NO127285B - - Google Patents
Download PDFInfo
- Publication number
- NO127285B NO127285B NO05100/68A NO510068A NO127285B NO 127285 B NO127285 B NO 127285B NO 05100/68 A NO05100/68 A NO 05100/68A NO 510068 A NO510068 A NO 510068A NO 127285 B NO127285 B NO 127285B
- Authority
- NO
- Norway
- Prior art keywords
- catalyst
- oxidation
- olefins
- uranium
- arsenic
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 claims description 48
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052770 Uranium Inorganic materials 0.000 claims description 10
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J21/08—Silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8432—Arsenic
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- 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
-
- 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
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrører oksydasjonskatalysatorer omfattende oksyder av uran og arsen, eventuelt også inneholdende aktivatorer, og som er anvendbare for den katalytiske oksydasjon av olefiner til umettede aldehyder og syrer, og for oksyderende dehydrogenering av olefiner til konjugerte diener, og videre for den katalytiske amm-oksydasjon av olefiner til umettede nitriler. Det her anvendte uttrykk "amm-oksydasjon" Skal forståes å om-fatte en oksydasjon ved nærvær av ammoniakk. Som eksempler på katalytiske oksydasjonsreaksjoner skal nevnes oksydasjon av propylen til akrolein og akrylsyre, oksydasjonen av isobutylen til metakrolein, oksydehydrogeneringen av et olefin med 4-8 karbonatomér, som f-.-eks oXsydéhydrogenering av buten-1•eller buten-2 til butadien-1,3, amm-oksydasjonen av propylen til akrylnitril og amm-oksydasjonen av isobutylen til metakrylnitril. The present invention relates to oxidation catalysts comprising oxides of uranium and arsenic, optionally also containing activators, and which are applicable for the catalytic oxidation of olefins to unsaturated aldehydes and acids, and for the oxidative dehydrogenation of olefins to conjugated dienes, and further for the catalytic ammonia oxidation of olefins to unsaturated nitriles. The expression "ammonia oxidation" used here shall be understood to include an oxidation in the presence of ammonia. Examples of catalytic oxidation reactions include the oxidation of propylene to acrolein and acrylic acid, the oxidation of isobutylene to methacrolein, the oxydehydrogenation of an olefin with 4-8 carbon atoms, such as, for example, the oxydehydrogenation of butene-1•or butene-2 to butadiene- 1,3, the amm oxidation of propylene to acrylonitrile and the amm oxidation of isobutylene to methacrylonitrile.
Basiskatalysatoren ifølge foreliggende oppfinnelse er en blanding av oksyder av uran og arsen-. Forholdet mellom mengdene av elementene i basiskatalysatoren kan variere innen vide grenser. Foruten oksyder av basiselementene uran og arsen, kan imidlertid katalysatoren inneholde mer begrensede mengder av oksyder av andre elementer, som fremmer-katalysatorens virkning, og som i det foreliggende kalles aktivatorer. -Basiskatalysatoren og dens sammensetning såvel som aktivatorelementene vil finnes nærmere angitt i kravene. The basic catalyst according to the present invention is a mixture of oxides of uranium and arsenic. The ratio between the amounts of the elements in the base catalyst can vary within wide limits. Besides oxides of the basic elements uranium and arsenic, the catalyst can however contain more limited amounts of oxides of other elements, which promote the catalyst's effect, and which are called activators in the present. - The basic catalyst and its composition as well as the activator elements will be found in more detail in the requirements.
Det foretrukne atomforhold mellom uran og arsen i basiskatalysatoren er fra 6:1 til 1:6. I katalysatoren ifølge oppfinnelsen kan valensen av uran variere fra 4 til 6, og valensen av molybden kan variere fra 2 til 6. Det antaes at i det minste en del. av oksydene i foreliggende katalysatorer er tilstede som et aktivt katalytisk oksyd-kompleks. Katalysatoren ifølge oppfinnelsen utmerker seg ved et ubetydelig tap av aktivitet og selektivitet over lengere tidsrom, til tross for de relativt høye reaksjons-tempe raturer som kommer i betraktning ved de katalytiske prosesser som katalysatoren kan anvendes i.. The preferred atomic ratio of uranium to arsenic in the base catalyst is from 6:1 to 1:6. In the catalyst according to the invention, the valence of uranium may vary from 4 to 6, and the valence of molybdenum may vary from 2 to 6. It is assumed that at least a part. of the oxides in the present catalysts are present as an active catalytic oxide complex. The catalyst according to the invention is distinguished by an insignificant loss of activity and selectivity over longer periods of time, despite the relatively high reaction temperatures that come into consideration in the catalytic processes in which the catalyst can be used.
