DE2311822C2 - Process for the production of catalysts of the metal / Si-oxide type and their use for the production of oxirane compounds - Google Patents
Process for the production of catalysts of the metal / Si-oxide type and their use for the production of oxirane compoundsInfo
- Publication number
- DE2311822C2 DE2311822C2 DE2311822A DE2311822A DE2311822C2 DE 2311822 C2 DE2311822 C2 DE 2311822C2 DE 2311822 A DE2311822 A DE 2311822A DE 2311822 A DE2311822 A DE 2311822A DE 2311822 C2 DE2311822 C2 DE 2311822C2
- Authority
- DE
- Germany
- Prior art keywords
- catalysts
- production
- treatment
- oxide
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 7
- 150000002924 oxiranes Chemical class 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 title description 5
- 239000002184 metal Substances 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 150000002927 oxygen compounds Chemical class 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000006884 silylation reaction Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- -1 olefin epoxides Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WVGXAWUYNHSWRO-UHFFFAOYSA-N N-propan-2-ylsilyl-N-silylpropan-2-amine Chemical compound CC(C)[SiH2]N([SiH3])C(C)C WVGXAWUYNHSWRO-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die vorliegende Anmeldung betrifft eine weitere Ausgestaltung des Verfahrens zur Herstellung von Katalysatoren vom Metall/Si-Oxid-Typ und deren Verwendung zur Herstellung von Oxiranverbindungen gemäß Patent 21 48 637.The present application relates to a further embodiment of the method for producing Catalysts of the metal / Si oxide type and their use for the production of oxirane compounds according to patent 21 48 637.
Gegenstand des Hauptpatentes ist ein Verfahren zur Herstellung von festen, eine anorganische Silicium-The subject of the main patent is a process for the production of solid, an inorganic silicon
OlefinrestOlefin residue
—C—Ο—Ο—Η—C — Ο — Ο — Η
HydroperoxydrestHydroperoxide residue
Sauerstoffverbindung und ein Metalloxid und/oder -hydroxid von Ti, Mo, V, Zr oder B enthaltenden Katalysatoren und die Verwendung dieser Katalysatoren zur Herstellung von Oxiranen durch Epoxidierung von Olefinen mit Hydroperoxiden gemäß nachstehender allgemeiner GleichungOxygen compound and a metal oxide and / or hydroxide of Ti, Mo, V, Zr or B containing Catalysts and the use of these catalysts for the production of oxiranes by epoxidation of olefins with hydroperoxides according to the general equation below
— C —Ο —Η- C —Ο —Η
OxiranrestOxirane residue
HydroxylgruppeHydroxyl group
Die gemäß dem Hauptpatent hergestellten Katalysatoren bestehen aus einer anorganischen Sauerstoffverbindung von Silicium und einem Metalloxid oder -hydroxid der vorstehend genannten Metalle, welche vor ihrer Verwendung bei erhöhten Temperaturen bis 450° C mit einem organischen Silylierungsmittel kontaktiert worden sind. Durch die Verwendung der festen Katalysatoren des Metall/Si-Oxid-Typs gemäß dem Hauptpatent kann die Selektivität dieser Katalysatoren hinsichtlich der erwünschten Olefin-Epoxide ganz wesentlich verbessert werden.The catalysts produced according to the main patent consist of an inorganic oxygen compound of silicon and a metal oxide or hydroxide of the aforementioned metals, which contacted prior to their use at elevated temperatures up to 450 ° C with an organic silylating agent have been. By using the solid catalysts of the metal / Si oxide type according to the The main patent can completely determine the selectivity of these catalysts with regard to the desired olefin epoxides can be significantly improved.
