CN1005685B - 钒-磷氧化物催化剂及其制备方法 - Google Patents
钒-磷氧化物催化剂及其制备方法 Download PDFInfo
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- CN1005685B CN1005685B CN85107878.8A CN85107878A CN1005685B CN 1005685 B CN1005685 B CN 1005685B CN 85107878 A CN85107878 A CN 85107878A CN 1005685 B CN1005685 B CN 1005685B
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 33
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001273 butane Substances 0.000 claims description 5
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 5
- 150000003682 vanadium compounds Chemical class 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001621 bismuth Chemical class 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 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 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- -1 muriate Chemical compound 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 7
- 239000011707 mineral Substances 0.000 claims 7
- 239000004215 Carbon black (E152) Substances 0.000 claims 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000003960 organic solvent Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007792 gaseous phase Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000531229 Caryopteris x clandonensis Species 0.000 description 1
- MOHVVPIVKLUCSZ-UHFFFAOYSA-N O.[O].[P].[V] Chemical compound O.[O].[P].[V] MOHVVPIVKLUCSZ-UHFFFAOYSA-N 0.000 description 1
- 235000001486 Salvia viridis Nutrition 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 1
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000009997 thermal pre-treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001784 vanadium mineral Inorganic materials 0.000 description 1
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- 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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/64—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/13—Dicarboxylic acids
- C07C57/145—Maleic 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
含有钒-磷-混合氧化物的催化剂,适用于使C4烃,特别是使n-丁烷氧化成顺丁烯二酸酐。催化剂中,钒/磷比例为1∶1-1∶1.3,半径为100-1000的孔体积至少占半径小于10000的总孔体积的30%。在一种C1~C6醇溶液中制备催化剂,先放含五价磷化合物,然后不断地把含4~5价钒的化合物加入到反应混合物中,并且将形成的水直接从反应混合物中除去。
Description
本发明涉及一种含钒-磷-混合氧化物,用来将碳氢化物局部氧化成顺丁烯二酸酐的催化剂,它的制备方法和一种提高转换和产率的还原方法。
