CN1232348C - 制备不饱和醛和不饱和羧酸用的催化剂 - Google Patents
制备不饱和醛和不饱和羧酸用的催化剂 Download PDFInfo
- Publication number
- CN1232348C CN1232348C CNB02107805XA CN02107805A CN1232348C CN 1232348 C CN1232348 C CN 1232348C CN B02107805X A CNB02107805X A CN B02107805XA CN 02107805 A CN02107805 A CN 02107805A CN 1232348 C CN1232348 C CN 1232348C
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- China
- Prior art keywords
- catalyst
- inorfil
- bismuth
- glass fibre
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 29
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 239000003365 glass fiber Substances 0.000 claims description 31
- 239000000835 fiber Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- WKSAUQYGYAYLPV-UHFFFAOYSA-N pyrimethamine Chemical compound CCC1=NC(N)=NC(N)=C1C1=CC=C(Cl)C=C1 WKSAUQYGYAYLPV-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead 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
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium 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
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 239000012808 vapor phase Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 239000012784 inorganic fiber Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 22
- 239000007788 liquid Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OLDOGSBTACEZFS-UHFFFAOYSA-N [C].[Bi] Chemical compound [C].[Bi] OLDOGSBTACEZFS-UHFFFAOYSA-N 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 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
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid 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
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- C07C45/37—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 >C—O—functional groups to >C=O 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
- B01J23/16—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
- B01J23/002—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