Beim vorgenannten Epoxidierungsverfahren werden vorteilhafterweise olefinisch ungesättigte Verbindungen mit 2 bis 60 Kohlenstoffatomen verwendet. Vorzugsweise werden Alkene mit 3 bis 40 Kohlenstoffatomen, die gegebenenfalls mit einer Hydroxylgruppe oder einem Halogenatom substituiert sind, wie Propylen, Allylalkohol und Allylchlorid, verwendet. Insbesondere wird Propylen verwendet.In the abovementioned epoxidation process, olefinically unsaturated compounds are advantageously used with 2 to 60 carbon atoms used. Preferably alkenes with 3 to 40 carbon atoms, which are optionally substituted with a hydroxyl group or a halogen atom, such as propylene, Allyl alcohol and allyl chloride are used. Propylene is used in particular.
Als Hydroperoxidverbindungen können vorteilhafterweise Kohlenwasserstoff-Hydroperoxide mit 3 bis 20 Kohlenstoffatomen, wie tert-Butylhydroperoxid, tert-Pentylhydroperoxid, und Aralkylhydroperoxide, bei denen die Hydroperoxygruppe mit dem Kohlenstoffatom einer Alkylseitenkette verbunden ist, das direkt an den aromatischen Ring gebunden ist, wie 1-Phenyläthyl-1-hydroperoxid und 2-Phenylpropyl-2-hydropercxid (die häufig als Äthylbenzol-Hydroperoxid bzw. Cumol-Hydroperoxid bezeichnet werden) eingesetzt werden.Hydroperoxide compounds which can advantageously be used are hydrocarbon hydroperoxides with 3 to 20 Carbon atoms, such as tert-butyl hydroperoxide, tert-pentyl hydroperoxide, and aralkyl hydroperoxides, in which the hydroperoxy group joins the carbon atom an alkyl side chain bonded directly to the aromatic ring, such as 1-phenylethyl-1-hydroperoxide and 2-phenylpropyl-2-hydroperoxide (often called ethylbenzene hydroperoxide and cumene hydroperoxide, respectively are designated).
Oxiranverbindungen sind bekanntlich wertvolle Materialien, und viele von ihnen sind handelsübliche Chemikalien, insbesondere Olefinoxide, wie Äthylenoxid und Propylenoxid. Propylenoxid kann z. B. durch Polymerisieren oder Mischpolymerisieren in wertvolle polymere Produkte überführt werden.Oxirane compounds are known to be valuable materials and many of them are commercially available Chemicals, particularly olefin oxides such as ethylene oxide and propylene oxide. Propylene oxide can e.g. B. by Polymerization or interpolymerization can be converted into valuable polymeric products.
Die beim Umsetzen erhaltenen Hydroxylverbindungen können gegebenenfalls durch anschließendes Dehydrieren, Hydrieren und Oxidieren wieder in die Hydroperoxidverbindung umgewandelt werden.The hydroxyl compounds obtained in the reaction can, if appropriate, by subsequently Dehydrating, hydrogenating and oxidizing can be converted back into the hydroperoxide compound.
Insbesondere aus einer festen anorganischen Sauerstoffverbindung von Silicium in chemischer Kombination
mit mindestens 0,1 Gewichtsprozent eines Oxids oder Hydroxids von Titan, Molybdän, Vanadium,
Zirkonium oder Bor bestehende Katalysatoren weisen nach Behandlung mit einem organischen Silylierungsmittel
gemäß dem Verfahren des Hauptpatents verbesserte katalytische Eigenschaften auf. Die siliciumhaltigen
Feststoffe weisen vorteilhafterweise eine mittlere spezifische Oberfläche von mindestens 1 mVg
und vorzugsweise von 25 bis 800 m2/g auf. Vorzugsweise werden siliciumhaltige Feststoffe mit einem Siliciumoxidgehalt
von mindestens 99 Gewichtsprozent verwendet
Geeignete Silylierungsmittel für die Silylierungsbehandlung gemäß dem Hauptpatent sind z. B. die
Organosilane, Organosilylamine und Organosilazane.In particular, catalysts consisting of a solid inorganic oxygen compound of silicon in chemical combination with at least 0.1 percent by weight of an oxide or hydroxide of titanium, molybdenum, vanadium, zirconium or boron have improved catalytic properties after treatment with an organic silylating agent according to the method of the main patent. The silicon-containing solids advantageously have an average specific surface area of at least 1 mVg and preferably from 25 to 800 m 2 / g. It is preferred to use silicon-containing solids with a silicon oxide content of at least 99 percent by weight
Suitable silylating agents for the silylation treatment according to the main patent are e.g. B. the organosilanes, organosilylamines and organosilazanes.