Skjønt katalysatoren ifølge oppfinnelsen gir gode resultater Although the catalyst according to the invention gives good results
uten anvendelse av en bærer, så inneholder en foretrukket katalysator fra 5 til 95 vekt% av en eller annen kjent katalysator-bærer, som fortrinnsvis er kiselsyre. without the use of a carrier, then a preferred catalyst contains from 5 to 95% by weight of some known catalyst carrier, which is preferably silicic acid.
Ved fremstillingen av basiskatalysatoren kan oksydene av elementene blandes sammen, eller de kan fremstilles særskilt og derpå blandes, eller de fremstilles særskilt eller sammen in situ. In the production of the base catalyst, the oxides of the elements can be mixed together, or they can be prepared separately and then mixed, or they can be prepared separately or together in situ.
Ved fremstillingen av basiskatalysatoren foretrekker man å anvende vannoppløselige salter av katalysatorelementene. En foretrukket kilde for uran er således uranylnitrat, for arsen orto-arsensyre og for molybden ammoniumheptamolybdat.. In the production of the base catalyst, it is preferred to use water-soluble salts of the catalyst elements. A preferred source for uranium is thus uranyl nitrate, for arsenic ortho-arsenic acid and for molybdenum ammonium heptamolybdate.
Det vil forståes av fagfolk på området at forskjellige andre salter, oppløselige i det minste i en viss grad i vann, kan anvendes for å danne oppløsningene, som ved behandling som nærmere beskrevet nedenfor vil gi de ønskede oksyder for basiskatalysatoren. På lignende måte vil det være klart at katalysatoren også kan fremstilles ved sam-utfelling av oksydene eller av salter som danner oksyder ved varmebehandling og impregnering av ett eller flere av metallene som ved varmebehandling resulterer i oksyder. It will be understood by those skilled in the art that various other salts, soluble at least to a certain extent in water, can be used to form the solutions, which when treated as described in more detail below will give the desired oxides for the base catalyst. In a similar way, it will be clear that the catalyst can also be produced by co-precipitation of the oxides or of salts that form oxides by heat treatment and impregnation of one or more of the metals that result in oxides by heat treatment.
Uansett den fremgangsmåte som anvendes for å innføre katalysator-komponentene i basiskatalysatoren, har det vist seg at komponentene som er tilstede innenfor de angitte områder, oppviser uventede og i høy grad ønskelige egenskaper for utførelse av den foran angitte fremgangsmåte. Regardless of the method used to introduce the catalyst components into the base catalyst, it has been shown that the components that are present within the indicated areas exhibit unexpected and highly desirable properties for carrying out the above-mentioned method.
Den katalytiske aktivitet av basiskatalysatoren økes ved oppheting av katalysatoren til en forhøyet temperatur. Fortrinnsvis tørkes katalysatorblandingen og opphetes ved en temperatur på 260-595°C, fortrinnsvis ved 315-425°C, i 2-24 timer. Hvis aktiviteten er utilstrekkelig, kan katalysatoren ytterligere varmebehandles ved en temperatur over ca. 425°C, men under en temperatur som er skadelig for katalysatoren, fortrinnsvis i området 425-760°C i 1-48 timer i nærvær av oksygen eller en oksygenholdig gass, f.eks. luft. The catalytic activity of the base catalyst is increased by heating the catalyst to an elevated temperature. Preferably, the catalyst mixture is dried and heated at a temperature of 260-595°C, preferably at 315-425°C, for 2-24 hours. If the activity is insufficient, the catalyst can be further heat-treated at a temperature above approx. 425°C, but below a temperature which is harmful to the catalyst, preferably in the range 425-760°C for 1-48 hours in the presence of oxygen or an oxygen-containing gas, e.g. air.
