NZ201909A - Gallium and/or indium-containing zeolites and use as olefin-producing catalysts - Google Patents

Gallium and/or indium-containing zeolites and use as olefin-producing catalysts

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Publication number
NZ201909A
NZ201909A NZ201909A NZ20190982A NZ201909A NZ 201909 A NZ201909 A NZ 201909A NZ 201909 A NZ201909 A NZ 201909A NZ 20190982 A NZ20190982 A NZ 20190982A NZ 201909 A NZ201909 A NZ 201909A
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NZ
New Zealand
Prior art keywords
indium
gallium
strong
oxides
expressed
Prior art date
Application number
NZ201909A
Inventor
H Baltes
E I Leupold
H Litterer
F Wunder
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Hoechst Ag
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Publication of NZ201909A publication Critical patent/NZ201909A/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £01 909 /b Priority Complete Specification Filed; Class: £?.> . • • <r*<?7ci ^ ' Pybtrcation Date: .... 3,1 .JUL. 1686* • • P O. Journal, Mo: ...... j?; 7?i H 4 it' 2 019 09 N.Z. No.
NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "GALLIUM- AND /OR INDIUM-CONTAINING ZEOLITES, PROCESS FOR THEIR MANUFACTURE, AND THEIR USE." We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany,of d-6230 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 201909 Zeolites are crystalline aluminosilicates, in which due to a three-dimensional linkage of SiO^ and AIO^ tetrahedra 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 pentasil series are known which contain boron, iron, arsenic, antimony, vanadium, chromium, or gallium in tetrahedral position.
Subject of the present invention are gallium- and/or indium-containing zeolites which 201909 - 3 - KQ3-C i"JfP^2 a) have the following composition: Si02 : (0.20 t 0.10) Z*A1203 + M20^7 : (0.15 - 0.1) /Na20 + K2Q7 : (0.15 - 0 44) R20 expressed as molar ratio of oxides; M being gallium 5 and/or indium and R being tetramethylammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table 1: Table 1 Interplanar Spacing Relative Intensity d Clj I/:[o 11.50 - 0.2 very strong 7.56 ± 0.1 weak to medium 6.62 ± 0.1 medium to strong 6.32 - 0.1 weak .74 ^ 0.1 n 4.56 i 0.1 medium 4.33 1 0.1 medium to strong 3.76 - 0.1 very strong 3-58 - 0.1 medium to strong 3.31 - 0.1 weak 3.15 - 0.1 weak to medium 2.84 - 0.1 strong to very strong 2.68 - 0.1 weak to medium 2.48 t o.1 weak IQ = intensity of the strongest line or peak.
The intensities of Table 1 are defined as follows: relative intensity 100 I/Xo very strong 80 - 100 strong 50 - 80 medium - 50 weak 0 - 20 201909 - i - The novel zeolites of the invention have a structure similar to offretite) however, they have a different composition.
The following is valid for the zeolite of the invention: generally ai2O3 AlgO^ + M2°3 preferably = 0.01 - 0.99 ai2O3 ai2O3 + M2O3 especially = 0.40 - 0.99 A12°3 ai2O3 M2°3 = 0.60 - 0.99 expressed as molar ratio of the oxides; M being gallium and/or indium.
The zeolites of the invention are prepared by mixing gallium and/or indium compounds with aluminum, silicon, 25 sodium, potassium, tetramethylammonium compounds and water, 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 : (0.03 - 0.028) A1203 : (0.03 - 0.028) M203 : (0.2 ± 0.08) Na20 : (0.2 ± 0.15) K20 : (0.1 ± 0.08) R20: (20 - 10) H20 preferably in a ratio of Si02 : (0.03 - 0.01) A1203 : (0.03 - 0.028) M203 (0.2 i 0.08) Na20 : : (0.035 - 0.015) R20: (20 - 10) H20 mi £ fc I \! ^ 201909 M being gallium and/or indium and R being tetramethylammonium.
