensities given in Table 1 have been classified as follows: 2 06144 Relative intensity 100 I/I0 very strong 80 - 100 strong 50 - 80 medium 20 - 50 weak 0 - 20 The zeolites according to the invention preferably have the following composition as expressed in molar ratios of the oxides: (Si02 + H02) : (0.08 - 0.18) A l203 : (0.05 - 0.30) (Na20 + K20) : 0.01 - 0.30) R20, where M is equal to titanium, zirconium and/or hafnium, R has the abovementioned meaning and is preferably (H0CH2- ch2)3r1n. 1 2 R and R have the abovementioned meanings, 15 and preferably are alkyl radicals of at most 5 carbon atoms each, or hydrogen, in particular methyl, ethyl or hydrogen. R^ and R2 can be different, but preferably R^ = R2, in particular R^ = R2 = methyl.

In general, the ratio of silicon to titanium, zii— 20 conium and/or hafnium in the zeolites according to the invention should be: Si02 =0.4-0.99 Si02 + M02 25 preferab ly Si02 = 0.7 - 0.99 Si02 + M02 expressed in molar ratios of the oxides, where M is equal 206144 to titanium, zirconium and/or hafnium.

The novel zeolites according to the invention have a structure similar to that of erionite (L.W. Staples, J.A. Card, Hinera logica I Magazine, Volume 32 (1959), page 261 5 et seq.) or that of the synthetic zeolites T (U.S. Patent 2,950 952) and ZSM-34 but they differ from these in the composition, in particular by the fact that they contain at least one element from the group consisting of titanium, zirconium and haf-10 nium and by the nature of the organic ammonium compound.

A further crystalline aluminosilicate of this structural type was recently described.

The zeolites according to the invention differ from this aluminosilicate by the fact 15 that they contain titanium, zirconium and/or hafnium and that they have different catalytical properties.

The titanium-, zirconium- and/or hafnium-containing zeolites according to the invention differ from the titanosi licates according to U.S. Patent 3,329,481 and the zirconosilicates described in U.S. Patent 3,429,480, in terms of the structure and by the nature of the organic ammonium compound.

The titanium-, zirconium and/or hafnium-containing zeolites according to. the invention differ from the titan-ium-containing and zirconium- and/or hafnium-containing 7 - 20614f zeolites of similar structure by the nature of the organic ammonium compound. The zeolites according to the invention are further distinguished by a different 5 crystal shape and by much bigger crystallites.

The zeolites according to the invention can be prepared by mixing an RX ammonium compound with aluminum, silicon, sodium and potassium compounds and water as well as at least one compound from the group consisting of 10 titanium, zirconium and/or hafnium compounds, and heating the mixture in a sealed vessel. The R of RX has the above-mentioned meaning. Seed crystals can also be added to the mixture before it is heated.

The starting compounds are generally used in the 15 following ratio as expressed in molar ratios of the oxides: (Si02 + M02> : (0.02 - 0.30) Al203 : (0.02 - 0.70) Na20 : 0.02 - 0.30) K20 : (0.02 - 0.5) R20 : <10 - 90) h2o, preferably in the ratio 20 (Si02 + M02) : 0.02 - 0.18) Al203 : (0.10 - 0.60) Na20 : (0.04 - 0.20) K20 : (0.10 - 0.40) R20 : (10 - 40) H20, where M is equal to titanium, zirconium and/or hafnium and R has the abovementioned meaning.

In general: Si02 =0.4-0.99 >\ Si02 + M02 preferably 206144- Si02 = 0.6 - 0.99 Si02 + M02 expressed in molar ratios of the oxides, where M is equal 5 to titanium, zirconium and/or hafnium.

An RX ammonium compound can be any watei—soluble salt of R. X can denote, for example, hydroxyl, chloride, bromide, iodide, sulfate, phosphate, sulfonate, carboxy-late, carbonate or sulfite.

The RX ammonium compound can be used as a substance, but it is preferably produced in situ in the reaction mixture by using a mixture of triethano lamine and/or dietha-nolamine on the one hand and a compound of the general formula R^Y on the other hand, R^ having the above-15 mentioned meaning. Y is generally hydroxyl, monoalkyl sulfate, halide or sulfonate, in particular hydroxyl.

