CN1571700A - 乙烷氧化催化剂及使用该催化剂的方法 - Google Patents
乙烷氧化催化剂及使用该催化剂的方法 Download PDFInfo
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- CN1571700A CN1571700A CNA028203739A CN02820373A CN1571700A CN 1571700 A CN1571700 A CN 1571700A CN A028203739 A CNA028203739 A CN A028203739A CN 02820373 A CN02820373 A CN 02820373A CN 1571700 A CN1571700 A CN 1571700A
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- Prior art keywords
- catalyst
- acetate
- ethane
- ethene
- carbon monoxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010955 niobium Substances 0.000 claims abstract description 36
- 239000010931 gold Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000005977 Ethylene Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229930194542 Keto Natural products 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- LGDAGYXJBDILKZ-UHFFFAOYSA-N [2-methyl-1,1-dioxo-3-(pyridin-2-ylcarbamoyl)-1$l^{6},2-benzothiazin-4-yl] 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 LGDAGYXJBDILKZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical class [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- QCSGLAMXZCLSJW-UHFFFAOYSA-L platinum(2+);diacetate Chemical compound [Pt+2].CC([O-])=O.CC([O-])=O QCSGLAMXZCLSJW-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
选择性氧化乙烷制备乙酸和/或选择性氧化乙烯制备乙酸的催化剂组合物及用途,所述催化剂含有与氧结合的元素钼,钒,铌,金,不含有钯,符合以下经验式:MoaWbAucVdNbeZf,其中Z是一种或几种选自以下组的元素:B,Al,Ga,In,Ge,Sn,Pb,Sb,Cu,Pt,Ag,Fe和Re;a,b,c,d,e和f表示所述元素的克原子比:0<a≤1;0≤b<1;a+b=1;10-5<c≤0.02;0<d≤2;0<e≤1;0.0001≤f≤0.05。
Description
本发明涉及选择性氧化乙烷制备乙酸和/或选择性氧化乙烯制备乙酸的催化剂,还涉及使用上述催化剂生产乙酸的方法。
含有钼,钒和铌结合氧的催化剂用于通过氧化乙烷和乙烯生产乙酸的方法是本领域公知的技术,例如公开于US 4250346,EP-A-1043064,WO99/20592和DE19630832。
USP №4250346公开了在气相反应中,以相对高的转化率和选择性由乙烷氧化脱氢制备乙烯的方法,乙烯的生产在低于550℃下使用催化剂进行,所述催化剂以MoaXbYc的比例含有钼,X和Y.其中X是Cr,Mn,Nb,Ta,Ti,V和/或W;优选Mn,Nb,V和/或W;Y是Bi,Ce,Co,Cu,Fe,K,Mg,Ni,P,Pb,Sb,Si,Sn,Ti和/或U;优选Sb,Ce和/或U,a是1,b是0.05-1.0;c是0-2,优选0.05-1.0;其条件是对于Co,Ni和/或Fe c的总值低于0.5。
WO99/20592涉及选择性地从乙烷,乙烯或其混合物及氧生产乙酸的方法,反应在高温于催化剂存在下进行,所述催化剂为MoaPdbXcYd,其中X是一个或几个Cr,Mn,Nb,Ta,Ti,V,Te和W;Y是一个或几个B,Al,Ga,In,Pt,Zn,Cd,Bi,Ce,Co,Rh,Ir,Cu,Ag,Au,Fe,Ru,Os,K,Rb,Cs,Mg,Ca,Sr,Ba,Nb,Zr,Hf,Ni,P,Pb,Sb,Si,Sn,Ti和U;a=1,b=0.0001-0.01,c=0.4-1,d=0.005-1。