As compounds, there are used for example silicic acid, potassium silicate, sodium silicate, aluminum hydroxide, 5 aluminum sulfate, sodium aluminate, potassium aluminate, aluminum halides, aluminum methahydroxyide, gallium(III) oxide, gallium(III) nitrate, gallium(III) sulfate, gallium(III) halides, gallium(III) hydroxide, indium(III) oxide, indium(III) nitrate, indiura(III) sulfate, indium(III) 10 halides, indium(III) hydroxide, sodium hydroxide, sodium sulfate, sodium halides, potassium hydroxide, potassium sulfate, potassium halides, tetramethylammonium hydroxide, tetramethylammonium chloride. Other silicon, aluminum, gallium, indium, potassium, sodium and tetramethylammonium 15 compounds are also suitable for the manufacture of the zeolites according to the invention.
The mixture of the compounds chosen and water is generally heated for 12 to 300, preferably 24 to 200, hours at a temperature of from 60 to 150°C, peferably 80 to 140°C, 20 in a closed vessel.
The crystalline zeolites which are formed are isolated 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 25 ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974).
After conversion to the catalytically active form, the zeolites of the invention display a considerably reduced deposition of coke and a pronouncedly increased activity especially in the conversion of methanol to hy-30 drocarbons, as compared to - n?Wgalliura- or indium-free offretites, *.'■ This reaction is carried out, for example, at temperatures between 350 and 430°C using methanol with a water content of 0 to 80 % by weight or raw methanol. 35 The following Examples illustrate the invention with out limiting it in its scope. All X-ray diffraction data as indicated were obtained by means of a comput'er-controlled powder diffractometer D-500 of the Siemens company. The radiation was the K-^f doublet of copper. ' ve o 101909 Example 1 98 g of 40 weight % colloidal silica gel are introduced into a solution of 4.3 g of galliura(III) oxide, 7.2 g of sodium hydroxide, 17-8 g of potassium hydroxide, 4.5 g of sodium 5 aluminate (54 weight % of A120^, 41 weight % of Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water. The mixture so obtained is homogenized by thorough stirring, and heated for 95 hours at 95°C in a closed vessel. The product obtained is filtered off, washed with 10 water and dried at 120°C. According to chemical analysis, the product is composed as folllows, expressed as molar ratio of oxides: Si02 : 0^088 Al^ : 0.056 Ga^ : 0.028 Na20 : 0.084 K20 : 0.034 RgO R = tetramethylammonium.
The result of X-ray diffraction is listed in Table 2.
Table 2 Interplanar Spacing d Ctj —— —*— Relative Intensity J/Io 11.48 83 7.52 24 6.60 48 6.34 12 .73 13 4.58 39 I 4.34 55 3.75 100 3-58 74 3.31 18 3.15 33 2.86 90 2.67 17 2.48 13 101909 Example 2 A mixture of 1.7 g of gallium(III) oxide, 21.4 g of sodium hydroxide, 35.6 g of potassium hydroxide, 7.0 g of aluminum hydroxide, 8.4 g of tetramethylammonium chloride, 5 250 g of water and 195 g of 40 weight % colloidal silica gel is manufactured, and heated for 72 hours in a closed vessel to 110°C. After work-up as indicated in Example 1 a crystalline product having the following composition, expressed as molar ratio of oxides, is obtained: Si02 : 0.101 A1203 : 0.011 Ga^ : 0.022 Na20 : 0.066 K20 : 0.042 R20 R = tetramethylammonium.
The X-ray diffraction data correspond to those indicated in Table 1.
Example 3 A mixture of 12.9 g of gallium(III) oxide, 21.4 g of 20 sodium hydroxide, 35.6 g of potassium hydroxide, 0.7 g of aluminum hydroxide, 8.4 g of tetramethylammonium chloride, 250 g of water and 195 g of 40 weight % colloidal silica gel is prepared, and heated for 120 hours at 95°C in a closed vessel. After work-up as in Example 1, a crystalline product 25 having the following composition, expressed as molar ratio of oxides, is obtained: Si02 : 0.018 A1203 : 0.102 Ga^ : 0.031 Na20 : 0.076 K20 : 0.043 R20 30 R = tetramethylammonium. v The X-ray diffraction data correspond to those indicated in Table 1.