R^'Y is preferably methanol, ethanol, propanol, butanol, ethylene glycol, 1,2-propy lene glycol, dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide, 20 propyl iodide, methyl p-toluenesuIfonate, ethyl p-toluene-sulfonate or propyl p-toluenesulfonate. R^Y is in pai— ticular methanol, ethanol or ethylene glycol. The molar ratio of R^Y to amine (triethano lamine and/or diethanol-amine) is in general 0.5 to 20, preferably 1 to 10, in par-25 ticular 4 to 10.

However, the zeolites according to the inventi can also be prepared with satisfactory crystallinity in.\ the absence of a compound of the general formula R^Y, in the presence of only triethanolamine and/or diet^gpol- 206j amine.

Examples of titanium, zirconium and hafnium compounds which can be used are titanium halide, titanium sulfate, titanium oxide sulfate, titanium alcoholates, 5 sodium titanate, potassium titanate, titanium dioxide, zirconium halide, zirconium sulfate, zirconium alcoholates, zirconium nitrate, zirconium dioxide, zirconyl halide, zirconyl sulfate, sodium zirconate, potassium zirconate, hafnium halide, hafnium dioxide and hafnium oxychloride. 10 However, other titanium, zirconium and hafnium compounds are also suitable for preparing the zeolites according to the i nventi on.

Examples of silicon, aluminum, sodium and potassium compounds which can be used are silica gel, potassium 15 silicate, sodium silicate, sodium aluminate, potassium aluminate, aluminum halides, aluminum metahydroxide, potassium hydroxide, potassium sulfate, potassium halides, sodium hydroxide, sodium sulfate and sodium halides. However, other silicon, aluminum, potassium and sodium 20 compounds are also suitable for preparing the zeolites according to the invention.

The mixture of whichever compounds have been chosen together with water is heated in a sealed vessel for 18 to 1,000 hours in general, preferably 24 to 500 hours, 25 at a temperature between 80 and 200°C, preferably between 110 and 160°C.

The zeolites formed are isolated in a customary manner, for example by filtration, washed and dried. They can be converted into the catalytically active forms by known methods, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).

After their conversion into the cata lytica I ly active form, the zeolites according to the invention are 5 distinguished in particular by a high degree of selectivity and by low coking in the course of converting methanol into low olefins. This reaction is carried out, for example, at temperatures of 350 - 430°C and with a water content in the methanol of 0 to 80% by weight or with 10 crude methanol.

The following examples are intended to illustrate the invention without limiting it in any way. All the X-ray diffraction data given were recorded using a Siemens computer-controlled D-500 powder diffractometer. 15 Copper-K-aIpha radiation was used.

Example 1 17.92 g of sodium aluminate C54% by weight of AI2O3, 41% by weight of Na20), and 9.5 g of sodium hydroxide, 10 g of potassium hydroxide, 77.6 g of triethan-.20 olamine and 56 g of ethylene glycol are dissolved in 240 ml of water (solution A). 14.2 g of titanium ethanolate, ^(002^)4, are dissolved in 40 g of ethylene glycol (solution B). 178 g of 40% by weight strength colloidal silica gel are then introduced with thorough stirring into 25 solution A, followed by solution B. The resulting mixture is homogenized and is then heated in a stirred autoclave at 150°C for 120 hours. The product formed is filtered off, washed with water and dried at 120°C.

The product has the X-ray diffraction pattern 206-] 4.4. 2 06144 reproduced in Table 2.

Chemical analysis reveals the following composition as expressed in molar ratios of oxides: Si02 : 0.147 Al203 : 0.058 Ti0? : 0.073 Na20 : 5 0.091 K20 : 0.060 R20, where R is equal to (H0CH2CH2)^N.