已知的是,钒-磷-氧-复合氧化物用作从n-丁烷中制备顺丁烯二酸酐的催化剂。美国专利说明书第3293268号所述的是一种从盐酸水溶液中制备钒-磷-氧复合物的方法,所采用的原材料为V2O3,H3PO4和草酸。通过将反应混合物蒸发至干燥状态而获得钒-磷-氧-复合物。当钒-磷-氧-复合物成形和焙烧后,温度为550-575℃时,其克分子浓度产率只是为35-40%。美国专利说明书第4100106号所述的是一种美国专利说明书第3293268号所述方法的改进方法。按照这种方法,通过加水使得钒-磷-氧-复合物从浓缩了的盐酸中沉淀下来,这样就莸得了一种晶体产品,并且用X-光谱图来进行鉴定,在作相应的调节后,当使用从丁烷氧化成顺丁烯二酸酐的催化剂,反应温度为400-420℃时,其产率大约可达55%。这种方法的缺点是要使用腐蚀性很强的盐酸。用有机化合物还原V2O5这是早为人知的,见J.S.利特(J.S.Litter),W.A.沃特斯(W.A.Waters),化学协会杂志1959,(J.Chem.Soc.1959)第1299-1305页。同样在含HCl的酒精溶液里还原V2O5也是已知的,见库珀尔等(Koppeletal),有机化学杂志45,1905(Zeit.Anorg.Chem.45,1905)第346-351页。
美国专利说明书第3864280描述了采用一种气体状态的HCl来制备钒-磷-氧-复合物的方法,一旦V2O3还原结束,加入H3PO4,通过有机溶液的蒸发使所形成的钒-磷-氧-复合物分离。在450℃以下的温度下,按严格规定的方法来调节钒-磷-氧-复合物,同时使其转变成结晶相,即“B-相”,制备成活性催化剂。这种催化剂的调节对催化剂生产能力具有很大的限制性,并且需要一种很特殊的方法。该方法必须作出精确的规定(温度升高为3℃/分),这在工业上很难实现。另外,合适的表面积为7-50平方米/克,需要指出的是,催化剂的活性随表面积增大而增大。关于在有机溶液中制备钒-磷-氧-合成物的方法,联邦德国公开说明书3010710号中认为,V2O5还原成四价钒,要采用H3PO3和H3PO4。所有试剂在反应开始时都要一起加入。催化剂在长期间活化后才能获得,但最佳结果在10-20天才可达到,这就降低了产量。
所有至今所知的制备钒-磷-氧-复合氧化物的方法中,从反应一开始起,反应混合物里就要有五价钒成份。有些情况下,当四价钒还原成五价钒结束时,加入磷成份。也有另外一些情况,从开始起,反应混合物里就含有磷成份。
本发明的任务在于提供一种催化剂及其制备方法。该催化剂与已知催化剂不同,其特点是调节比较方便,比较快,特别是其活性、选择性和生产率都比较好。
本发明的催化剂的特征在于半径为100-1000的孔体积至少占半径小于10000的总孔体积的30%。优先考虑的是半径为100-1000的孔体积至少占半径小于10000的总孔体积的40%。理想情况是,半径为100-1000的孔体积约占半径小于10000的总孔体积的100%。
本发明的催化剂在制备后和皮带运输前呈细粉末状。根据本发明90%粉末直径为1-5微米,平均为2-4微米。
还特别发现,对催化效率有决定作用的,不是绝对内表面积,而是孔尺寸和孔大小分配。
本发明的催化剂,选择性好,活性好,效率高,这就可能使催化剂在长时间间隔后,以很高的添加速度,例如每小时每公斤催化剂可加入150克以下的n-丁烷,都不会降低其效率,并且产率很高,每100公斤所加的丁烷可产接近100公斤的顺丁烯二酸酐,相当于每公斤催化剂每小时的顺丁烯二酸酐产量为150克。
如果调换碳氢化物,例如调换n-丁烷,催化剂采用较低的单位添加速度。那么就可能获得110%左右的产率。
在一个适宜的实施例中,催化剂内钒和磷原子数之比为1∶1~1.3,优先考虑1∶1.05~1.2。另外,催化剂还可以含有一种或者多种提高活性添加剂(促进剂),从锂,钛,锆,铪,铬,钼,锰,铁,钴,镍,铜,锌,硼,硅,锡或者铋系列中选择。
本发明方法的特征在于C1~C6醇里含有含五价磷化合物,在0.5-4小时内,优先考虑在0.8-2小时内,连续加入含4~5价钒的化合物,其中钒与磷原子数之比为1∶1~1.3,将在反应中形成的水直接不断地从反应混合物中除去,至钒的最终价数为3.9~4.2,随后将反应混合物分离而得到钒-磷-氧-混合物固体,在95~150℃温度下,优先考虑130~140℃温度下,将固体干燥并且在200~300℃温度下将其活化成催化剂。
本发明的催化剂有确定的晶体结构,下列X-射线光谱(Cuk)来评定:
活化后,催化剂以上述结构形式被应用。在一个优先考虑采用的实施例中,催化剂紧接着还要被还原。还原是在无分子氧的情况下通过将催化剂和一种气体状态具有2-6碳原子的碳氢化物,在300-500℃温度下处理来进行的,适宜的碳氢化物为丁二烯,n-丁烷,1-丁烯,顺式-2-丁烯,反式-2-丁烯或者它们的混合物,优先考虑采用n-丁烷。气体状态的碳氢化物也可以含有惰性气体,优先考虑的惰性气体为二氧化碳和氮气。这种还原过程就其本身而言虽然在美国专利说明书41816、8号里有过描述。但是,采用本发明的新催化剂时,仍可提高生产率,即使当使用本发明的标准的催化剂使其生产率下降时,也可重新达到原来的全部生产率。还原反应也可靠装在反应锅里的催化剂来实现。
可以采用一种1-6碳原子的醇类作为有剂溶剂。适宜的醇类为甲醇,乙醇,丙醇,丁醇,1-丙醇,2-丙醇,1-丁醇,2-丁醇,异丁醇异戊醇或者它们的混合物,优先考虑采用异丁醇。
含适当磷的化合物为五价磷化合物,适宜的化合物为P2O5,或者重量百分比为85%的H3PO4,优先考虑采用重量百分比为100%的H3PO4。
可以采用四价钒和(或者)五价钒的无机和(或者)有机化合物,或者采用四价钒无机化合物,优先考虑采用V2O5来作为含钒化合物。
钒化合物的形状对催化剂质量是很重要的。粉末状钒化合物的效果最好,其颗粒直径应该等于或者小于2微米,优先考虑采用1微米或者更小的颗粒。这种细粉可以通过用喷射式磨碎机研磨而成。
钒和磷的原子数比P/V为1∶1-1.3∶1,优先考虑1.05∶1-1.2∶1。