- B01J23/24—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also 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
- 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
-
- 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
- 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
-
- 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
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Abstract
提供了一种适合于异丁烯,叔丁醇或丙烯的催化气相氧化生产相应的不饱和醛和不饱和羧酸用的催化剂。所述催化剂由环状成形体组成,环状成形体由(i)至少含有钼和铋作为活性组分的催化剂组合物和(ii)无机纤维。这种机械强度更佳的催化剂可以高产率地获得目的产物并且表现出活性随时间的降低很小。
Description
发明领域
本发明涉及制备不饱和醛和不饱和羧酸用的催化剂。更特别地,本发明涉及适用于由异丁烯、叔丁醇(下文称为叔丁醇)、或丙烯的气相催化氧化生产甲基丙烯醛和甲基丙烯酸或丙烯醛和丙烯酸的催化剂。本发明还涉及使用所述催化剂生产这些不饱和醛和不饱和羧酸的方法。
现有技术
对于在由异丁烯、叔丁醇或丙烯的气相催化氧化分别生产对应的不饱和醛和不饱和羧酸的情况下所用的催化剂,已经提出了许多方案。
众所周知,当催化剂形状由球形变成环形时,产品产率提高。例如,关于采用环形催化剂的优点,JP 59(1984)-46132A(=US4,511,671A,EP 102,641 A1)已经进行了阐述:(1)由于几何表面积增加,反应转化率提高,(2)由于催化剂壁厚减少增强了催化剂热量排除效率,产品产率提高,(3)压力损失减小,(4)由于热负荷降低,催化剂的寿命延长。为了再增大这些作用,使环的厚度减小是优选的。然而,该厚度的减小,引起催化剂机械强度降低,并产生一些问题:例如,当最终的环形催化剂装载在鼓状罐中时,在罐底部的催化剂可能破碎并变得无用,或当它们被装入反应管时可能破碎,引起反应管中的压力降低的分散性增加。
作为改善催化剂强度的方法,加入纤维材料是已知的。例如,涉及五氧化钒催化剂、铬酸铜催化剂、镍-硅藻土催化剂和铬酸锰催化剂的JP 51(1976)-20357 B公开了一种向通过干燥、煅烧和随后的破碎所获得的催化剂粉末中加入纤维材料如兰石棉的方法。然而,向含有钼和铋作为基本成分的催化剂中加入纤维材料的作用至今是未知的。同时作为环形催化剂,纤维材料的加入引起了各个催化剂环之间的机械强度分散程度增加的问题,虽然可以提高其机械强度。
JP 59(1984)-183832 A(=US 4,564,607 A)公开了一种在杂多酸基催化剂的制备过程中加入平均直径不大于5μm的晶须作为增强剂的方法。而对于包含钼和铋作为基本成分的催化剂,晶须材料的加入导致产率降低,虽然提高催化剂机械强度。
JP 6(1994)-381 A(=US 5,532,199A,EP 574,895 A1)公开了一种在制备含有钼和铋为基本成分的载体催化剂过程中,使用平均直径为2-200μm的无机纤维作为辅助载体。这种方法的目的在于制备载体催化剂,在载体催化剂中,载体承载大量催化剂,并且为了实现该目的,制备方法必须使催化活性组分和无机纤维分散在液体中所形成的浆料沉积在一种载体上,同时使液体蒸发和汽化。然而,这种制备方法是不容易操作的,并且催化活性变化取决于制备条件的变化。因此,存在制备具有均匀催化性能的催化剂方面困难的问题。
本发明要解决的问题
因此,本发明的目的是通过提供一种催化剂来解决现有技术中的上述问题,该催化剂适用于由异丁烯、叔丁醇、或丙烯的气相催化氧化生产相应的不饱和醛和不饱和羧酸,即具有优良的机械强度、能够以高产率提供目的产物,并且表现出催化剂性能随时间降低很小的催化剂。
发明内容
通过我们的研究工作,已经发现一种生产不饱和醛和不饱和羧酸的催化剂可以实现上述目的,该催化剂通过把至少含有钼和铋作为活性成分的催化剂组合物成型成环而获得,该催化剂在催化剂组合物中另外含有无机纤维如玻璃纤维、氧化铝纤维、氧化硅纤维、碳纤维等。本发明是基于上述知识完成的。