Gemäß der Lehre des Hauptpatentes kann vor der Behandlung mit dem organischen Silylierungsmittel wahlweise auch noch eine Hydratisierungsbehandlung durchgeführt werden, indem man die Katalysatoren entwederAccording to the teaching of the main patent, before the treatment with the organic silylating agent optionally a hydration treatment can also be carried out by using the catalysts either
a) mit Wasser behandelt und anschließend erhitzt odera) treated with water and then heated or
b) bei erhöhten Temperaturen oberhalb 1000C, insbesondere bei Temperaturen von 150 bis 4000C, mit Wasserdampf behandelt.b) at elevated temperatures above 100 ° C., in particular at temperatures from 150 to 400 ° C., treated with steam.
Es wurde nun gefunden, daß man bei Verwendung bestimmter Organosilazane, nämlich von Organodisila-It has now been found that when using certain organosilazanes, namely from Organodisila-
zanen, besonders gute Ergebnisse erhält Die erfindungsgemäße Verwendung von Organodisilazanen als Steuerungsmittel weist außerdem den Vorteil auf, daß bei der Silyliening der Metelloxidkatalysatoren auf dem Siliciumoxidträgermaterial keine korrodierenden Komponenten gebildet werden, was ein Nachteil der Verwendung von Chlorsilanen als Silylierungsmittel ist Außerdem wurde gefunden, daß die Silyliening unter Verwendung von Organodisilazanen im allgemeinen bei niedrigeren Temperaturen als die Silyliening unter Verwendung von Organosilanen durchgeführt werden kann. Die Selektivität bei Verwendung der erfindungsgemäß silylierten Katalysatoren hinsichtlich gebildetem Epoxid hat sich als ausgezeichnet erwiesen.zanen, particularly good results obtained The inventive use of organodisilazanes as Control means also has the advantage that in the silyliening of the metal oxide catalysts on the Silica support material no corrosive components are formed, which is a disadvantage of the Use of chlorosilanes as a silylating agent is It has also been found that silyliening using organodisilazanes generally contributes to lower temperatures than the silyliening can be carried out using organosilanes can. The selectivity when using the inventively silylated catalysts with respect to the formed Epoxy has proven to be excellent.
Die erfindungsgemäße Abwandlung des Verfahrens gemäß Hauptpatent ist daher dadurch gekennzeichnet, daß man ais Silylierungsmittel ein Organodisilazan verwendet und die Behandlung bei 100 bis 450° C durchführtThe modification of the method according to the invention according to the main patent is therefore characterized that an organodisilazane is used as the silylating agent and the treatment is carried out at 100 to 450.degree performs
Die erfindungsgemäß verwendeten Organodisilazane können durch die nachstehende FormelThe organodisilazanes used according to the invention can be represented by the following formula
Ri R*Ri R *
R2—Si-N-Si-R5 R 2 -Si-N-Si-R 5
R3 H R6 R 3 HR 6
dargestellt werden, in der die Reste Ri, R2, R* R«, R^ und Re jeweils unabhängig voneinander ein Wasserstoffatom oder eine organische Gruppe sind. Vorzugsweise werden Organodisilazane verwendet in denen die verschiedenen Reste R Wasserstoffatome oder Alkylreste mit bis zu 8 Kohlenstoffatomen, wie Methyl-, Äthyloder Isopropylgruppen, sind.are represented in which the radicals Ri, R 2 , R * R «, R ^ and Re are each independently a hydrogen atom or an organic group. Organodisilazanes in which the various radicals R are hydrogen atoms or alkyl radicals with up to 8 carbon atoms, such as methyl, ethyl or isopropyl groups, are preferably used.
