NZ201908A - 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
NZ201908A
NZ201908A NZ201908A NZ20190882A NZ201908A NZ 201908 A NZ201908 A NZ 201908A NZ 201908 A NZ201908 A NZ 201908A NZ 20190882 A NZ20190882 A NZ 20190882A NZ 201908 A NZ201908 A NZ 201908A
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NZ
New Zealand
Prior art keywords
indium
gallium
strong
weak
oxides
Prior art date
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NZ201908A
Inventor
H Baltes
E I Leupold
H Litterer
F Wunder
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Hoechst Ag
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Publication of NZ201908A publication Critical patent/NZ201908A/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
    • 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
    • B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
    • 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 £01 908 2 019 0 8 Priority Dau^}: . J k.~. ?.......... I Complete Specification FiJed: I Class: £?.XPM I?-&•,.
PubSicsticrv Data: ... J) ?■. JUL J995...
PJX Wo: N! ill N.Z. No.
NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "GALLIUM-CONTAINING AND/OR INDIUM-CONTAINING ZEOLITES, A PROCESS FOR THEIR PREPARATION, AND THEIR USE." We, HOECHST AKTIENGESELLSCHAFT, a corporation,; :| 415 "JCf/yig 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 , 201908 Zeolites are crystalline aluminosiIicates in which, as a result of threedimensionaI linking of SiO^- and AlO^-tetrahedra, regular structures having cavities and pores are formed. In the hydrated state, these pores and cavi-5 ties are filled with water. This may be removed or replaced by other molecules without affecting the crystal structure. The negative charges of the AlO^ tetrahedra are compensated by cations. These can be replaced by other positively charged ions. The properties described 10 make it possible to use zeolites as ion exchangers, adsorbents and catalysts (D.W. Breck: Zeolite Molecular Si eves, 1974).
Zeolites of the X, Y, mordenite, erionite and offretite type, for example, are of considerable intei— 15 est industrially as catalysts for conversion reactions of hydrocarbons, such as cracking, hydrocracking or isomer i zat i ons . Zeolites of the pentasil type (for example Zeolite ZSM-5) are becoming increasingly important as catalysts for converting methanol to hydrocarbons. 20 Because of the large number of possible uses as catalysts, there is considerable interest in novel zeolites with specific catalytic properties.
For example, very interesting zeolites are obtained when, instead of aluminum and/or silicon, other elements 25 are incorporated into the zeolite structure. Thus, inter alia, zeolites of the pentasil series which contain boron 201908 iron, arsenic antimony, vanadium, chromium or galiium in tetrahedral sites have been disclosed.
The invention relates to gallium-containing and/or indium-containing zeolites which a) have the following composition: Si02 : (0,09 i 0,07) £~M-203 + M203_7 : (0,12 - 0,10) I bJa20 + K20J ; (0,12 ~ 0,10) R00 expressed as molar ratios of oxides, wherein R is choline C(CH3)3NCH2CH2CHD+ and M is gallium and/or indium, and b) exhibit, in the X-ray diffraction diagram, the characteristic signals listed in Table 1: Table 1 Interlayer spacing d c)b Relative intensity I/I0 11.5 ♦ 0.2 very strong 9.2 + 0.2 weak 7.6 + 0.2 weak to medi urn 6.6 + 0.1 medi um to strong .7 + 0.1 weak to medium .35 + 0.1 weak 4.98 + 0.1 weak 4.56 + 0.1 nedi um to strong y, W T |s. *. v ;10 ;15 ;20 ;4 ;- 4 - ;Interlayer spacing d c h ;Relative intensity ino ;4.32 + 0.1 ;strong ;4.16 + 0.1 ;weak ;3.81 + 0.1 ;strong to very strong ;3.75 + 0.1 ;strong to very strong ;3.59 + 0.1 ;strong to very strong ;3.30 + 0.1 ;medium ;3.15 + 0.1 ;medium ;2.92 + 0.1 ;weak ;2.86 + 0.1 ;strong to very strong ;2.80 + 0.1 ;weak ;2.67 + 0.1 ;weak ;2.49+0.1 ;weak ;In the above table, IQ denotes the intensity of the strongest signal. ;The following applies to the intensity data in ;Table 1: ;Relative intensity ;100 ;X/Io very strong ;80 - ;100 ;strong ;50 ■ ;- 80 ;medium ;20 - ;50 ;weak ;0 ■ ;• 20 ;The following applies in general to the zeolites 25 according to the invention: ;Al2°3 ;Al2°3 + M2°3 ;= 0,01 - 0.99, ;preferab ly ;- 5 - ;201908 ;Al^O^ ;= 0.40 - 0.99, ;A12°3 + M2°3 ;in parti cular ;A12°3 ;A12°3 + M2°3 ;= 0.60 - 0.99, ;expressed as molar ratios of the oxides, wherein M is 5 gallium and/or indium. ;The novel zeolites according to the invention have a structure similar to those of the zeolites T (U.S. Patent 2,950,952). and ZSM-34,-_ - ' ;but differ from these in composition, 10 in particular in the gallium or indium content. ;The zeolites according to the invention can be prepared by mixing gallium compounds and/or indium compounds with aluminum compounds, silicon compounds, sodium compounds, potassium compounds, choline compounds and 15 water, and heating the mixture in a closed vessel. ;The starting compounds are employed in general in the following ratio, expressed as molar ratios of the oxides: ;Si-O- : (0.06 - 0.058) Al-O,. : (0,06 - 0.058) : ;2 0 . 