因此,根据本发明,提供了一种用于生产不饱和醛和不饱和羧酸的催化剂,该催化剂特征在于它由至少含有钼和铋作为活性成分的催化组合物和无机纤维的环状体组成。
另外,根据本发明,提供了一种方法,其特征在于在异丁烯、叔丁醇或丙烯与分子氧的催化气相氧化中使用上述催化剂,从而分别生产相应的甲基丙烯醛和甲基丙烯酸或丙烯醛和丙烯酸。
根据本发明加入无机纤维不仅获得了催化剂机械强度的提高,而且获得了催化剂性能的提高,以及抑制催化剂随时间而中毒的原因目前还不十分清楚。估计可能是因为催化剂组合物用无机纤维稀释,在反应过程中产生的热量被耗散,所以,后续反应被抑制并且催化剂的热降解被抑制。同时由于当所加入的无机纤维具有特定尺寸时,实现了催化剂机械强度的提高,假设无机纤维被充分地分散在催化剂中,以保持与催化剂组合物充分混合和接触的条件。
本发明实施方案
本发明的催化剂是通常称为成型催化剂的类型,该催化剂是环状催化剂形式的,由含有钼和铋作为基本成分的催化剂组合物和无机纤维制成的。该催化剂不是通过把催化剂组合物承载在载体上形成的所谓载体催化剂。
作为催化剂组合物的典型实例,可以提出由下列通式(1)表示的催化剂组合物:
MoaBibFecAdBeOx (1)
(其中,Mo是钼;Bi是铋;Fe是铁;A是选自镍和钴的至少一种元素;B是选自碱金属元素、碱土金属元素、铊、磷、碲、锑、锡、铈、铅、铌、锰、砷、锌、硅、铝、钛、锆和钨中的至少一种元素;O是氧;a、b、c、d、e和x代表Mo,Bi,Fe,A,B和O各自的原子数,这里a为12,b为0.1-10,c为0.1-20,d为2-20;e为0-30,x是由其它元素的氧化程度决定的数值)。
由通式(1)表示的催化剂组合物可以根据制备这类催化剂的常用方法来配制。作为每种成分的起始物料,可以适当地选择使用这些成分的氧化物或在加热条件下形成氧化物的这些成分的盐,如硝酸盐、铵盐,有机酸盐,碳酸盐,碱金属盐等。
作为无机纤维,可以使用玻璃纤维、陶瓷纤维、碳纤维等,其中玻璃纤维,氧化铝纤维,氧化硅纤维是优选的。尤其是玻璃纤维更适合应用。一种以上的无机纤维可以适当地联合使用,或者具有不同平均纤维长度和纤维直径的纤维可以联合使用。在使用玻璃纤维时,具有不同玻璃组成的纤维也可以适当地联合使用。
作为这种无机纤维,平均纤维长度为50μm-1.5mm,优选的是50μm-1.2mm,平均纤维直径为2μm-20μm,优选的是5μm-15μm的无机纤维适合于使用。在最终的成型催化剂中平均纤维长度在上述范围内是足够的。所以,除了使用其平均长度进一步调节到50μm-1.5mm的无机纤维外,还可以使平均长度超过1.5mm的无机纤维与部分或全部催化剂组合物混合,并在剧烈搅拌条件下打碎这些纤维,最终使其平均长度在50μm-1.5mm范围内。然而,后面的实践往往降低无机纤维的分散性。使用其平均纤维长度和平均纤维直径分别偏离50μm-1.5mm和2μm-20μm的无机纤维产生一些问题,例如不能获得具有均匀性能的催化剂,所以是不能采用的。
按催化剂重量计,合适的无机纤维含量为0.01-30%,优选的是0.05-20%,尤其是0.1-10%,百分比是按重量计的。当纤维含量太低时,改善催化剂机械强度的作用不够,当纤维含量太高时,催化剂中所含的催化剂组合物变少且催化剂性能降低。
除了向催化剂组合物中加入无机纤维和把该体系成型成环以外,本发明的那些催化剂可以按制备生产不饱和醛和不饱和羧酸用的已知催化剂常用的方法制备。
更具体地,令人满意的催化剂可以通过例如向由所述通式(1)表示的催化剂组合物中加入无机纤维,然后通过常规使用的成型方法如挤制成型、压制成型等把该体系成型成环来制备。加入无机纤维的方法并不重要,并且可以使用任何方法,只要它能保证所加入的无机纤维均匀分散在最终的催化剂中。例如,无机纤维可以加入到催化剂组合物的起始混合物中,所得的浆料干燥、成型,然后煅烧;或者把催化剂组合物干燥、煅烧并粉碎,并把无机纤维加入到所得的粉末中,充分混合并把混合物成型。特别地,前一种方法是有利的,因为这种方法获得提高了机械强度,提高了目的产品产率,延长了催化剂的寿命,以及良好的重现性的催化剂。煅烧处理通常在400-800℃进行。无机纤维可以全部立即加入或分批加入。例如,部分纤维可以加入到含有起始混合物的悬浮液中,其余的纤维加入到干燥并煅烧的粉末中。
在成型的情况下,如果需要,可以使用常规所用的粘结剂,如聚乙烯醇、硬脂醇、硝酸铵、石墨、水、醇等。
环状成型催化剂颗粒的每个颗粒优选的是外径为3-10mm,内径是外径的0.1-0.7倍,长度(高度)是外径的0.5-2倍。