Geeignete Disilazane sind z. B. i,2-Diäthyldisilazan, 1,3,2,2-Tetramethyldisilazan, 1,1,1,2,2,2-Hexamethyldisilazan, 1,1,2,2-Tetraäthyldisilazan und 1,2-di-IsopropyIdisilazan. Vorzugsweise werden gemäß der vorliegenden Erfindung organische Disilazane, die ols Reste R 4 oder 6 niedere Alkylreste mit 1 bis 4 Kohlenstoffatomen enthalten und insbesondere Hexamethyldisilazan verwendetSuitable disilazanes are, for. B. i, 2-diethyldisilazane, 1,3,2,2-tetramethyldisilazane, 1,1,1,2,2,2-hexamethyldisilazane, 1,1,2,2-tetraethyldisilazane and 1,2-di-isopropyldisilazane. Preferably, according to the present Invention organic disilazanes, the ols radicals R 4 or Contain 6 lower alkyl radicals with 1 to 4 carbon atoms and in particular hexamethyldisilazane is used
Im allgemeinen enthalten die erfindungsgemäß zu silylierenden Katalysatoren von 0,2 bis 10 Gewichtsprozent, bezogen auf den gesamten Katalysator, an einem Oxyd oder Hydroxyd von Titan, Vanadium, Bor, Molybdän und Zirkonium in chemischer Kombination mit Siliciumoxyd und/oder einem anorganischen Silikat. Sehr geeignete Katalysatoren enthalten von 0,5 bis 8 Gewichtsprozent eines Oxyds oder Hydroxyds von Titan in chemischer Kombination mit Siliciumoxyd. Insbesondere wird ein Katalysator zur erfindungsgemäßen Behandlung verwendet, der im wesentlichen aus Siliciumoxyd in chemischer Kombination mit von 0,5 bis 5 Gewichtsprozent an Titanoxyd bestehtIn general, the catalysts to be silylated according to the invention contain from 0.2 to 10 percent by weight, based on the total catalyst, of one Oxide or hydroxide of titanium, vanadium, boron, molybdenum and zirconium in chemical combination with silicon oxide and / or an inorganic silicate. Very suitable catalysts contain from 0.5 to 8 Percentage by weight of an oxide or hydroxide of titanium in chemical combination with silicon oxide. In particular, a catalyst is used for the treatment according to the invention, which essentially consists of Silicon oxide in chemical combination with from 0.5 to 5 percent by weight of titanium oxide
Die erfindungsgemäß zu behandelnden Katalysatorgemische können außerdem nicht störende Substanzen und/oder Katalysatorpromotoren enthalten. Geeignete Promotoren sind z. B. die Alkalimetalle oder Erdalkalimetalle als Oxyde oder Hydroxyde. Das Alkalimetall wird vorzugsweise in einer Menge von 0,01 bis 5 Gewichtsprozent, bezogen auf den gesamten Katalysator, verwendet Ein ausgezeichnet für die erfindungsgemäße Silyliening geeigneter Katalysator besteht im wesentlichen aus Siliciumoxyd in chemischer Kombination mit 0,5 bis 5 Gewichtsprozent Titanoxyd und 0,01 bis 5 Gewichtsprozent an Calcium in Form vonThe catalyst mixtures to be treated according to the invention can also contain non-interfering substances and / or catalyst promoters. Suitable promoters are e.g. B. the alkali metals or alkaline earth metals as oxides or hydroxides. The alkali metal is preferably used in an amount of 0.01 to 5 percent by weight, based on the total catalyst essentially of silicon oxide in chemical combination with 0.5 to 5 percent by weight of titanium oxide and 0.01 up to 5 percent by weight of calcium in the form of
Die Silyliening kann ebenso wie gemäß der Lehre des Hauptpatentes auf viele Arten durchgeführt werden. Die Silylierung kann absatzweise oder in einem halbkontinuierlichen oder kontinuierlichen Verfahren durchgeführt werden. Es wurde gefunden, daß man unabhängig von dem im Einzelfall verwendeten Verfahren die besten Ergebnisse erzielt, wenn die entsprechende Silylierung unter Verwendung vonThe silyliening can be carried out in many ways, just as in accordance with the teaching of the main patent. The silylation can be batchwise or in a semicontinuous or continuous process be performed. It has been found that regardless of which one is used in the individual case Method achieves best results when using the appropriate silylation
ι ο Organodisilazanen bei Temperaturen von 100 bis 300° Cι ο Organodisilazanes at temperatures from 100 to 300 ° C und insbesondere von 150 bis 25O0C, durchgeführt wird.and is in particular from 150 to 25O 0 C performed.