2 3 ;(0,2 - 0.15) Na20 : (0.12 - 0.10) K20 ;(0,22 i 0.2) R20 : (50 ± 40) H20 ;preferably in the ratio: ;1908 ;- 6 - ;Si02 : (0.05 - 0.04) Al2C>3 : (0.05 - 0.048) M2C>3 : (0.2 i 0.1) N^O : (0.09 ~ 0.05) K20 : ;(0.22 - 0.10) R20 : (20 - 10) H20 ;wherein R is choline and M is gallium and/or indigm. ;5 The following are examples of compounds which may be employed: silica gel, potassium silicate, sodium silicate, aluminum hydroxide, aluminum sulfate, sodium alu-minate, potassium aluminate, aluminum halides, aluminum metahydroxide, gallium(III) oxide, gallium(III) nitrate, 10 gal lium (III) sulfate, gallium(III) halides, gallium(III) hydroxide, indium(III) oxide, indium(III) nitrate, indium(III) sulfate, indium(III) halides, indium(III) hydroxide, sodium hydroxide, sodium sulfate, sodium halides, potassium hydroxide, potassium sulfate, potassium 15 halides, choline hydroxide and choline chloride. However, other silicon, aluminum, gallium, indium, potassium, sodium and choline compounds are also suitable for the preparation of the zeolites according to the invention. ;The mixture, with water, of the compounds selec-20 ted in each case is heated in a closed vessel in general for from 48 to 2,000 hours, preferably from 48 to 1,000 hours, at a temperature between 80 and 160°C, preferably between 90 and 150°C. ;The zeolites formed are isolated in a conventional 25 manner, for example by filtration, and are washed and dried. They can be converted into the cata lytica 11 y ;9 08 ;- 7 - ;active forms by known methods, for example by calcination and/or ion exchange (D.W. Breck, Zeolite Molecular Sieves, 1974). ;After their conversion to the cata lytica I ly active 5 form, the zeolites according to the invention are distinguished in particular by high selectivity and by low coke formation in the conversion of methanol to lower olefins. This reaction is carried out, for example, at temperatures between 350 and 430°C using methanol with a water content of 10 0 to 80% by weight or raw methanol. ;The examples which follow are intended to illustrate the invention, but are not intended to be restrictive in any way. All X-ray diffraction data given were recorded with a computer-controlled D-500 powder diffracto-15 meter from Siemens. Copper Kcc radiation was used. ;Example 1 ;11.2 g of sodium alurninate (54% by weight of AI2O3, 41% by weight of Na20>/ 11.15 g of gallium trioxide, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide 20 and 45.6 g of choline chloride were dissolved in 150 g of water. 117 g of 40% strength by weight colloidal silica gel were introduced into this solution. The mixture formed was homogenized, and heated at 150°C for 8 days in a closed vessel. The product formed was filtered 25 off, washed with water and dried at 120°C. ;Chemical analysis gave the following composition, ;expressed as molar ratios of oxides: Si02 : 0.0 ;0.051 R20, ;Si02 : 0.098 A12C>3 : 0.031 Ga203 : 0.050 Na20 : 0.046 K20 ;8 - ;wherein R is choline. ;The result of the X-ray diffraction analysis is reproduced in Table 2. ;Table 2 ;10 ;15 ;20 ;25 ;Interlayer spacing d ifo ;Relative intensity 100 I/IQ ;11.50 ;100 ;9.16 ;5 ;7.58 ;18 ;6.62 ;49 ;6.33 ;8 ;5.74 ;16 ;5.35 ;3 ;4.98 ;2 ;4.56 ;37 ;4.33 ;60 ;4.16 ;6 ;3.81 ;92 ;3.76 ;91 ;3.59 ;80 ;3.30 ;33 ;3.16 ;41 ;2.92 ;10 ;2.85 ;88 ;2.80 ;6 ;2.67 ;7 ;2.49 ;8 ;Examp le 2 ;2.23 g of gallium trioxide, 7.41 g of aluminum ;?, 9 1 9 0 8 ;- 9 - ;hydroxide, 10.6 g of sodium hydroxide, 5.30 g of potassium hydroxide and 45.6 g of choline chloride were dissolved in 150 g of water. 117 g of 40% strength by weight colloidal silica gel were introduced into this solution. 5 The mixture formed was homogenized, and heated at 105°C for 720 hours in a closed vessel. After the mixture had been worked up as described in Example 1, a crystalline product of the following composition, expressed as molar ratios of oxides, was obtained: ;10 : 0-0*71 Al2C>3 • 0.014 Ga^O^ : 0.040 Na„0 : 0.031 K~0 ^ 2 0.020 R20, wherein R = choline.
The X-ray data correspond to those given in T a b I e 1.
Example 3 As in Example 2, a mixture was prepared from 5.6 g of sodium aluminate, 11.0 g of gallium trioxide, 7.2 g of sodium hydroxide, 5.3 g of potassium hydroxide, 45.6 g of choline chloride, 117 g of 40% strength by weight col-20 loidal silica gel and 150 g of water. This mixture was heated at 100°C for 1,200 hours in a closed vessel.
After the mixture had been worked up as in Example 1, a crystalline product with the following composition, expressed as molar ratios of oxides, was obtained: Si02 : 0.040 Al2°3 : 0.044 Ga2C>3 : 0.024 Na20 : 0.033 K20 0.051 R2Of wherein R = choline.
The product exhibited the X-ray signals given in Table 1.