在制备过程中或者在固态催化剂成形以前,可以加入一种提高活性的添加剂(促进剂)。从锂,钛,锆,铪,铬,钼,锰,铁,钴,镍,铜,锌,硼,硅,锡或者铋系列中选择,可以是单独形式,也可以是相互混合形式。如果采用一种提高活性的添加剂,那么其与钒原子数之比要成0.01∶1-0.3∶1,优先考虑0.05∶1-0.15∶1。上述提高活性的添加剂可以以它们的氧化物或者盐类形式来使用,适宜的氧化物或者盐类为碳酸盐,硝酸盐,氯化物,溴化物,硫酸盐或者醋酸盐。
譬如,催化剂的制备可以以下列方法来进行。在一个具有搅拌器,带冷凝器的蒸馏塔和水分离器的反应锅里,放入溶剂和磷化合物。就1公斤磷化物来讲,每公斤磷配5-50公斤溶剂,这是适宜的,优先考虑配10-20公斤溶剂。混合物被加热到沸点,并进行搅拌,在一定的时间里,适宜的时间为0.5-4小时,优先考虑0.8-2小时,将钒化合物以固态形式或者悬浮体形式慢慢加入到反应锅里,后者悬浮在与通常所用的溶剂相一致的悬浮剂里。在制备过程中,钒的价数降至五价以下。反应过程中形成的水靠水分离器来分离。如果钒加完,反应混合物还要在回流状态下维持1-2小时,同样,所形成的水仍要连续分离,这时,钒的最终价数被调节到3.9-4.2。接着将含有钒-磷-氧-复合物的悬浮体冷却。所形成的钒-磷-氧-混合氧化物可以通过过滤分离,紧接着进行干燥,或者将溶剂蒸发至干燥状态。两种情况下,都可获得已干燥的固态钒-磷-氧-混合氧化物。还有其它合适的途径,譬如,可以通过将溶剂蒸发或者蒸馏,获得具有40-50%固态浓度的悬浮体,这样就可以通过吹干,给定情况下,借助结合剂,来进一步加工处理这种泥浆形状的反应混合物。
钒-磷-氧-混合氧化物的适宜干燥温度为90-150℃,优先考虑为130-140℃温度。
如果要用固定床反应锅的话,应当使固体成形,譬如压成片状,那么上述后一种方法最合适将钒-磷-氧-混合氧化物从反应混合物中分离,通过吹开,获得的粉末流动性很好,这就容易加工成性能均匀的片状。其它一些可采用的成形装置有,譬如靠一个成粒化盘或者一个成粒转筒来挤压成形或者加工成片的装置。
催化剂的成形可以在活化前,也可以在活化后,活化和成形之间本身没有一定的顺序。通过加热到200-300℃温度进行活化,这通常需要2-24小时。
如上所述,可以使固定床反应锅用的催化剂成形,或者可以使本发明的催化剂通过适当的处理,譬如通过吹开,而用于沸腾层反应锅。
本发明的催化剂用来使1.3-丁二烯,n-丁烷,n-丁烯,1-丁烯,顺式2-丁烯,反式-2-丁烯或者它们的混合物氧化成顺丁烯二酸酐,优先考虑用来使n-丁烷局部氧化成顺丁烯二酸酐。
图中曲线表示:
○钒-磷-氧-混合氧化物,按本发明制备(实施例1);
*钒-磷-氧-复合物,按美国专利说明书第4100106号制备(比较实施例1);
△钒-磷-氧-合成物,在异丁醇作为溶剂中制备,从反应一开始起全部V2O5就在反应混合物里(比较实施例2)。
实施例
为了试验在下列实施例1-5中制备的催化剂和查明催化剂效能,应用三种不同的反应锅。
反应锅A:反应锅直径φi=21毫米
催化剂床高度=900毫米
反应管道装在一个铝块里,由电加热线圈加热。
反应锅B:反应锅直径φi=21毫米
催化剂高度3000毫米
反应管道浸在盐池里,由电加热线圈加热。
反应锅C:反应锅直径φi=25毫米
催化剂床高度=3000毫米
反应管道浸在盐池里,由电加热线圈加热。
所有三种反应锅,内部都有一个轴向安置的热电偶,用来测量温度,催化剂效能由下列规定的参数来确定:
碳氢化物转换%转换成产品的克分子碳氢化物/供入的克分子碳氢化物·100
重量百分比 产率=顺丁烯二酸酐(克)/供入的碳氢化物(克)·100
重量百分比 选择性=制备成的顺丁烯二酸(克)/转换成产品的碳氢化物(克)·100
实施例1
在装有一个热电偶,一个机械搅拌器,一个带回流冷却器一体型玻璃蒸馏塔和一个迪安(Dean)一斯塔克(Stark)一水分离器的5升容量三颈烧瓶里,放入2升异丁醇和404克重量百分比为100%的H3PO4,将混合物加到回流温度,然后在1小时里,在100立方厘米异丁醇中加入326克V2O5成悬浮液,添加V2O5期间,与V2O5一起加入的同样数量异丁醇从反应混合物中蒸馏出来,同时,在VO还原的反应过程中所形成的水也被蒸馏出来。加完V2O5后,为了去掉所有在反应期间形成的水,还要在回流状态下加热二小时,然后将形成的浆冷却,分滤出兰色固体,并且在140℃温度下干燥。根据这种所述方法,获得了钒-磷-氧-混合氧化物,它可作为原来催化剂的初馏物和初始产品,所得到的粉末孔分配如下,即半径为100-1000的孔体积占半径小于10000的总孔体积的36%,图1清楚地表明了这一点,它对两种技术,本发明和已知技术,所制备的孔体积的分配进行了比较,参见比较实施例1和2。采用硬脂酸作附加物,将干燥粉末压制成3毫米直径,3毫米高的圆柱状片,在300℃温度下焙烧6小时。然后将300克催化剂,在300℃温度下放入实验反应锅A里。催化剂在空气流(500标准升/小时)中加热到350℃温度。其时,温度每小时升高20℃温度。接着加入30克n-丁烷。在2小时内,温度升到380℃,反应锅在该条件下保持16小时。这时,催化剂达到最好的和恒定的效能。
表1 试验期间的催化剂效能
实施例2