zum Teil von der verwendeten Temperatur ab. Impartly on the temperature used. in the allgemeinen reicht eine Zeitspanne von 0,1 bis 48 Stunden aus. Vorzugsweise wird die Silylierung 0,1 bis 5 Stunden lang durchgeführtgenerally a range of 0.1 to 48 is sufficient Hours off. Preferably the silylation is carried out for 0.1 to 5 hours
Es können erheblich schwankende Mengen an Silylierungsmittel verwendet werden. GeeigneterweiseSignificantly varying amounts of silylating agent can be used. Appropriately werden von 1 bis 75 Gewichtsprozent und vorzugsweise von 2 bis 50 Gewichtsprozent, bezogen auf das gesamte Katalysatorgemisch, an Silylierungsmittel verwendet. Die Silylierungsbehandlung kann einige Male wiederholt werden. Aus Gründen eines wirtschaftlichenare from 1 to 75 percent by weight, and preferably from 2 to 50 percent by weight, based on the total Catalyst mixture, used in silylating agent. The silylation treatment can be repeated several times. For the sake of an economic Betriebs wird jedoch im allgemeinen eine einmalige Behandlung bevorzugtIn operation, however, a one-time treatment is generally preferred
Die besten Ergebnisse lassen sich häufig erzielen, wenn man den Metall/Siliciumoxydkatalysatcr gemäß der Lehre dts Hauptpatents vor der SilylierungThe best results are often obtained by following the metal / silica catalysts the teaching of the main patent before the silylation hydratisien. Diese Hydratisierungsbehandlung besteht entweder aus dem Kontaktieren des Katalysatoren mit Wasser und anschließendem 0,5- bis 6ständigem Erhitzen oder aus dem Kontaktieren des Katalysators mit Wasserdampf bei erhöhten Temperaturen oberhalbhydration. This hydration treatment consists of either contacting the catalyst with Water and then heating for 0.5 to 6 hours or from contacting the catalyst with water vapor at elevated temperatures above 1000C. Bei der erfindungsgemäßen Verwendung von Organodisilazanen als Silylierungsmittel werden die besten Ergebnisse erzielt, wenn die Hydratisierungsbehandlung durch 1- bis östündiges Kontaktieren mit Wasserdampf bei Temperaturen von 300 bis 4500C100 0 C. In the inventive use of organodisilazanes as the silylating agent will give the best results when the hydration by 1 to östündiges contacting with steam at temperatures of 300 to 450 0 C. durchgeführt wird.is carried out.