Det har også vist seg at en del av de foreliggende katalysatorer kan aktiveres ytterligere ved at den varmebehandlede katalysator utsettes for en reduserende atmosfære i 4-48 timer ved en temperatur innen området 205-540°C. Denne reduserende behandling utføres hensiktsmessig ved å la en reduserende gass, som ammoniakk, hydrogen e.l. strømme over katalysatoren. Det viste seg at katalysatorer behandlet med en reduserende gass ga en høyere grad av omdannelser etter en kort tidsperiode, enn når det i samme tid ble anvendt de samme katalysatorer som ikke var utsatt for den reduserende behandling. It has also been shown that some of the present catalysts can be further activated by exposing the heat-treated catalyst to a reducing atmosphere for 4-48 hours at a temperature within the range 205-540°C. This reducing treatment is suitably carried out by letting a reducing gas, such as ammonia, hydrogen etc. flow over the catalyst. It turned out that catalysts treated with a reducing gas gave a higher degree of conversions after a short period of time, than when the same catalysts that were not subjected to the reducing treatment were used at the same time.
De aktivatorer som med fordel kan anvendes, er forskjellige metalloksyder fra gruppene I-A, I-B, II-A, II-B, III-B, IV-A, IV-B, V-B, VI-B, VII-B og VIII i det periodiske system. Særlig effektive er oksydene av molybden, bor, vanadium, tinn,, nikkel, vismut, krom, jern, mangan, sink og wolfram i en mengde svarende til mindre .enn 1 atomekvivalent av enten uran eller arsen. Aktivåtoroksydene kan innføres i basiskatalysatoren ved inn-blanding i slammet eller gelen før kalsineringen, eller ved inn-blanding i den ovnstørkede basiskatalysator før kaMneringen. The activators that can be advantageously used are various metal oxides from the groups I-A, I-B, II-A, II-B, III-B, IV-A, IV-B, V-B, VI-B, VII-B and VIII in the Periodic Table. Particularly effective are the oxides of molybdenum, boron, vanadium, tin, nickel, bismuth, chromium, iron, manganese, zinc and tungsten in an amount corresponding to less than 1 atomic equivalent of either uranium or arsenic. The activator oxides can be introduced into the base catalyst by mixing it into the sludge or gel before calcination, or by mixing it into the oven-dried base catalyst before calcination.
En foretrukket måte til å innføre aktivatorelementet er å frem-stille' én vandig oppløsning av dettes salt, blande denne opp-løsning med oppløsningene av salter av basiskatalysatorens elementer og omrøre mens det kontinuerlig opphetes inntil opp-løsningen gelerer. Gelen føres ved hjelp av en skje over til skåler og ovnstørkes ved 120°C over natten. Den tørkede katalysator kalsineres derpå ved 425°C. En ytterligere kalsinering ved en høyere temperatur kan også anvendes for å øke aktiviteten av katalysatorkomplekset. A preferred way to introduce the activator element is to prepare an aqueous solution of its salt, mix this solution with the solutions of salts of the base catalyst elements and stir while continuously heating until the solution gels. Using a spoon, the gel is transferred to bowls and oven-dried at 120°C overnight. The dried catalyst is then calcined at 425°C. A further calcination at a higher temperature can also be used to increase the activity of the catalyst complex.
Oksydasjon av olefiner med 3 karbonatomer i en rett kjede ut-føres ved et reaktortrykk i områo det fra 0,3 til 7 kg/cm 2, en reaktortemperatur i området fra 260 til 595°C og tilsynelatende kontakttider som kan variere fra 0,1 til 50 sekunder. Et mol-forhold av oksygen til olefin nellom 0,5:1 til 5:1 gir tilfreds-stillende resultater. Oxidation of olefins with 3 carbon atoms in a straight chain is carried out at a reactor pressure in the range from 0.3 to 7 kg/cm 2 , a reactor temperature in the range from 260 to 595°C and apparent contact times that can vary from 0.1 to 50 seconds. A molar ratio of oxygen to olefin between 0.5:1 and 5:1 gives satisfactory results.
Olefiner med 3 karbonatomer i en rett kjede kan omdannes til nitrilene under lignende betingelser som beskrevet foran, med unntagelse av at ammoniakk innføres i reaktoren sammen med oksygen. Et ønsket ammoniakk-til-olefin-forhold er ca. 1:1, da det har vist seg at generelt uønskede, olefinisk umettede oksyderte produkter dannes når dette forhold er i omradet over 0,15:1 til 0,75:1. Vann dannes som et reaksjonsprodukt og ytterligere vann kan tilsettes både for å forbedre omdannelsen og også for å regulere de termiske forhold i reaktoren. Olefins with 3 carbon atoms in a straight chain can be converted to the nitriles under similar conditions as described above, with the exception that ammonia is introduced into the reactor together with oxygen. A desired ammonia-to-olefin ratio is approx. 1:1, as it has been found that generally undesirable, olefinically unsaturated oxidized products are formed when this ratio is in the range above 0.15:1 to 0.75:1. Water is formed as a reaction product and additional water can be added both to improve the conversion and also to regulate the thermal conditions in the reactor.