德国专利申请DE 19630832A1涉及类似的催化剂组合物,其中a=1,b>0,c>0,d=0-2;优选a=1,b=0.0001-0.5,c=0.1-1.0,d=0-1.0。
WO99/20592和DE 19630832的催化剂需要有钯存在。
EP-A-1043064公开了氧化乙烷制备乙烯和/或乙酸,和/或氧化乙烯制备乙酸的催化剂组合物,所述催化剂含有与氧结合的元素钼,钒,铌,金,并且在钯存在下符合以下经验式:
MoaWbAucVdNbeYf (I)
其中Y是一个或几个选自以下组的元素:Cr,Mn,Ta,Ti,B,Al,Ga,In,Pt,Zn,Cd,Bi,Ce,Co,Rh,Ir,Cu,Ag,Fe,Ru,Os,K,Rb,Cs,Mg,Ca,Sr,Ba,Zr,Hf,Ni,P,Pb,Sb,Si,Sn,Ti,U,Re,Te,La和Pd;a,b,c,d,e和f表示所述元素的克原子比:0<a≤1;0≤b<1;a+b=1;10-5<c≤0.02;0<d≤2;0<e≤1;0≤f≤2。
仍然需要开发一种氧化乙烷和/或乙烯制备乙酸的催化剂,以及使用所述催化剂生产乙酸的方法,其中的催化剂能够高选择性地得到乙酸。
目前惊奇地发现可以使用一种催化剂,该催化含有和氧结合的元素钼,钒,铌,和金以及一种或几种选自以下组的元素:硼,铝,镓,铟,锗,锡,铅,锑,铜,铂,银,铁,和铼,并且没有钯,能够氧化乙烷和/或乙烯以高选择性制备乙酸,而且还发现使用本发明的催化剂以高选择性地制备乙酸的同时,能够稍稍降低(若有的话),例如对乙烯的选择性。
因此本发明提供选择性氧化乙烷制备乙酸和/或选择性氧化乙烯制备乙酸的催化剂组合物,所述催化剂含有与氧结合的元素钼,钒,铌,金,不含有钯,符合以下经验式:
MoaWbAucVdNbeZf (I)
其中Z是一种或几种选自以下组的元素:B,Al,Ga,In,Ge,Sn,Pb,Sb,Cu,Pt,Ag,Fe和Re;a,b,c,d,e和f表示所述元素的克原子比:
0<a≤1;0≤b<1;a+b=1;
10-5<c≤0.02;
0<d≤2;
0<e≤1;和
0.0001≤f≤0.05。
包括在式(I)中的催化剂有
MoaWbAucVdNbeSnf
MoaAucVdNbeSnf
优选Z是Sn,Ag,Fe和Re;特别是Sn。
式(I)的合适的催化剂的实例包括:
Mo1.000 V0.423 Nb0.115 Au0.008Ag 0.008Oy;
Mo1.000 V0.423 Nb0.115 Au0.008Fe 0.0156Oy;
Mo1.000 V0.423 Nb0.115 Au0.008Re 0.008Oy;
Mo1.00 V0.423 Nb0.115 Au0.0008Sn 0.0008Oy;和
Mo1.00 V0.423 Nb0.117 Au0.0008Sn 0.0156Oy;
其中Y的数值满足组合物中元素对氧的价数。
优选0.01<a≤1;优选0.1<d≤2;优选0.01<e≤0.5例如0.05≤e≤0.15;优选0.0005≤f≤0.02。
本发明催化剂组合物的优点是它们能够高选择性地将乙烷和/或乙烯转化为乙酸,通常使用本发明的催化剂组合物对乙酸的选择性至少为50mol%,优选至少60mol%,,例如可以达到至少70mol%。
特别是使用本发明的催化剂组合物可以高选择性地制备乙酸,同时对乙烯(若有的话)选择性低。
通常使用本发明的催化剂组合物对乙烯的选择性低于25mol%,优选低于10mol%,例如低于5mol%。
优选使用本发明的催化剂组合物对乙酸的选择性至少为60mol%,例如至少70mol%,对乙烯的选择性低于15mol%,例如低于10mol%。
本文使用的选择性是指反映产生的所需乙酸产品数量和形成产品中的总碳比较的百分数:
%选择性=100*产生的乙酸的摩尔数/S
其中S=与全部含碳产品总合(以碳为基准)相当的酸的摩尔数,流出物中的烷除外。
本发明催化剂组合物可以使用制备催化剂的任何常规方法制备,从溶解性化合物和/或配合物和/或每一金属化合物的溶液制备是合适的,所述溶液优选是含水体系,pH为1-12,优选2-8,温度为20-100℃。
通常含有元素的化合物的混合物是通过溶解足够数量的溶解性化合物或分散不溶解性化合物制备,以提供催化剂组合物中所需的克-原子比,然后从混合物中除去溶剂,再将催化剂通过加热到200-500℃进行煅烧,通常在空气或氧气中煅烧1分钟-24小时,优选使空气或氧气慢慢流动制备催化剂组合物。
催化剂能够以无载体或有载体的形式使用,合适的载体包括二氧化硅,氧化铝,氧化锆,二氧化钛,碳化硅以及它们的两种或两种以上的混合物。
制备本发明催化剂组合物的更详细的合适的方法记载于例如EP-A-0166438。
催化剂可以以固定床或流动床方式使用。
在另一实施方案中,本发明提供从含有乙烷和/或乙烯的气体混合物生产乙酸的方法,该方法包括将气体混合物在提高温度及上述催化剂组合物存在下与含有分子氧的气体接触。