mit einer Teilchengröße von 0,595 bis 1,41 mm, wird mit einer Lösung von 130 g Tetraisopropyltitanat und 97 g Acetylaceton in 1,25 Liter Isopropanol kontaktiert. Das imprägnierte Kieselsäuregel wird in ein elektrisch beheiztes Calzinierungsrohr überführt und unter Stickwith a particle size of 0.595 to 1.41 mm, is with a solution of 130 g of tetraisopropyl titanate and 97 g of acetylacetone in 1.25 liters of isopropanol. That Impregnated silica gel is transferred to an electrically heated calcination tube and placed under a stick stoff auf eine Bett-Temperatur von 5000C erhitzt Man läßt dann Luft eintreten und erhöht die Temperatur auf 8000C. Diese Temperatur wird zum Wegbrennen des restlichen Kohlenstoffs und zur Herstellung einer engen chemischen Verbindung des Siliciumoxyds mit demmaterial heated to a bed temperature of 500 0 C air is then allowed to enter and the temperature is increased to 800 0 C. This temperature is used to burn off the remaining carbon and to produce a close chemical bond between the silicon oxide and the Titan 4 Stunden lang aufrechterhalten und dann 1183 g des auf diese Weise hergestellten Materials durch dreistündiges Kontaktieren mit Dampf bei 4000C wieder hydratisiert Das wiederhydratisierte Material wird auf 2000C abgekühlt und dann eine Stunde beiTitanium maintained for 4 hours and then 1183 g of the material prepared in this manner by three-hour contact with steam at 400 0 C again hydrated wiederhydratisierte The material is cooled to 200 0 C and then for one hour at 2000C mit Hexamethyldisilazandampf kontaktiert, wodurch man einen erfindungsgemäß silylierten Katalysator erhält. Der Katalysator nimmt 75 g Hexamethyldisilazan auf. Der vorstehend beschriebene Katalysator sowie ein200 0 C contacted with hexamethyldisilazane vapor, whereby a catalyst silylated according to the invention is obtained. The catalyst takes up 75 g of hexamethyldisilazane. The catalyst described above as well as a ähnlicher Katalysator, der jedoch nicht mit Hexamethyldisilazan behandelt worden ist, werden hinsichtlich ihrer katalytischen Wirkung bei der Epoxydierung von Olefinen verglichen. In jedem Prüfversuch wird einesimilar catalyst, which however has not been treated with hexamethyldisilazane, are in terms of their compared to the catalytic effect in the epoxidation of olefins. In each test, a
l-g-Probe des jeweiligen Katalysators in einem 100 ml fassenden Glasreaktionsgefäß mit 17 g Octen-1 und 28,6 g einer 12gewichtsprozentigen Lösung von Äthylbenzolhydroperoxyd in Äthylbenzol kontaktiert Die Reaktion wird eine Stunde bei 100°C durchgeführt Die Ergebnisse sind in der nachstehenden Tabelle zusammengefaßt 1 g sample of the respective catalyst in a 100 ml Glass reaction vessel with a capacity of 17 g of 1-octene and 28.6 g of a 12 percent strength by weight solution of ethylbenzene hydroperoxide contacted in ethylbenzene The reaction is carried out for one hour at 100 ° C Results are summarized in the table below
Katalysator Hydroperoxyd- Epoxidselektivität (%)Catalyst hydroperoxide- epoxide selectivity (%)
umwandlungsgrad (%)conversion rate (%)
Unsilyliert 95
Silyliert 95 72
93Unsilylated 95
Silylated 95 72
93
Claims (2)
a) mit Wasser behandelt und anschließend erhitzt1. A process for the production of solid, an inorganic silicon / oxygen compound and a metal oxide and / ode 'hydroxide of Ti, Mo, V, Zr or B-containing catalysts, wherein correspondingly composed catalysts at elevated temperatures up to 450 0 C with an organic Treated backup agent and optionally carried out before the treatment with the organic silylating agent a hydration treatment by either the catalysts
a) treated with water and then heated
nach Patent 2148637, dadurch gekennzeichnet, daß man als Silylierungsmittel ein Organodisilazan verwendet und die Behandlung bei 100 bis 4500C durchführttreated at elevated temperatures above 100 0 C, particularly at temperatures of 300 to 450 ° C with steam,
as claimed in Patent 2148637 in that there is used as silylating agent and an organodisilazane performing the treatment at 100 to 450 0 C.