方法与实施例1相同,在装有搅拌器,一体型蒸馏塔和水分离器反应锅里加入250升异丁醇和38.7公斤重量百分比为100%的磷酸。反应锅用AIS1316不锈钢制成,容量为400升。在100升异丁醇中配以31.3公斤V2O5所成的悬浮液,在1小时内连续加入。在加悬浮液时,相应量的异丁醇被蒸馏出来,同时在V2O5还原时所形成的水也被分离出来。加完悬浮液后,还要在回流状态下烧煮2小时,并且将所有的水从混合物中除去。含钒-磷-氧-混合氧化物的浆通过异丁醇的蒸馏分离而浓缩。浆中固体含量达到35%(重量百分比)后,将其冷却和吹干,这样,溶液可重新使用。将获得的微球型产品,放在空气中,在280℃温度下进行12小时热处理。然后加入硬脂酸,把混合物压制成4×4毫米大的圆柱片状。将其在300℃温度下放入反应锅B,通过输入空气,温度连续上升到370℃,在这温度下,开始加入n-丁烷,直至达到最佳工作范围(空间速度3200/小时),n-丁烷浓度1.8%克分子百分比)。大约8000小时后,与美国专利说明书第4181628号所述相同,将催化剂进行再活化。为此,在12小时内,430℃温度下,将一种n-丁烷-氮-混合物(n-丁烷50%体积百分比)加到反应锅中的催化剂上。得到的催化剂效能如下:盐温度400℃,C4一转换83%,产率重量百分比97%,选择性重量百分比117%。表2列出该催化剂的效能。
表2 催化剂的效能
长期工作后,该催化剂会失效。但如美国专利说明书第4181628所述一样的方法,该催化剂也很容易能够进行再生。
实施例3
应用如实施例2的设备和方法,反应结束时,将钒-磷-氧-混合氧化物在一个压滤机里进行过滤。滤饼在一个真空烘干设备中用80℃温度烘干,加入硬脂酸后制成颗粒。然后将其磨碎,并且将50-100微米颗粒尺寸的粉末压成5毫米外径,4毫米高和1.5毫米厚的环形圆片。在300℃温度下,采用空气进行7小时热处理后,在300℃温度下,将环形圆片放入反应锅C内。工作参数:空间速度为2300/小时,n-丁烷浓度1.8%克分子百分比。
表3 催化剂的效能
实施例4
根据实施例1来制备,成形和焙烧钒-磷-氧-混合氧化物。将30克圆柱形块(3毫米直径,3毫米高),在300℃温度下放入实验反应锅A中,反应参数连续调节到:
空气流量 500标准升/小时
C4-馏份-加入速度 15克/小时
反应温度 365℃
C4-馏份成份是:
n-丁烷 18%
异丁烷 5%
1-丁烯 55%
顺式-2-丁烯 7%
反式-2-丁烯 15%
12小时后,催化剂转换成:
C4-转换 91%
对全部C4量而讲,其重量产率为:90%
实施例5
制备催化剂,如实施例2所述,通过喷射空气,加工成微球粒(平均大小为100微米)。将其进行8小时预热处理,温度为250℃。然后将500克这种催化剂放入玻璃液态床一实验反应锅(φi=40毫米)里,吹入空气,温度连续上升到370℃,在此温度下加入n-丁烯,调节反应条件至:
空气流量 150标准升/小时
n=丁烷浓度 5%(克分子百分数)
10小时后,催化剂效能就稳定了
反应温度 380℃
n-丁烷转换 75%
重量产率 92%
比较实施例1:
按照美国专利说明书第4100106号实施例1加工钒-磷-氧-复合物。将1000毫克V2O5添加在8000克含36%HCl的水溶液里成悬浮状,然后将悬浮液仔细地搅拌加热。在100℃温度下,在回流状态下烧煮2小时,接着慢慢加入溶解在700毫升水中的70毫克无水草酸,最后加入1370克85%的H3PO4,该混合物浓缩至2000毫升体积,然后对形成的粘性溶液再加上2000毫升水。这样形成兰色晶体沉淀物,然后过滤出固体,并且将其干燥。粉末孔分配的测量结果,由图1中曲线给出:半径为100-1000的孔体积仅仅占半径为10000以下总孔体积的4%。
比较实施例2
为比较起见,转换开始前,放入全部钒化合物来制备钒-磷-氧-复合物。将2升异丁醇,404克100%的H3PO4和326克V2O5组成的混合物在回流状态下煮10小时,并且将V2O5还原时和钒-磷-氧-混合氧化物形成时产生的水立即连续不断地去掉。将形成的浆冷却,分离出固体,并且在130℃温度下干燥。所得到的粉末孔分配见图1:半径为100-1000的孔体积仅仅占半径为10000以下的总孔体积的18%。干燥粉末被成形为圆柱状(直径3毫米,高3毫米),并且在300℃温度下焙烧6小时,然后将300克催化剂放入反应锅A中,按照实施例1进行活化。在360小时后,催化剂才能达到其最好的效能:88%转换和98%产率(重量百分比),反应锅温度为380℃。
Claims (25)
3、根据权利要求1或2的催化剂,其特征在于至少90%的催化剂的颗粒直径为1-5微米。
4、根据权利要求1或2的催化剂,其特征在于催化剂中钒与磷原子数之比为1∶1.05-1.2。
5、根据权利要求1或2的催化剂,其特征在于催化剂中还含有提高活性的添加剂,从锂,钛,锆,铪,铬,钼,锰,铁,钴,镍,铜,锌,硼,硅,锡或者铋系列中进行选择,可以是单种形式,也可以是相互混合形式,但其与钒原子数之比为0.01-0.3∶1。
6、根据权利要求5的催化剂,其特征在于提高活性的催化剂与钒原子数之比为0.05∶1~0.15∶1。
7、一种制备权利要求1所述的催化剂的方法,其特征在于先在C1~C6醇中放入含五价磷的无机化合物,然后在0.5~4小时内连续加入含4~5价钒的无机化合物,其中钒与磷的原子数之比为1∶1~1.3,直接不断地从反应混合物中除去反应所生成的水,直至钒的最终价数为3.9~4.2,然后分离反应混合物,将分离得的钒-磷混合氧化物固体在90~150℃的温度下干燥,并在200~300℃的温度下活化成催化剂。
8、根据权利要求7的方法,其特征在于在0.8~2小时内加入所述的钒化合物。
9、根据权利要求7或8的方法,其特征在于所述的C1~C6醇选自甲醇,乙醇,1-丙醇,2-丙醇,1-丁醇,2-丁醇,异丁醇,异戊醇,或者它们的混合物。
10、根据权利要求9的方法,其特征在于所述的C1~C6醇为异丁醇。
11、根据权利要求7或8的方法,其特征在于所述的含五价磷的无机化合物是P2O5或85%(重量)的H3PO4或100%(重量)的H3PO4。
12、根据权利要求11的方法,其特征在于所述的含五价磷无机化合物是100%(重量)的H3PO4。
13、根据权利要求7或8的方法,其特征在于所述含4~5价钒的无机化合物是V2O5。