Olefiner med i det minste 4 og opptil ca. 8 ikke-kvaternære karbonatomer, av hvilke i det minste 4 er anordnet i rekkefølge i en rett kjede eller i en ring, kan bli oksydativt dehydro-genert til diolefiner og aromatiske forbindelser. Foretrukne olefiner er enten normale rettkjedede eller tertiære olefiner, og både cis- og trans-isomerer kan brukes. Fra ca. 0,3 til 3 mol oksygen pr. mol olefin kan anvendes for oksydehydrogenering av olefinene, og et svakt moloverskudd av oksygen foretrekkes. Reaksjon^'-emperaturene kan variere fra 325 til 1000°C, og det sørges for fjernelse av den eksoterme reaksjonsvarme, særlig når reaktortemperåturen over-skrider 550°C. Trykket, temperaturen og kontakttidene er i det samme området som for de foran beskrevne reaksjoner. Olefins with at least 4 and up to approx. 8 non-quaternary carbon atoms, of which at least 4 are arranged in sequence in a straight chain or in a ring, can be oxidatively dehydrogenated to diolefins and aromatic compounds. Preferred olefins are either normal straight chain or tertiary olefins, and both cis and trans isomers can be used. From approx. 0.3 to 3 mol of oxygen per moles of olefin can be used for oxydehydrogenation of the olefins, and a slight molar excess of oxygen is preferred. The reaction temperatures can vary from 325 to 1000°C, and care is taken to remove the exothermic heat of reaction, particularly when the reactor temperature exceeds 550°C. The pressure, temperature and contact times are in the same range as for the reactions described above.
Den tilsynelatende kontakttid defineres som tidslengden i sekunder som volumenheten av gass målt under reaksjonsbetingelsene er i kontakt med den tilsynelatende volumenhet av katalysatoren. Kon-takttiden beregnes ut fra det tilsynelatende volum av katalysator-skiktet, middeltrykket og temperaturen i reaktoren og strøm-hastighetene av de forskjellige komponenter i reaksjonsblandingen. The apparent contact time is defined as the length of time in seconds that the unit volume of gas measured under the reaction conditions is in contact with the apparent unit volume of the catalyst. The contact time is calculated from the apparent volume of the catalyst layer, the mean pressure and temperature in the reactor and the flow rates of the various components in the reaction mixture.
Prosent omdannelse pr. passering defineres som mol umettet produkt som utvinnes dividert med mol monoolefin som innføres, multi-plisert med 100. Percentage conversion per passage is defined as moles of unsaturated product recovered divided by moles of monoolefin introduced, multiplied by 100.
Et hvilket som helst reaksjonsapparat som er egnet for utførelse av dampfaseoksydasjonsreaksjoner kan anvendes, fortrinnsvis reaktorer av typen med fast skikt eller med fluidisert.skikt. Eksempler på basiskatalysatorer skal anføres i det følgende, hvor alle deler er basert på vekt hvis det ikke er anført noe annet. Any reaction apparatus suitable for carrying out vapor phase oxidation reactions can be used, preferably reactors of the fixed bed or fluidized bed type. Examples of base catalysts shall be given below, where all parts are based on weight unless otherwise stated.
Eksempel 1. Example 1.
Ved en typisk fremstilling av en ikke aktivert katalysator ble 87,8 g uranylnitrat (U02)(N03)2.6H20 oppløst i ca. 100 ml varmt vann, 154,3 g orto-arsensyre H3As04.l/2H20 ble oppløst i ca. In a typical preparation of an unactivated catalyst, 87.8 g of uranyl nitrate (U02)(N03)2.6H20 were dissolved in approx. 100 ml of hot water, 154.3 g of ortho-arsenic acid H3As04.1/2H20 were dissolved in approx.