除了使用上述成型催化剂作为催化剂以外,根据本发明的催化气相氧化反应可以按使用氧分子进行异丁烯、叔丁醇或丙烯的催化气相氧化以生产相应的甲基丙烯醛和甲基丙烯酸或丙烯醛和丙烯酸的常用方法进行。例如,含有1-10体积%的异丁烯、叔丁醇或丙烯,3-20体积%的分子氧,0-60体积%的水蒸气和20-80体积%的惰性气体如氮气、二氧化碳气等的气体混合物可以在250-450℃、在常压-1MPa和300-5,000h-1(STP)空速条件下引入到所述成型的催化剂上。
在实施根据本发明的催化蒸气氧化过程中,显然可以使用这样一种方法,即每个反应管中填充两种或多种具有不同活性的催化剂,它们通过改变组成、煅烧条件、催化剂尺寸或形状来制备,由于催化剂以层状形式堆积,因此从反应器气体入口到气体出口,催化剂的活性持续增加,阻止热点处热量的累积,或者采用各种其它已知的抑制方法的任一种。
根据本发明,可以容易地制备机械强度高、能够高产率获得作为目标产物的不饱和醛和不饱和羧酸,并且表现出催化活性随时间的降低(产率降低)很小的均匀催化性能的催化剂。另外,根据本发明,可以长时间高产率地生产丙烯醛和丙烯酸或甲基丙烯醛和甲基丙烯酸。
实施例
下文中,参考工作实施例更具体地解释了本发明。实施例和对比实施例中所给出的转化率和产率定义如下:
通过下面的方法进行了催化剂的性能试验和破损强度试验。
催化性能试验-1
把100毫升的催化剂装在内径为25毫米的钢质反应管中,向其中引入包含6体积%的异丁烯,13体积%的氧气,15体积%的水蒸气和66体积%的氮气。在空速1600h-1、反应温度340℃下进行反应。分析30小时后的反应气体。
催化性能试验-2
把1500毫升的催化剂装在内径为25毫米的钢质反应管中,向其中引入包含6体积%的异丁烯,13体积%的氧气,15体积%的水蒸气和66体积%的氮气。在空速1600h-1、反应温度340℃下进行反应。分析8,000小时后的反应气体。
催化性能试验-3
把100毫升的催化剂装在内径为25毫米的钢质反应管中,向其中引入包含7体积%的丙烯,14体积%的氧气,25体积%的水蒸气和54体积%的氮气。在空速1800h-1、反应温度310℃下进行反应。分析30小时后的反应气体。
破损强度试验
使30克催化剂从内径25毫米、长5毫米的垂直竖立的不锈钢管顶部落下,并用4目筛网回收。测量筛网上所保留的催化剂重量,并应用下列方程确定催化剂的破损强度:
实施例1
把6000毫升的水加热到40℃,并在搅拌的条件下向其中溶解2118克的仲钼酸铵和530克的仲钨酸铵。从而制备了一种溶液(液体A)。独立地,把486克硝酸铋被溶解在由60毫升硝酸(浓度:65重量%)和240毫升水组成的硝酸水溶液中,制备另一种溶液(液体B)。再独立地,把2912克硝酸钴和404克硝酸铁溶解在2000毫升水中形成溶液(液体C),并把78.0克硝酸铯溶解在400毫升水中形成溶液(液体D)。然后在加热、搅拌条件下将液体B,液体C,液体D按所述次序滴加到液体A中并混合。此外,把406克20重量%的硅胶和68.9克平均纤维直径为10μm、平均纤维长度为500m的无碱玻璃纤维加入到该混合物中,然后充分搅拌。
将所获得的悬浮液在搅拌下加热,蒸发该体系到干燥,把所得的固体物质成型为外径6.0毫米、内径1.0毫米、高6.6毫米的环,将这种环在500℃煅烧6小时,同时通入空气,以提供一种催化剂。
除玻璃纤维和氧外,这种催化剂组成是:
Mo12W2Bi1Fe1Co10Cs0.4Si1.35其玻璃纤维含量为2.0重量%。
催化剂性能试验-1和破损强度试验是使用这种催化剂进行的。这种催化剂的催化性能、在反应过程中压力损失和破损强度性能在表1中表示。
实施例2-9和对比实施例1-4
重复实施例1,但是所用的玻璃纤维或催化剂的形状发生如表1所示的变化,以制备催化剂。
使用这些催化剂进行催化剂性能试验-1和破损强度试验。它们的催化性能、反应过程中的压力损失和破损强度表示在表1中。
表1
无机纤维 | 无机纤维加入量(wt%) | 催化剂形状外径×内径×长(mm) | 异丁烯转化率(mol%) | 甲基丙烯醛和甲基丙烯酸总产率(mol%) | 破损强度(%) | 反应过程中的压力损失(kPa) | |
实施例 | 玻璃纤维(10μmφ/500μm-长) | 2.0 | 6.0×1.0×6.6 | 99.1 | 89.1 | 98.5 | 16.4 |
实施例 | 玻璃纤维(7μmφ/500μm-长) | 2.0 | 6.0×1.0×6.6 | 98.9 | 89.0 | 98.1 | 16.2 |