Applications Claiming Priority (1)
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US00234301A US3829392A (en) | 1970-10-01 | 1972-03-13 | Heterogeneous catalysts for olefin epoxidation |
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DE2311822A1 DE2311822A1 (en) | 1973-09-27 |
DE2311822C2 true DE2311822C2 (en) | 1982-11-04 |
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DE2311822A Expired DE2311822C2 (en) | 1972-03-13 | 1973-03-09 | Process for the production of catalysts of the metal / Si-oxide type and their use for the production of oxirane compounds |
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JP (1) | JPS5635941B2 (en) |
AR (1) | AR196234A1 (en) |
BE (1) | BE796437R (en) |
BR (1) | BR7301701D0 (en) |
CA (1) | CA1015761A (en) |
CH (1) | CH582021A5 (en) |
DE (1) | DE2311822C2 (en) |
DK (1) | DK150593C (en) |
ES (2) | ES412496A2 (en) |
FR (1) | FR2175844B2 (en) |
GB (1) | GB1424284A (en) |
IE (1) | IE37389B1 (en) |
IT (1) | IT1053715B (en) |
NL (1) | NL168835C (en) |
NO (1) | NO143520C (en) |
SE (2) | SE409034B (en) |
ZA (1) | ZA731655B (en) |
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DE19545042A1 (en) * | 1995-12-02 | 1997-06-05 | Studiengesellschaft Kohle Mbh | Amorphous microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis adsorption and material separation |
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JPS5253678A (en) * | 1975-10-29 | 1977-04-30 | Hitachi Ltd | Semiconductor integrated circuit and productin of the same |
JPS63120437A (en) * | 1986-11-10 | 1988-05-24 | Agency Of Ind Science & Technol | Structure of semiconductor integrated circuit |
DE3734138A1 (en) * | 1987-10-09 | 1989-04-20 | Scharmer Klaus Dr Ing | ACID CATALYST AND METHOD FOR PRODUCING THE CATALYST |
WO2006087522A2 (en) * | 2005-02-17 | 2006-08-24 | Bp Exploration Operating Company Limited | Silyl-modified catalyst and use of this catalyst for the conversion of synthesis gas to hydrocarbons |
JP2007031449A (en) * | 2006-10-19 | 2007-02-08 | Repsol Quimica Sa | Method for epoxidization of olefinic compound with hydrogen peroxide in the presence of solvent |
CN101801525A (en) * | 2007-09-10 | 2010-08-11 | 国际壳牌研究有限公司 | Process for stabilising a fischer tropsch catalyst |
TWI628146B (en) * | 2016-11-28 | 2018-07-01 | 東聯化學股份有限公司 | Preparation method and application of titanium-containing cerium oxide material with high thermal stability |
CN113636991A (en) * | 2021-08-13 | 2021-11-12 | 中国天辰工程有限公司 | Synthesis method of epoxy cyclohexane |
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- 1973-02-13 CA CA163,568A patent/CA1015761A/en not_active Expired
- 1973-03-08 BE BE1004871A patent/BE796437R/en active
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- 1973-03-09 JP JP2721573A patent/JPS5635941B2/ja not_active Expired
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- 1973-03-12 NL NLAANVRAGE7303415,A patent/NL168835C/en active
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1974
- 1974-02-09 ES ES423071A patent/ES423071A1/en not_active Expired
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FR2175844B2 (en) | 1976-09-10 |
JPS492795A (en) | 1974-01-11 |
CA1015761A (en) | 1977-08-16 |
NL168835B (en) | 1981-12-16 |
FR2175844A2 (en) | 1973-10-26 |
IE37389L (en) | 1973-09-13 |
DE2311822A1 (en) | 1973-09-27 |
GB1424284A (en) | 1976-02-11 |
BR7301701D0 (en) | 1974-07-11 |
ES423071A1 (en) | 1976-06-16 |
CH582021A5 (en) | 1976-11-30 |
ZA731655B (en) | 1974-01-30 |
DK150593C (en) | 1987-11-23 |
IE37389B1 (en) | 1977-07-06 |
NO143520B (en) | 1980-11-24 |
AU5316473A (en) | 1974-09-12 |
NL168835C (en) | 1982-05-17 |
SE7602414L (en) | 1976-02-25 |
SE415146B (en) | 1980-09-15 |
ES412496A2 (en) | 1976-03-01 |
BE796437R (en) | 1973-09-10 |
NO143520C (en) | 1981-03-04 |
JPS5635941B2 (en) | 1981-08-20 |
AR196234A1 (en) | 1973-12-10 |
IT1053715B (en) | 1981-10-10 |
NL7303415A (en) | 1973-09-17 |
SE409034B (en) | 1979-07-23 |
DK150593B (en) | 1987-04-06 |
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