14、根据权利要求7或8的方法,其特征在于所述含4~5价钒的无机化合物的粒径小于或等于2μm。
15、根据权利要求14的方法,其特征在于所述含4~5价钒的无机化合物的粒径小于或等于1μm。
16、根据权利要求7或8的方法,其特征在于所采用的钒与磷原子数之比为1∶1.05~1∶1.2。
17、根据权利要求7或8的方法,其特征在于在制备过程中,要加入一种提高活性的添加剂,从锂,钛,锆,铪,铬,钼,锰,铁,钴,镍,铜,锌,硼,硅,锡或者铋系列中选择,可以是单独形式,也可以是相互混合形式,但其与钒原子数之比为0.01∶1-0.3∶1,它们是氧化物或盐,适宜的氧化物或盐是碳酸盐、硝酸盐、氯化物、溴化物、磺酸盐或醋酸盐。
18、根据权利要求17的方法,其特征在于所述提高活性的添加剂以与钒原子数之比为0.05∶1~0.15∶1的比例加入。
19、根据权利要求7或8的方法,其特征在于所述固体在130~140℃的温度下干燥。
20、根据权利要求7或8的方法,其特征在于催化剂被激活后,在300~500℃的温度下,在无分子氧存在下,通过用2~6个碳原子的气态烃处理而使催化剂还原。
21、根据权利要求20的方法,其特征在于所述的气态烃化合物选自1,3-丁二烯,正丁烷,1-丁烯,顺式-2-丁烯,反式-2-丁烯或它们的混合物。
22、根据权利要求20的方法,其特征在于所述的气态烃为正丁烷。
23、根据权利要求20的方法,其特征在于所述的气态烃以和CO2和/或N2的混合物而使用。
24、一种催化剂的使用,其特征在于权利要求1的催化剂被用来将1,3-丁二烯,正丁烷,1-丁烯,顺式-2-丁烯,反式-2-丁烯和它们的混合物氧化成顺丁烯二酸酐。
25、根据权利要求24的使用,其特征在于优先考虑将正丁烷氧化成顺丁烯二酸酐。
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Application Number | Priority Date | Filing Date | Title |
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IT23671A/84 | 1984-11-20 | ||
IT23671/84A IT1177272B (it) | 1984-11-20 | 1984-11-20 | Catalizzatore per reazioni di ossidazione e procedimento per la sua produzione |
ITNO.23671A/84 | 1984-11-20 |
Publications (2)
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CN85107878A CN85107878A (zh) | 1986-05-10 |
CN1005685B true CN1005685B (zh) | 1989-11-08 |
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CN85107878.8A Expired CN1005685B (zh) | 1984-11-20 | 1985-10-25 | 钒-磷氧化物催化剂及其制备方法 |
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US (2) | US4668652A (zh) |
EP (1) | EP0182078B1 (zh) |
JP (1) | JPS61181540A (zh) |
KR (1) | KR860003849A (zh) |
CN (1) | CN1005685B (zh) |
AR (1) | AR240877A1 (zh) |
AT (1) | ATE60256T1 (zh) |
BR (1) | BR8505808A (zh) |
CA (1) | CA1264728A (zh) |
DE (1) | DE3581496D1 (zh) |
ES (1) | ES8608927A1 (zh) |
IN (1) | IN166342B (zh) |
IT (1) | IT1177272B (zh) |
NO (1) | NO167552C (zh) |
TR (1) | TR22772A (zh) |
ZA (1) | ZA858253B (zh) |
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US4996179A (en) * | 1989-01-17 | 1991-02-26 | Amoco Corporation | Maleic anhydride catalysts and process for their manufacture |
US5070060A (en) * | 1990-05-21 | 1991-12-03 | Scientific Design Company, Inc. | Phosphorous/vanadium oxidation catalyst |
US5155235A (en) * | 1990-07-12 | 1992-10-13 | Mitsui Toatsu Chemicals, Inc. | Catalyst for producing maleic anhydride from butane and process for preparing same |