乙烷选择性地被氧化成乙酸和/或乙烯选择性地被氧化成乙酸,优选乙烷和任选的乙烯被氧化成含有乙酸的混合物,上述混合物在加入或除去,或不加入或不除去乙酸的情况下,用于通过在后续方法中和含分子氧的气体反应生产醋酸乙烯酯。
原料气体包括乙烷和/或乙烯,优选乙烷。
乙烷和/或乙烯能够以基本上纯的形式使用,或者是和一种或几种氮气,甲烷,二氧化碳和水的混合物以蒸气形式使用,例如它们能够以较大范围的数量例如大于5体积%的一种或几种氢气,一氧化碳,C3/C4烷烃或链烯烃存在,或者以较小范围的数量例如小于5体积%存在。
含有分子氧的气体可以是空气或者是比空气含有分子氧多或少的气体,例如氧气,合适的气体例如是用合适的稀释气体,例如氮气稀释的氧气。
除了乙烷和/或乙烯以及含分子氧的气体以外,加入水(水蒸气)是优选的,因为这样能够提高对乙酸的选择性。
在200-500℃范围提高温度是合适的,优选200-400℃。
压力可以是大气压或高于大气压,例如在1-50巴范围,优选1-30巴。
在使用本发明方法前优选将催化剂组合物煅烧,煅烧在含分子氧的气体,可如空气存在下通过加热到250-500℃范围进行是合适的。
用于实现本发明的操作条件和其它情况记载于上述现有技术中,例如USP №4250346。
参考以下实施例进一步说明本发明的方法。
催化剂的制备
催化剂A的制备(比较例)
搅拌下在100ml蒸馏水中于70℃溶解22.935g钼酸铵和0.0357g氯化金铵制备溶液A;搅拌下在150ml蒸馏水中于70℃溶解6.434g钒酸铵制备溶液B;搅拌下在100ml蒸馏水中于70℃溶解7.785g草酸铌铵制备溶液C,每种溶液A,B,C放置15分钟使组份充分溶解,然后搅拌下于70℃将溶液C迅速加入到溶液B中,混合的溶液B/C于70℃搅拌15分钟,然后迅速加入到溶液A中,最终的混合溶液A/B/C于70℃搅拌15分钟,再将溶液加热到沸腾,使水蒸发,充分蒸发反应混合物1.5小时,得到干燥的膏状物,将带膏状物的烧杯转移到烘箱中进一步于120℃干燥2小时,干燥后将催化剂前体研磨为细粉末,过0.2mm的筛,得到的粉末状催化剂膏饼于烘箱中400℃的稳定空气中煅烧4小时,得到的氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008Ag 0.0008Oy;
这种催化剂不是本发明的催化剂,因为它不含有以下的元素:B,Al,Ga,In,Ge,Sn,Pb,Sb,Cu,Pt,Ag,Fe和Re。
催化剂B的制备
除了再往溶液A中加入0.0190g氯化锡(II)以外,催化剂B和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.0008 Sn0.0008Oy;
催化剂C的制备
除了往溶液A中加入0.3792g氯化锡(II)以外,催化剂C和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.117 Au0.0008 Sn0.0156Oy;
催化剂D的制备
除了往溶液A中加入0.0299g乙酸锑(III)(FW298.88)以外,催化剂D和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Sb0.008Oy;
催化剂E的制备
除了往溶液A中加入0.0200g乙酸铜(II)(FW199.65)以外,催化剂E和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Cu0.008Oy;
催化剂F的制备
除了往溶液A中加入0.0027g乙酸铂(FW352.66)以外,催化剂F和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Pt0.0006Oy;
催化剂G的制备
除了往溶液A中加入0.0174g乙酸银(I)(FW166.92)以外,催化剂G和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Ag0.008Oy;
催化剂H的制备
除了往溶液A中加入0.8080g硝酸铁(III)(FW404.00)以外,催化剂H和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Fe0.0156Oy;
催化剂I的制备
除了往溶液A中加入0.0268g铼酸铵(FW268.24)以外,催化剂I和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Re0.008Oy;
催化剂J的制备
除了往溶液A中加入0.0256g硝酸镓(FW255.74)以外,催化剂J和催化剂A制备方法相同,该氧化催化剂的分子式为:
Mo1.000 V0.423 Nb0.115 Au0.008 Ga0.008Oy;
乙烷氧化反应的一般方法