Table 2 Lattice plane distances Relative intensity d(X) 100 I/ID 11.3 84 9.2 4 7.55 17 6.60 62 6.29 6 5.70 4 • .34 3 4.51 12 4.28 59 4.14 5 20 3.80 24 3.74 100 3.56 65 3.31 22 3.15 45 25 2.91 2 2.86 65 2.84 79 2.80 18 2.67 24 20614 4 Examp le 2 11.2 g of sodium aluminate (54% by weight of AI2O3, 41% by weight of ^2^, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide, 48.7 g of triethanolamine and 5 31 g of methanol are dissolved in 150 ml of water. To this solution are added, first, 100 g of 40% by weight strength colloidal silica gel and then 22.2 g of titanium tetrachloride. The resulting mixture is homogenized and is heated in a sealed vessel at 140°C for 226 hours. 10 The product formed is filtered off, washed with water and dri ed at 120°C.

The product has the X-ray data given in Table 1 and the following chemical composition as expressed in molar ratios of oxides: Si02 : 0.180 Ti02 : 0.125 Al203 Example 3 11.2 g of sodium aluminate, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide and 34.3 g of dieth-anolamine are dissolved in 150 ml of water. To this solu-20 tion are added, in succession, 110 g of 40% by weight strength colloidal silica gel, a solution of 17.8 g of titanium ethanolate, ^(002^)4 in 85 g of ethanol, and 2 g of seed crystals from Example 1. The resulting mixture is homogenized and is heated in a sealed vessel 25 at 150°C for 192 hours. The product formed is filtered off, washed with water and dried at 120°C. The product has the X-ray diffraction pattern given in Table 1 and the following chemical composition as expressed in molar ratios of oxides:

Claims (20)