US5280003A (en) * | 1992-08-24 | 1994-01-18 | Scientific Design Company, Inc. | Static condition process for the preparation of phosphorous/vanadium oxidation catalyst |
US5296436A (en) * | 1993-01-08 | 1994-03-22 | Scientific Design Company, Inc. | Phosphorous/vanadium oxidation catalyst |
US5641722A (en) * | 1994-09-15 | 1997-06-24 | Huntsman Petrochemical Corporation | High performance VPO catalyst and process of preparation thereof |
IT1290407B1 (it) * | 1996-04-29 | 1998-12-03 | Lonza Spa | Procedimento per la trasformazione di un precursore di catalizzatore a base di ossido misto di vanadio/fosforo nel catalizzatore attivo |
EP1029591B1 (en) * | 1999-02-19 | 2005-11-02 | Nippon Shokubai Co., Ltd. | Method for the production of acrylic acid and method for the preparation of the catalyst |
ITMI991233A1 (it) * | 1999-06-01 | 2000-12-01 | Lonza Spa | Procedimento per preparare un precursore di catalizzatore di ossido misto vanadio/fosforo |
DE10011307A1 (de) * | 2000-03-10 | 2001-09-13 | Basf Ag | Katalysator und Verfahren zur Herstellung von Maleinsäureanhydrid |
DE10211447A1 (de) * | 2002-03-15 | 2003-10-02 | Basf Ag | Katalysator und Verfahren zur Herstellung von Maleinsäureanhydrid |
DE10211449A1 (de) * | 2002-03-15 | 2003-09-25 | Basf Ag | Katalysator-Precursor für die Herstellung von Maleinsäureanhydrid und Verfahren zu dessen Herstellung |
CN1520927A (zh) * | 2003-01-30 | 2004-08-18 | ƽ | 丁烷氧化制顺丁烯二酸酐V-P-Si复合氧化物催化剂前驱体 |
EP1514598A1 (en) * | 2003-09-15 | 2005-03-16 | Lonza S.p.A. | Niobium doped vanadium/phosphorus mixed oxide catalyst |
US7357977B2 (en) * | 2005-01-13 | 2008-04-15 | International Business Machines Corporation | Ultralow dielectric constant layer with controlled biaxial stress |
US20090061649A1 (en) * | 2007-08-28 | 2009-03-05 | International Business Machines Corporation | LOW k POROUS SiCOH DIELECTRIC AND INTEGRATION WITH POST FILM FORMATION TREATMENT |
US20090061237A1 (en) * | 2007-08-28 | 2009-03-05 | International Business Machines Corporation | LOW k POROUS SiCOH DIELECTRIC AND INTEGRATION WITH POST FILM FORMATION TREATMENT |
MY155387A (en) | 2008-10-21 | 2015-10-15 | Huntsman Petrochemical Llc | High pore volume vpo catalyst for maleic anhydride production |
CN103108694A (zh) * | 2010-09-10 | 2013-05-15 | 亨斯迈石油化学有限责任公司 | 用于生产马来酸酐的具有低钒氧化态的改进型vpo催化剂 |
CN103691466B (zh) * | 2012-09-27 | 2016-07-06 | 中国石油化工股份有限公司 | 一种催化剂前驱体及其制备方法和催化剂及其应用 |
CN106622315B (zh) * | 2015-11-02 | 2019-05-17 | 中国石油化工股份有限公司 | 一种钒磷氧化物及其制备方法 |