5ml粉末催化剂A-J和15ml直径为0.4mm的玻璃珠混合,得到体积为20ml的稀释催化剂床,将该稀释的催化剂放入固定床反应器(Hastelloy)中,所述反应器尺寸为内径12mm和长度为40cm,在催化剂床上下使用惰性填料的石英隔离塞使催化剂保持在反应器中间的位置,用氦于20巴压力试验检查设备是否漏气。1小时内以5℃/分钟速度于16巴氦气中加热到220℃活化催化剂,保证催化剂前体完全分解。
将所需的乙烷,乙烯和于氦气中的20%氧气流和水引入到反应器中,保证所需进口的组成,该组合物为:乙烷52%v/v,氧6.7%v/v,乙烯10%v/v,水5%v/v及平衡的氦气,总加入的流速保持保证GHSV2000-9000/h,60分钟平衡以后,从出口气流中取出气体样品,送到GC系统(Unicam 4400),检查乙烷,乙烯,氧和氦气含量。
反应器的温度给定值提高到293℃,使每种催化剂A-J达到类似的反应器温度299-301℃,以便容易直接进行比较。然后进一步平衡60分钟,开始收集液体产品,并且一般继续18小时。在此期间使用GC分析(ProGC,Unicam)测定流出物的气体组成,在运行中通过水-气计量计测定流出气体的体积,收集液体产品并且在运行期后称重。使用气相色谱分析(分别带有TCD和FID检测器的Unicam4400和4200)测定液体产品的组成。
由分析原料和产品的流速及组成计算以下参数:
转化率:
乙烷=(入口乙烷mol/出口乙烷mol)/入口乙烷mol*100
氧气=(入口氧气mol/出口氧气mol)/入口氧气mol*100
选择性:
对乙酸(C-mol%)=(出口mol乙酸*2)/((出口mol乙烯*2-入口mol乙烯*2)+出口mol CO+出口mol CO2+出口mol乙酸*2)*100
对乙烯(C-mol%)=(出口mol乙烯*2)/((出口mol乙烯*2-入口mol乙烯*2)+出口mol CO+出口mol CO2+出口mol乙酸*2)*100
对CO(C-mol%)=(出口molCO)/((出口mol乙烯*2-入口mol乙烯*2)+出口mol CO+出口mol CO2+出口mol乙酸*2)*100
对CO2(C-mol%)=(出口molCO2)/((出口mol乙烯*2-入口mol乙烯*2)+出口mol CO+出口mol CO2+出口mol乙酸*2)*100
对COX=对CO(C-mol%)的选择性+对CO2(C-mol%)的选择性
STY(空时产率)%=g乙酸/kg催化剂床/小时
通常多于反应的物质平衡和碳平衡是100±5%。
试验A和实施例1-9
在上述一般反应方法中使用每一催化剂A-J,结果列于表1,在表1所指的标准条件下评价每种催化剂。
表1
试验 | 催化剂 | 乙烷转化率%C-mol | 乙酸选择性%C-mol | 乙烯选择性%C-mol | COX选择性%C-mol | STY乙酸g/kg-cat/h |
A | A | 7.8 | 47.0 | 34.4 | 18.5 | 163 |
实施例1 | B | 4.2 | 71.3 | 0.0 | 28.7 | 118 |
实施例2 | C | 3.8 | 70.8 | 0.0 | 29.2 | 105 |
实施例3 | D | 6.3 | 56.9 | 24.7 | 18.5 | 133.6 |
实施例4 | E | 4.1 | 58.4 | 12.9 | 28.7 | 85.9 |
实施例5 | F | 5.1 | 59.9 | 12.6 | 27.4 | 112.7 |
实施例6 | G | 3.1 | 63.4 | 1.7 | 34.9 | 99.8 |
实施例7 | H | 4.7 | 68.1 | 5.6 | 26.4 | 119.3 |
实施例8 | I | 5.0 | 70.1 | 5.7 | 24.2 | 131.1 |
实施例9 | J | 5.8 | 53.9 | 27.5 | 18.7 | 115.8 |
条件:
乙烷52%v/v,氧6.7%v/v,乙烯10%v/v,水5%v/v及平衡的氦气,GHSV=3200h-1;16巴。
表1的结果清楚地说明,和比较催化剂A比较,本发明的催化剂对于乙酸有较高的选择性,并且在对乙酸有高选择性的同时,还降低了对乙烯的选择性。
Claims (12)
1.选择性氧化乙烷制备乙酸和/或选择性氧化乙烯制备乙酸的催化剂组合物,所述催化剂含有与氧结合的元素钼,钒,铌,金,不含有钯,符合以下经验式:
MoaWbAucVdNbeZf (I)
其中Z是一种或几种选自以下组的元素:B,Al,Ga,In,Ge,Sn,Pb,Sb,Cu,Pt,Ag,Fe和Re;a,b,c,d,e和f表示所述元素的克原子比:
0<a≤1;0≤b<1;a+b=1;
10-5<c≤0.02;
0<d≤2;
0<e≤1;和
0.0001≤f≤0.05。
2.按照权利要求1的催化剂组合物,其中0.01<a≤1;0.1<d≤2;0.01<e≤0.5和0.0005≤f≤0.02。
3.按照上述任何一项权利要求的催化剂组合物,其中Z是Sn,Ag,Fe或Re。