206f 44 - 13 - S i 0 2 : 0.100 Ti02 : 0.132 Al203 Example 4 17.92 g of sodium a luminate (54% by weight of A*-2^3' ^ ^ weight of Na20), 9.5 g of sodium hyd-5 roxi de, 10 g of potassium hydroxide, 77.6 g of triethan-olamine and 96 g of ethylene glycol are dissolved in 240 ml of water. To this solution are added, with thorough stii— ring, first 178 g of 40% by weight strength colloidal silica gel and then 17.7 g of zirconium sulfate in a I i t — 10 tie water. The resulting mixture is homogenized and then heated at 150°C in a stirred autoclave for 120 hours. The product formed is filtered off, washed with water and dried at 120°C.;The product has the Xwray diffraction pattern 15 reproduced in Table 1.;Chemical analysis reveals the following composition as expressed in molar ratios of oxides:;Si02 : 0.143 Al203 : 0.049 Zr02 : 0.052 Na20 :;0.068 K20 : 0.062 R20,;20 where R is equal to (H0CH2CH2>4N.;206144-;... - 14 -;WHAT«*/WE CLAIM IS. or
1. I. A titanium-, zirconium- and/hafnium-containing zeolite which a) contains silicon, aluminium sodium, potassium, at least one element from the group consisting of titanium, zirconium and hafnium and an organic ammonium compound in the following ratio: (Si02 + M02) : CO.02 - 0.30) Al203 : <0.05 -0.30) (Na20 + K20) : (0.01 - 0.30) R20, expressed in molar ratios of the oxides, where M is equal to titanium, zirconium and/or hafnium, R denotes ammonium radicals of the general formulae (H0CH2CH2>4N, (H0CH2CH2)3R1N or (H0CH2CH2)2R1R2N,and the 1 O radicals R and Rc can be identical or different and denote alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and b) has, in the X-ray diffraction diagram, the charac teristic signals listed in Table 1: Table 1 Lattice plane distances Relative intensity d<8) I/I0 , II.5 0.3 strong to very strong 9.2+^0.2 weak 7.6 '+_ 0.2 — weak to medium 6.6 +_ 0.1 medium to strong 6.3 _+ 0.1 weak 5.7+0.1 weak 5.35+^0.1 weak .' 4.56 + 0.1 weak to medium t - 15 - 2 06144 Table 1 (continued) Lattice plane distances dCfi) Relative intensity I/I„ 4.32 + 0.1 4.16 -+ 0.1 3.81 '+ 0.1 3.75 + 0.1 3.59 + 0.1 3.30 + 0.1 3.15 + 0.1 2.86 + 0.1 2.80 + 0.1 2.67 + 0.1 2.49 + 0.1 strong weak medium to strong strong to very strong strong to very strong medi urn medium strong to very strong weak to medium weak to medium weak to medium In the Table, IQ denotes the intensity of the strongest signal.
2. 2. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in claim 1, which has the following composition: (Si02 + M02) : (0.08 - 0.18) Al203 : (0.05 - 0.30) (Na20 + K20) : (0.01 - 0.30) R20.
3. 3. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in either of claims 1 or 2, wherein R^ and R2 are alkyl radicals of at most 5 carbon atoms each or hydrogen.
4. 4. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in either of claims 1 or 2, wherein R^ and R2 are methyl, ethyl or hydrogen.
5. 5. A titanium-, zirconiurn- and/or hafnium-containing 206144 - 16 - zeolite as claimed in any one of claims 1 to 4, wherein R1 is equal to R2.
6. 6. A titanium-, zirconium- and/or hafniurn-containing zeolite as claimed in either of claims 1 or 2, wherein 1 ? R\ and R®- are equal to methyl.
7. 7. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in either of claims 1 or 2 , wherein Si02 = 0.4 - 0.99, Si02 + M02 expressed in molar ratios of the oxides.
8. 8. A titanium-, zirconium- and/or hafnium-containing zeolite as claimed in either of claims 1 or 2, wherein Si02 = 0.7 - 0.99, Si02 + M02 expressed in molar ratios of the oxides.
9. 9. A process for preparing a titanium-, and/or hafnium-containing zeolite as claimed in any one of claims 1 to 8, which comprises preparing a mixture of,/ silicon, aluminium, sodium, potassium, an RX water-soluble ammonium R is as defined in claim 1 and X is an anion salt where / and water as we IT as at least one compound from the group consisting of titanium, zirconium and/or hafnium compounds, which has the following composition as expressed in molar ratios of the oxides: (Si02 + M02) : (0.02 - 0.30) Al203 : (0.02 - 0.70) Na20 : (0.02 - 0.50) K20 : (0.02 - 0.50) R20 : (10 - 90.) H20, and heating this mixture in a sealed vessel. 206144 - 17 -
10. 10. The process as claimed in claim 9, wherein the mixture to be heated has the following composition as expressed in molar ratios of the oxides: CSi02 + H02> : (0.02 - 0.18) Al203 : (0.10 - 0.60) Na20 : (0.04 - 0.20) K20 : (0.10 - 0.40) R20 : (10 -40) H20.
11. 11. The process as claimed in either of claims 9 or 10, wherein the RX ammonium salt is replaced by an equivalent amount of triethano lamine and/or diethanolamine together with a compound of the formula R^Y where R^ is equal to alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl or hydrogen, and Y is equal to hydroxyl, monoalkyl sulfate, halide or sulfonate.
12. 12. The process as claimed in claim 11, wherein R^Y is equal to methanol, ethanol,. propanol, butanol, ethylene glycol, 1,2-propylene glycol, dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl iodide, propyl iodide, methyl p-toluenesuIfonate, ethyl p-toluenesu Ifonate or propyl p-toluene sulfonate.
13. 13. The process as claimed in claim 11, wherein R^Y is equal to methanol, ethanol or ethylene glycol.
14. 14. The process as claimed in either of claims 9 or 10, wherein the RX ammonium salt is replaced by an equivalent amount of triethanolamine.
15. 15. The process as claimed in either of claims 9 or 10, wherein the ammonium compound is replaced by an equi- v 6 ^ valent amount of diethanolamine.
16. 16. The process as claimed in either of 'claims. 9 or '// - 18 - 206144 10, wherein the mixture of the starting compounds is in accordance with: Si02 = 0.4 - 0.99, Si02 + M02 expressed in molar ratios of the oxides.
17. 17. The process as claimed in either of claims 9 or 10, wherein the mixture of the starting compounds is in accoi— dance with: Si02 = 0.6 - 0.99, Si02 + M02 expressed in molar ratios of the oxides.
18. 18. Use of a titanium-, zirconium- and/or hafnium-containing zeolite as claimed in any one of claims 1 to 8, as a catalyst in the preparation of C2~ to C^olefins from methanol.
19. 19. A zeolite according to claim 1 substantially as herein described or exemplified.
20. 20. A process according to claim 9 substantially as herein described and exemplified. 71 HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: /©/^W£ -