400 ml varmt vann. Uranylnitratoppløsningen ble tilsatt til den fortynnede orto-arsensyre, og blandingen omrørt. Til denne blanding ble tilsatt 116,8 g "Ludox" (kolloidal oppløsning av polymerisert kiselsyre). Blandingen ble kontinuerlig opphetet under konstant omrøring inntil den dannet en gel. Gelen ble ved hjelp av skjeer overført til skåler, anbragt i en ovn med luftsirkulasjon ved 120°C og tørket ever natten. Den ovnstørkede katalysator ble derpå varmebehandlet i en ovn åpen til atmosfæren, og man startet med en temperatur på 425°C og derpå ble temperaturen økt til 480°C over en periode på 2 timer. Katalysatoren ble kalsinert over natten ved 480°C. Katalysatoren som man fikk hadde en sammensetning som kan skrives som 82,5% UAs,. q°ii 5" 17,5% Si02. 400 ml warm water. The uranyl nitrate solution was added to the dilute ortho-arsenic acid and the mixture stirred. To this mixture was added 116.8 g of "Ludox" (colloidal solution of polymerized silicic acid). The mixture was continuously heated with constant stirring until it formed a gel. The gel was transferred to bowls using spoons, placed in an oven with air circulation at 120°C and dried overnight. The oven-dried catalyst was then heat-treated in an oven open to the atmosphere, starting with a temperature of 425°C and then increasing the temperature to 480°C over a period of 2 hours. The catalyst was calcined overnight at 480°C. The catalyst that was obtained had a composition that can be written as 82.5% UAs. q°ii 5" 17.5% SiO 2 .
Den følgende tabell viser de resultater man fikk ved anvendelse The following table shows the results obtained by application
av katalysatoren for de ovenfor angitte formål. of the catalyst for the purposes stated above.
Eksempel nr. 2 og 3 angår dannelse av akrylnitril ved amm-oksydasjon av et olefin. Examples no. 2 and 3 concern the formation of acrylonitrile by amm-oxidation of an olefin.
Eksempel 4 og 5 angår oksydasjon av et olefin til akrolein (mindre mengder av umettede syrer som også dannes, er ikke angitt). Examples 4 and 5 relate to the oxidation of an olefin to acrolein (smaller amounts of unsaturated acids which are also formed are not indicated).
Eksempel nr. 6 angår oksy-dehydrogenering av butener til butadien. Det omtrentlige mol-forhold av buten til luft var 1:12; som i de andre eksemplene i tabellen er mindre mengder av biprodukter som dannes, ikke angitt. Example No. 6 concerns the oxy-dehydrogenation of butenes to butadiene. The approximate mole ratio of butene to air was 1:12; as in the other examples in the table, smaller amounts of by-products formed are not indicated.
Varmebehandling ved 540°C og høyere som er angitt i tabellen, er generelt for å øke aktiveringen etter kalsinering ved 425°c i 16-24 timer. Heat treatment at 540°C and above as indicated in the table is generally to increase activation after calcination at 425°C for 16-24 hours.
Claims (3)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO57573A NO128101B (en) | 1967-12-20 | 1973-02-13 | |
NO57473A NO128100B (en) | 1967-12-20 | 1973-02-13 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69193467A | 1967-12-20 | 1967-12-20 | |
US69194367A | 1967-12-20 | 1967-12-20 | |
US69199267A | 1967-12-20 | 1967-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO127285B true NO127285B (en) | 1973-06-04 |
Family
ID=27418552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO05100/68A NO127285B (en) | 1967-12-20 | 1968-12-19 |
Country Status (14)
Country | Link |
---|---|
JP (3) | JPS5227118B1 (en) |
AT (1) | AT311385B (en) |
BE (1) | BE725697A (en) |
BR (1) | BR6804931D0 (en) |
CH (1) | CH500762A (en) |
DE (1) | DE1808990C3 (en) |
ES (1) | ES361612A1 (en) |
FR (1) | FR1595237A (en) |
GB (1) | GB1257335A (en) |
IL (1) | IL31274A (en) |
LU (1) | LU57596A1 (en) |
NL (1) | NL167670C (en) |
NO (1) | NO127285B (en) |