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US3293268A (en) * | 1964-03-23 | 1966-12-20 | Princeton Chemical Res Inc | Production of maleic anhydride by oxidation of n-butane |
US3864280A (en) * | 1972-06-19 | 1975-02-04 | Chevron Res | Catalyst for a n-butane oxidation to maleic anhydride |
US4187235A (en) * | 1972-09-18 | 1980-02-05 | Chevron Research Company | Method for preparing maleic anhydride |
CH598863A5 (zh) * | 1975-01-10 | 1978-05-12 | Lonza Ag | |
US4178298A (en) * | 1976-05-21 | 1979-12-11 | Lonza, Ltd. | Process for preparing maleic anhydride |
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US4151116A (en) * | 1977-08-05 | 1979-04-24 | Halcon Research And Development Corporation | Preparation of maleic anhydride |
SU727217A1 (ru) * | 1978-05-03 | 1980-04-15 | Институт Физической Химии Им. Л.В. Писаржевского Ан Украинской Сср | Способ приготовлени ванадий-фосфорного катализатора дл окислени бутана в малеиновый ангидрид |
DE3010710A1 (de) * | 1980-03-20 | 1981-09-24 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur herstellung von katalysatoren fuer die gasphaseoxidation von gesaettigten und/oder ungesaettigten c(pfeil abwaerts)4(pfeil abwaerts)-kohlenwasserstoffen zu maleinsaeureanhydrid |
US4283288A (en) * | 1980-05-14 | 1981-08-11 | Standard Oil Company (Indiana) | Oxidation of butane to maleic anhydride |
US4283307A (en) * | 1980-06-02 | 1981-08-11 | Denka Chemical Corporation | Catalyst structure for the partial oxidation of n-butane to produce maleic anhydride |
US4410752A (en) * | 1980-07-10 | 1983-10-18 | The Standard Oil Company | Process for the oxydehydrogenation of ethane to ethylene |
US4448893A (en) * | 1981-07-24 | 1984-05-15 | The Standard Oil Company | Preparation of improved mixed vanadium phosphorus oxide catalyst and their use in oxidation processes |
US4472527A (en) * | 1982-03-31 | 1984-09-18 | Mitsubishi Chemical Industries Ltd. | Process for preparing an oxidation catalyst composition |
US4435521A (en) * | 1982-05-24 | 1984-03-06 | Exxon Research & Engineering Co. | Heterogeneous process for preparing vanadium phosphorus oxygen containing catalyst composition |
US4416803A (en) * | 1982-05-26 | 1983-11-22 | Standard Oil Company (Indiana) | Process for the manufacture of catalysts useful for the oxidation of butane to malelic anhydride |
US4525471A (en) * | 1982-09-23 | 1985-06-25 | The Standard Oil Company | Attrition resistant microspheroidal fluid bed catalysts containing the mixed oxides of vanadium and phosphorus |