Claims (5)

- 8 - 201909 Example 4 98 g of 40 weight % colloidal silica gel are introduced into a solution of 10.1 g of indium trichloride, 7.2 g of sodium hydroxide, 17.8 g of potassium hydroxide, 4.5 g 5 of sodium aluminate (54 weight % A^O^, k 1 weight % Na20) and 4.2 g of tetramethylammonium chloride in 125 g of water. The mixture so obtained is homogenized by thorough stirring and heated for 95 hours at 95°C in a closed vessel. The product obtained is filtered, washed with water, and 10 dried at 120°C. A chemical analysis results in the following composition, expressed as molar ratio of oxides: Si02 : 0.099 AlgOg : 0.038 ln203 : 0.032 Na20 : 0.084 KgO : 0.032 R20 15 R = tetramethylammonium. The X-ray diffraction data correspond to those listed in Table
1. 201909 - 9 - MHAXT/WE CLAIM JS; Gallium and/or indium-containing zeolites which a) have the following composition: Si02 : (0.20 - 0.10) /"A^CU + M20J7 : (0.15 - 0.1) /Na20 + K2Q7 : (0.15 - 0.(4) R20 expressed as molar ratio of oxides; M being gallium and/or indium and R being tetramethylammonium, and b) have the characteristic X-ray diffraction pattern set forth below in Table 1: 10 Table 1 15 20 25 Interplanar Spacing d clj Relative Intensity I/xo 11.50 - 0.2 very strong 7.56 ± 0.1 weak to medium 6.62 - 0.1 medium to strong 6.32 - 0.1 weak 5.74 ± 0.1 it 4.56 - 0.1 medium 4.33 - 0.1 medium to strong 3.76 t o.1 very strong 3.58 t 0.1 medium to strong 3-31 - 0.1 weak 3.15 - 0.1 weak to medium 2.84 t 0.1 strong to very strong 2.68 t o.1 weak to medium 2.48 t o.1 weak 30 IQ = intensity of the strongest line or peak.
2. Gallium- and/or indium-containing zeolites as claimed in Claim 1, for which the following is valid: 35 A12°3 = 0.01 - 0.99 , A1203 + ^2^3 - 10 - 301909 ..JMfl (M/r Q52 expressed as molar ratio of oxides; M being gallium and/or indium.
3. Gallium- and/or indium-containing zeolites as claimed in 5 Claim 1 or 2, for which the following is valid: ai o hx2u3 = 0.40 - 0.99 , 10 expressed as molar ratio of oxides; M being gallium and/or indium.
4. Gallium- and/or indium-containing zeolites as claimed in one of 15 Claims 1 to 3, for which the following is valid: A12°3 = 0.60 - 0.99 , 20 AlgO^ + ^2^3 expressed as molar ratio of oxides; M being gallium and/or indium.
5. A process for the manufacture of gallium- and/or indium-25 containing zeolites as claimed in one of Claims 1 to 4, which comprises preparing a mixture of silicon, aluminum, sodium, potassium and tetramethylammonium compounds, water, and gallium- and/or indium compounds having the following composition, expressed in molar ratio of 30 oxides: Si02 : (0.03 - 0.028) A1203 : (0.03 - 0.028) M203 : (0.2 - 0.08) Na20 : (0.2 ± 0.15) K20 : (0.1 ± 0.08) RgO: 35 (20 t 10) H20 "M being gallium and/or indium and R being tetramethylammonium, and heating this mixture in a closed vessel. '■s. - 11 - 20190 The process as claimed in Claim 5, wherein the mixture to be heated has the following composition, expressed as molar ratio of oxides: Si02 : (0.03 - 0.01) A1203 : (0.03 - 0.028) M^: (0.2 - 0.08) Na20 : (0.2 t 0.10) K20 : (0.035 - 0.015) R20 (20 ± 10) H20 M being gallium and/or indium, and R being tetramethylammonium. Use of gallium- and/or indium-containing zeolites as claimed in one of Claims 1 to 4 as catalysts for the manufacture of C^C^-olefins from methanol. HOECHST AKT1ENGESELLSCHAFT Per t By m/Their Attorneys, henry hughes limited,
NZ201909A 1981-09-16 1982-09-14 Gallium and/or indium-containing zeolites and use as olefin-producing catalysts NZ201909A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813136686 DE3136686A1 (en) 1981-09-16 1981-09-16 "GALLIUM- AND / OR INDIUM-CONTAINING ZEOLITHES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE"