Claims (7)

- 10 - 2019 08 Example 4 11.2 g of sodium aluminate (54% by weight of AIjO^, 41% by weight of Na20>/' 5.28 g of indium trichloride, 5.9 g of sodium hydroxide, 5.3 g of potassium hydroxide 5 and 45.6 g of choline chloride were dissolved in 150 g of water. 117 g of 40% strength by weight colloidal silica gel were introduced into this solution. The mixture formed was homogenized, and heated at 150°C for 8 days in a closed vessel. The product formed was filtered 10 off, washed with water and dried at 120°C. Chemical analysis gave the following composition, expressed as molar ratios of oxides: Si02 : 0.078 A1203 : 0.008 ln203 : 0.031 Na20 : 0.032 K20 : 0.038 R20, 15 wherein R = choline. The product exhibited the X-ray signals given in Table 1. 7> Q 1 9 0 8 - 11 - WHAT^/WE CLAIM IS:
1. A gallium-containing and/or indium-containing zeolite which a) has the following composition: Si02 : (0.09 - 0.07) /~A12C>3 + M203_7 : * (0.12 ~ 0.10) /~Na20 + K20J : (0.12 - 0.10) B20 expressed as molar ratios of oxides, wherein R is choline and M is gallium and/or indium, and b) exhibits, in the X-ray diffraction diagram, the characteristic signals listed in Table 1: Table 1 Interlayer spacing d :5b 11.5 + 0.2 9.2 + 0.2 7.6 + 0.2 6.6 + 0.1 5.7 + 0.1 5.35 + 0.1 4.98 + 0.1 4.56 + 0.1 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 Relative intensity I/I„ very strong weak weak to medium medium to strong weak to medium weak weak medi um to strong strong weak strong to very strong strong to very strong strong to very strong medium medi um 9 - 12 - ^01908 Interlayer spacing d ill Relative intensity I/In 2.92 +_ 0.1 weak 2.86 + 0.1 strong to very strong 2.80 + 0.1 weak 2.67 + 0.1 weak 2.A 9 + 0.1 weak of the strongest signal.
2. A gaI Iium-containing and/or indium-containing zeolite as claimed in claim 1, wherein the following a ppIi es: A12°3 = 0.01 - 0.99, A12°3 + M2°3 expressed as molar ratios of the oxides, wherein M is gallium and/or indium.
3. A gallium-containing and/or indium-containing zeolite as claimed in claim 1 or 2, wherein the following applies: — = 0.40 - 0.99, Al2°3 + M203 expressed as molar ratios of the oxides, wherein M is gallium and/or indium.
4. A gallium-containing and/or indium-containing zeolite as claimed in any one of claims 1 to 3, wherein the following applies: = 0.60 - 0.99, Al2°3 A12°3 + M2°3 expressed as molar ratios of the oxides, wherein, M i E •. gallium and/or indium. * L 201908 - 13 -
5. A process for the preparation of a gallium- containing and/or indium-containing zeolite as claimed in any one of claims 1 to 4, wherein a mixture of silicon compounds, aluminum compounds, sodium compounds, potassium compounds and choline compounds, water and gallium compounds and/or indium compounds is prepared, the mixture having the following composition, expressed as molar ratios of the oxides: Si02 : (0.06 i 0.058) A12C>3 : (0.06 ^ 0.058) : (0.2 - 0.15) Na20 : (0.12 - 0.10) K20 : (0.22 i 0.2) R20 : (50 - 40) H20 wherein R is choline and M is gallium and/or indium, and this mixture is heated in a closed vessel.
6. A process as claimed in claim 5, wherein the mix ture to be heated has the following composition, expressed as molar ratios of the oxides: Si02 : (0.05 - 0.04) A1203 : (0.05 i 0.048) M2C>3 : c ^ T (0.2 i 0.1) Na20 : (0.09 - 0.05) K20 : (0.22 - 0.10) R2C : (20 ~ 10) h'O V2 5®l%5 K'7/--1 >!,?-• wherein R is choline and M is gallium and/or indium. -14- 201908
7. Use, as catalysts, in the production of C2-C4- olefins from methanol, of gallium-containing and/or indium containing zeolites as claimed in any one of claims* 1 to 4 HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED
NZ201908A 1981-09-16 1982-09-14 Gallium and/or indium-containing zeolites and use as olefin producing catalysts NZ201908A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813136684 DE3136684A1 (en) 1981-09-16 1981-09-16 "GALLIUM- AND / OR INDIUM-CONTAINING ZEOLITES AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE"