SE (1) | SE374736B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR17506A (en) * | 1971-01-25 | 1975-07-23 | Snam Progetti | WITHOUT CATALYZOER AND ITS MANUFACTURING OF UNSATERATED NITTILES AND OXIDATION OF OLEFINS |
CA975382A (en) * | 1971-02-04 | 1975-09-30 | Arthur F. Miller | Process for the manufacture of acrylonitrile and methacrylonitrile |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL302849A (en) * | 1963-01-04 |
-
1968
- 1968-11-15 DE DE1808990A patent/DE1808990C3/en not_active Expired
- 1968-12-12 JP JP43090616A patent/JPS5227118B1/ja active Pending
- 1968-12-16 IL IL31274A patent/IL31274A/en unknown
- 1968-12-17 FR FR1595237D patent/FR1595237A/fr not_active Expired
- 1968-12-17 CH CH1876768A patent/CH500762A/en not_active IP Right Cessation
- 1968-12-17 GB GB1257335D patent/GB1257335A/en not_active Expired
- 1968-12-18 ES ES361612A patent/ES361612A1/en not_active Expired
- 1968-12-18 LU LU57596D patent/LU57596A1/xx unknown
- 1968-12-18 BR BR204931/68A patent/BR6804931D0/en unknown
- 1968-12-19 SE SE6817506D patent/SE374736B/xx unknown
- 1968-12-19 NO NO05100/68A patent/NO127285B/no unknown
- 1968-12-19 BE BE725697D patent/BE725697A/xx unknown
- 1968-12-20 NL NL6818481A patent/NL167670C/en not_active IP Right Cessation
- 1968-12-20 AT AT1246268A patent/AT311385B/en active
-
1977
- 1977-03-18 JP JP2935277A patent/JPS5334194B1/ja active Pending
- 1977-03-18 JP JP2935377A patent/JPS5339397B1/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
LU57596A1 (en) | 1969-08-04 |
SE374736B (en) | 1975-03-17 |
AT311385B (en) | 1973-11-12 |
NL167670C (en) | 1982-01-18 |
BE725697A (en) | 1969-06-19 |
DE1808990A1 (en) | 1969-07-03 |
GB1257335A (en) | 1971-12-15 |
DE1808990B2 (en) | 1979-06-07 |
NL6818481A (en) | 1969-06-24 |
NL167670B (en) | 1981-08-17 |
JPS5334194B1 (en) | 1978-09-19 |
DE1808990C3 (en) | 1980-01-31 |
JPS5339397B1 (en) | 1978-10-20 |
IL31274A (en) | 1972-09-28 |
BR6804931D0 (en) | 1973-01-04 |
JPS5227118B1 (en) | 1977-07-18 |
FR1595237A (en) | 1970-06-08 |
ES361612A1 (en) | 1970-12-01 |
CH500762A (en) | 1970-12-31 |
IL31274A0 (en) | 1969-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3956181A (en) | Oxidation catalyst | |
US3932551A (en) | Process for the preparation of diolefins from olefins | |
US4162234A (en) | Oxidation catalysts | |
US4423281A (en) | Process for producing conjugated diolefins | |
US4397771A (en) | Oxidation catalysts | |
US8367885B2 (en) | Method of preparing multicomponent bismuth molybdate catalysts with controlling pH and a method of preparing 1,3-butadiene using thereof | |
NO145184B (en) | Oxidation catalysts. | |
US3546138A (en) | Promoted antimony-iron oxidation catalyst | |
JP2011178719A (en) | Process for producing butadiene | |
US3542842A (en) | Ammoxidation of propylene or isobutylene to acrylonitrile or methacrylonitrile | |
NO138476B (en) | SCISSORS FOR CUTTING METAL AND THE LIKE | |
NO143740B (en) | PROCEDURE FOR THE PREPARATION OF ACRYLIC NITRIL OR METACRYL NITRIL. | |
US4174354A (en) | Oxidative dehydrogenation using chromium-containing catalysts | |
US4190556A (en) | Production of unsaturated nitriles using catalysts promoted with various metals | |
US3544616A (en) | Ammoxidation of propylene or isobutylene to acrylonitrile or methacrylonitrile | |
NO119083B (en) | ||
US4046833A (en) | Dehydrogenation of paraffins | |
US4255284A (en) | Dehydrogenation catalyst | |
NO148936B (en) | Vapor trap with free-flowing floats | |
NO127285B (en) | ||
US4111983A (en) | Oxidation of unsaturated aldehydes to unsaturated acids | |
US3666822A (en) | Uranium-molybdenum oxidation catalysts | |
US3929899A (en) | Process for the oxidation of olefins to unsaturated aldehydes and catalysts therefore | |
US4131631A (en) | Dehydrogenation of paraffins | |
US4334116A (en) | Dehydrogenation using promoted molybdenum-copper-tin catalysts |