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NZ201909A true NZ201909A (en) 1985-07-31

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NZ201909A NZ201909A (en) 1981-09-16 1982-09-14 Gallium and/or indium-containing zeolites and use as olefin-producing catalysts

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EP (1) EP0074652B1 (en)
JP (1) JPS5864213A (en)
AU (1) AU8840482A (en)
CA (1) CA1182096A (en)
DE (2) DE3136686A1 (en)
NZ (1) NZ201909A (en)
ZA (1) ZA826758B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3240870A1 (en) * 1982-11-05 1984-05-10 Hoechst Ag, 6230 Frankfurt ZEOLITES CONTAINING TITANIUM, ZIRCONIUM AND / OR HAFNIUM AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
GB8308684D0 (en) * 1983-03-29 1983-05-05 British Petroleum Co Plc Production of gallium loaded hydrocarbon conversion catalyst
EP0230356B1 (en) * 1986-01-09 1991-06-12 Research Association For Utilization Of Light Oil Production of high-octane gasoline blending stock
EP0252742B1 (en) * 1986-07-11 1991-10-02 Mobil Oil Corporation Process for conversion of lower aliphatic oxygenates to olefins and aromatics with gallium containing zsm-5 catalyst
US5133951A (en) * 1986-09-04 1992-07-28 Union Oil Company Of California Process for making a crystalline galliosilicate with the offretite structure
US4994250A (en) * 1989-09-29 1991-02-19 Union Oil Company Of California Process for synthesizing a molecular sieve having the offretite structure and containing aluminum and gallium
US4931266A (en) * 1986-10-22 1990-06-05 Union Oil Company Of California Crystalline galliosilicate with the erionite-type structure
US5064793A (en) * 1986-10-22 1991-11-12 Union Oil Company Of California Catalyst composition containing a crystalline galliosilicate having the erionite-type structure
US4995963A (en) * 1986-12-22 1991-02-26 Union Oil Company Of California Crystalline galliosilicate with the zeolite L type structure and its use in chemical catalytic conversions
US5035868A (en) * 1986-12-22 1991-07-30 Union Oil Company Of California Catalyst composition containing a crystalline galliosilicate having the zeolite L type structure
US4919907A (en) * 1986-12-22 1990-04-24 Union Oil Company Of California Crystalline galliosilicate with the zeolite L type structure
US6007790A (en) * 1998-08-13 1999-12-28 Uop Llc Family of microporous indium silicate compositions
WO2002036489A1 (en) * 2000-11-03 2002-05-10 Uop Llc Uzm-5, uzm-5p and uzm-6; crystalline aluminosilicate zeolites and processes using the same
US6419895B1 (en) * 2000-11-03 2002-07-16 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-4
US6776975B2 (en) * 2002-05-09 2004-08-17 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-4M

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL238953A (en) * 1958-05-08
US3431219A (en) * 1967-03-08 1969-03-04 Mobil Oil Corp Crystalline galliosilicates
US4046826A (en) * 1974-12-06 1977-09-06 N L Industries, Inc. Process for alkylating aromatic hydrocarbons with synthetic hectorite-type clay catalyst
DE2848849A1 (en) * 1978-11-10 1980-05-22 Mobil Oil Corp Metal-contg. ZSM-5 type zeolites - useful as hydrocarbon conversion catalysts
CA1142500A (en) * 1979-03-28 1983-03-08 Grace (W.R.) & Co. Cyclic process for forming high purity zsm-5 catalyst

Also Published As

Publication number Publication date
EP0074652B1 (en) 1984-11-14
DE3261241D1 (en) 1984-12-20
JPS5864213A (en) 1983-04-16
DE3136686A1 (en) 1983-04-21
AU8840482A (en) 1983-03-24
CA1182096A (en) 1985-02-05
EP0074652A1 (en) 1983-03-23
ZA826758B (en) 1983-07-27

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