US4518523A (en) * | 1983-03-04 | 1985-05-21 | The Standard Oil Company | Method for adding make-up fluid bed oxidation catalysts for fluid bed oxidation catalysts containing the mixed oxides of vanadium and phosphorus |
-
1984
- 1984-11-20 IT IT23671/84A patent/IT1177272B/it active
-
1985
- 1985-10-04 ES ES547602A patent/ES8608927A1/es not_active Expired
- 1985-10-11 CA CA000492780A patent/CA1264728A/en not_active Expired - Fee Related
- 1985-10-11 AT AT85112927T patent/ATE60256T1/de not_active IP Right Cessation
- 1985-10-11 EP EP85112927A patent/EP0182078B1/de not_active Expired - Lifetime
- 1985-10-11 DE DE8585112927T patent/DE3581496D1/de not_active Expired - Fee Related
- 1985-10-16 IN IN820/MAS/85A patent/IN166342B/en unknown
- 1985-10-18 US US06/789,151 patent/US4668652A/en not_active Expired - Lifetime
- 1985-10-18 JP JP60233140A patent/JPS61181540A/ja active Granted
- 1985-10-25 CN CN85107878.8A patent/CN1005685B/zh not_active Expired
- 1985-10-28 ZA ZA858253A patent/ZA858253B/xx unknown
- 1985-11-18 TR TR46797A patent/TR22772A/xx unknown
- 1985-11-19 BR BR8505808A patent/BR8505808A/pt unknown
- 1985-11-19 NO NO854616A patent/NO167552C/no unknown
- 1985-11-20 AR AR302326A patent/AR240877A1/es active
- 1985-11-20 KR KR1019850008660A patent/KR860003849A/ko not_active Application Discontinuation
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1986
- 1986-01-27 US US06/819,599 patent/US4713464A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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NO854616L (no) | 1986-05-21 |
JPH0582261B2 (zh) | 1993-11-18 |
IT8423671A1 (it) | 1986-05-20 |
IT1177272B (it) | 1987-08-26 |
KR860003849A (ko) | 1986-06-13 |
NO167552C (no) | 1991-11-20 |
EP0182078A2 (de) | 1986-05-28 |
ES8608927A1 (es) | 1986-09-01 |
EP0182078B1 (de) | 1991-01-23 |
US4668652A (en) | 1987-05-26 |
AR240877A1 (es) | 1991-03-27 |
ATE60256T1 (de) | 1991-02-15 |
US4713464A (en) | 1987-12-15 |
ZA858253B (en) | 1986-06-25 |
EP0182078A3 (en) | 1988-01-13 |
CA1264728A (en) | 1990-01-23 |
AR240877A2 (es) | 1991-03-27 |
CN85107878A (zh) | 1986-05-10 |
NO167552B (no) | 1991-08-12 |
IT8423671A0 (it) | 1984-11-20 |
BR8505808A (pt) | 1986-08-12 |
JPS61181540A (ja) | 1986-08-14 |
TR22772A (tr) | 1988-07-01 |
ES547602A0 (es) | 1986-09-01 |
DE3581496D1 (de) | 1991-02-28 |
IN166342B (zh) | 1990-04-14 |
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