4.按照权利要求3的催化剂组合物,其中Z是Sn。
5.按照权利要求4的催化剂组合物,其中式I选自MoaWbAucVdNbeSnf和MoaAucVdNbeSnf。
6.按照权利要求1的催化剂组合物,其中式I选自:
Mo1.000V0.423Nb0.115Au0.008Ag0.008Oy;
Mo1.000V0.423Nb0.115Au0.008Fe0.0156Oy;
Mo1.000V0.423Nb0.115Au0.008Re0.008Oy;
Mo1.00V0.423Nb0.115Au0.0008Sn0.0008Oy;
Mo1.00V0.423Nb0.117Au0.0008Sn0.0156Oy;
其中Y的数值满足组合物中元素对氧的价数。
7.从含有乙烷和/或乙烯的气体混合物生产乙酸的方法,该方法包括在提高温度下、在上述任何一项权利要求记载的催化剂组合物存在下使所述气体混合物和含有分子氧的气体接触。
8.按照权利要求7的方法,其中乙烷和任选的乙烯被氧化为含有乙酸的混合物。
9.按照权利要求7或8的方法,其中提高的温度范围是200-500℃。
10.按照权利要求7-9任何一项的方法,其中压力范围是1-50巴。
11.按照权利要求7-10任何一项的方法,其中乙烷和/或乙烯的氧化反应对乙酸的选择性至少为50mol%。
12.按照权利要求11的方法,其中乙烷和/或乙烯的氧化反应对乙酸的选择性至少为60mol%。
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CN107949433A (zh) * | 2015-09-14 | 2018-04-20 | 诺瓦化学品(国际)股份有限公司 | 固定床反应器中的散热稀释剂 |
CN110330331A (zh) * | 2019-07-12 | 2019-10-15 | 无锡工艺职业技术学院 | 一种柔性压电陶瓷材料及其制备方法 |
CN110330330A (zh) * | 2019-07-12 | 2019-10-15 | 无锡工艺职业技术学院 | 一种具有高磁导率的微波介电陶瓷材料及其制备方法 |
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DE102010001399A1 (de) | 2010-01-29 | 2011-08-04 | Wacker Chemie AG, 81737 | Verfahren zur Herstellung von Carbonsäuren mit 1-3 Kohlenstoff-atomen aus nachwachsenden Rohstoffen |
RU2462307C1 (ru) * | 2011-05-30 | 2012-09-27 | Учреждение Российской академии наук Институт катализа им. Г.К. Борескова Сибирского отделения РАН | Катализатор и способ получения уксусной кислоты или смеси уксусной кислоты и этилацетата |
US8921257B2 (en) * | 2011-12-02 | 2014-12-30 | Saudi Basic Industries Corporation | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
KR102312033B1 (ko) * | 2017-11-30 | 2021-10-13 | 롯데케미칼 주식회사 | 에탄의 산화탈수소화 반응용 촉매 시스템, 이의 제조방법 및 이를 이용한 에탄으로부터 에틸렌의 제조방법 |
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CN107949433A (zh) * | 2015-09-14 | 2018-04-20 | 诺瓦化学品(国际)股份有限公司 | 固定床反应器中的散热稀释剂 |
US11110423B2 (en) | 2015-09-14 | 2021-09-07 | Nova Chemicals (International) S.A. | Heat dissipating diluent in fixed bed reactors |
CN110330331A (zh) * | 2019-07-12 | 2019-10-15 | 无锡工艺职业技术学院 | 一种柔性压电陶瓷材料及其制备方法 |
CN110330330A (zh) * | 2019-07-12 | 2019-10-15 | 无锡工艺职业技术学院 | 一种具有高磁导率的微波介电陶瓷材料及其制备方法 |
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