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NZ201908A true NZ201908A (en) 1985-07-12

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EP (1) EP0074651B1 (en)
JP (1) JPS5860613A (en)
AU (1) AU8840382A (en)
CA (1) CA1182095A (en)
DE (2) DE3136684A1 (en)
NZ (1) NZ201908A (en)
ZA (1) ZA826759B (en)

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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
US4698217A (en) * 1985-02-26 1987-10-06 Mobil Oil Corporation Crystalline silicate ZSM-58 and process for its preparation using a methyltropinium cation
DE3773439D1 (en) * 1986-07-11 1991-11-07 Mobil Oil Corp METHOD FOR CONVERTING OXYGEN-BASED LOWER ALIPHATES TO OLEFINS AND AROMATES BY MEANS OF A 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
US4849567A (en) * 1987-12-28 1989-07-18 Mobil Oil Corporation Catalytic dehydrogenation of hydrocarbons over indium-containing crystalline microporous materials
US4830729A (en) * 1987-12-28 1989-05-16 Mobil Oil Corporation Dewaxing over crystalline indium silicates containing groups VIII means
US4922050A (en) * 1987-12-28 1990-05-01 Mobil Oil Corporation Catalytic dehydrogenation of hydrocarbons over indium-containing crystalline microporous materials
GB8818452D0 (en) * 1988-08-03 1988-09-07 British Petroleum Co Plc Process for preparation of crystalline(metallo)silicates & germanates
US5124497A (en) * 1989-10-11 1992-06-23 Mobil Oil Corporation Production of mono-substituted alkylaromatics from C8 +N-paraffins
JP2528717Y2 (en) * 1990-09-17 1997-03-12 大和製衡株式会社 Charge scale with printer
US5122489A (en) * 1990-10-15 1992-06-16 Mobil Oil Corporation Non-acidic dehydrogenation catalyst of enhanced stability
US5147837A (en) * 1990-10-22 1992-09-15 Mobil Oil Corporation Titania containing dehydrogenation catalysts
US5103066A (en) * 1990-12-10 1992-04-07 Mobil Oil Corp. Dehydrogenation of alcohols over non-acidic metal-zeolite catalysts
US6007790A (en) * 1998-08-13 1999-12-28 Uop Llc Family of microporous indium silicate compositions
CN102947224A (en) * 2010-06-21 2013-02-27 环球油品公司 Uzm-35 zeolitic composition, method of preparation and processes
US8158104B2 (en) * 2010-07-01 2012-04-17 Uop Llc UZM-7 aluminosilicate zeolite, method of preparation and processes using UZM-7
DE202012010851U1 (en) 2012-11-13 2012-12-11 Frank Besinger Jar with tea bag

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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
NZ185397A (en) * 1976-11-04 1979-12-11 Mobil Oil Corp Crystalline aluminosilicate zeolites and use as catalysts

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DE3261205D1 (en) 1984-12-13
JPS5860613A (en) 1983-04-11
EP0074651B1 (en) 1984-11-07
ZA826759B (en) 1983-07-27
AU8840382A (en) 1983-03-24
EP0074651A1 (en) 1983-03-23
DE3136684A1 (en) 1983-04-21
CA1182095A (en) 1985-02-05

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