实施例3 | 玻璃纤维(13μmφ/500μm-长) | 2.0 | 6.0×1.0×6.6 | 99.0 | 89.2 | 97.9 | 16.7 |
实施例4 | 玻璃纤维(10μmφ/150μm-长) | 2.0 | 6.0×1.0×6.6 | 98.8 | 89.1 | 98.8 | 16.5 |
实施例 | 玻璃纤维(10μmφ/3mm-长) | 2.0 | 6.0×1.0×6.6 | 98.9 | 88.8 | 94.9 | 17.2 |
实施例6 | 玻璃纤维(10μmφ/500μm-长) | 0.5 | 6.0×1.0×6.6 | 99.0 | 88.7 | 95.5 | 17.3 |
实施例 | 玻璃纤维(10μmφ/500μm-长) | 7.0 | 6.0×1.0×6.6 | 99.2 | 89.0 | 99.1 | 16.4 |
实施例8 | 玻璃纤维混合物(10μmφ/500μm-长&10μmφ/3mm长) | 2.02.0 | 6.0×1.0×6.6 | 98.9 | 89.6 | 99.0 | 16.8 |
实施例9 | 玻璃纤维(10μmφ/500μm-长) | 2.0 | 5.0×3.0×5.5 | 99.2 | 90.2 | 95.4 | 13.1 |
表1(续)
无机纤维 | 无机纤维加入量(wt%) | 催化剂形状外径×内径×长(mm) | 异丁烯转化率(mol%) | 甲基丙烯醛和甲基丙烯酸总产率(mol%) | 破损强度(%) | 反应过程中的压力损失(kPa) | |
对比实施例1 | - | 6.0×1.0×6.6 | 99.0 | 88.2 | 90.4 | 18.1 | |
对比实施例2 | 玻璃粉末(40μmφ) | 2.0 | 6.0×1.0×6.6 | 99.1 | 88.4 | 89.7 | 18.0 |
对比实施例3 | 碳化硅(04μmφ/40μm-长) | 2.0 | 6.0×1.0×6.6 | 99.0 | 88.3 | 99.1 | 15.4 |
对比实施例4 | - | - | 5.0×3.0×5.5 | 98.9 | 89.0 | 75.0 | 18.2 |
实施例10
使用实施例1的催化剂进行催化性能试验-2。结果为:异丁烯转化率为90.2mol%,甲基丙烯醛和甲基丙烯酸总产率为82.3mol%。
对比施例5
使用对比实施例1中的催化剂进行催化性能试验-2。异丁烯转化率为85.1mol%,甲基丙烯醛和甲基丙烯酸总产率是76.6mol%。
实施例11
在搅拌下在加热到40℃的6000毫升水中溶解2000克的仲钼酸铵和50克的仲钨酸铵,形成溶液(液体A)。独立地,把778克硝酸铋溶解在由100毫升硝酸(浓度:61重量%)和400毫升水形成的硝酸水溶液中,提供一种溶液(液体B)。再独立地,把1100克硝酸钴,824克硝酸镍和572克硝酸铁溶解在2000毫升水中,形成溶液(液体C),把7.6克硝酸钾溶解在100毫升水中,形成溶液(液体D)。然后在连续搅拌条件下和混合条件下,将液体B,液体C,液体D按所述次序加入到在加热、搅拌条件下的液体A中,另外,把242克20重量%的硅溶胶和151克平均纤维直径为10μm、平均纤维长度为500μm的无碱玻璃纤维加入到混合物中,然后充分搅拌。
把所获得的悬浮液加热和搅拌,以蒸发到干燥,并成型为外径6.0毫米、内径1.0毫米、长6.6毫米的环,把它们在480℃煅烧8小时,同时通入空气,提供了一种催化剂。
除玻璃纤维和氧外,催化剂的组成是:
Mo12W0.2Bi1.7Fe1.5Co4Ni3K0.08Si1其玻璃纤维含量为5重量%。
使用这种催化剂进行了催化剂性能试验-3和破损强度试验,给出了98.3mol%的丙烯转化率,丙烯醛加丙烯酸的总产率为91.8mol%,反应期间的压力损失为18.9kPa,破损强度为98.9%。
对比实施例6
重复实施例11,但是不使用玻璃纤维,以提供一种催化剂。
使用这种催化剂进行催化剂性能试验-3和破损试验。丙烯转化率为98.5mol%,丙烯醛加丙烯酸的总产率为90.9mol%,反应期间的压力损失为21.6kPa,破损强度为94.1%
在下列实施例12和对比实施例7中,把两种具有不同活性的催化剂堆积并填充在反应管中,催化剂的填充方式是较低活性的催化剂装在反应管的入口端,较高活性的催化剂填充在反应管出口端,并进行反应。
实施例12
[要堆积的催化剂1的制备]
按照实施例1制备用于堆积的催化剂1,但是硝酸铯量改变为136.4克且环成型成为外径5.0毫米,内径3.0毫米,长度5.5毫米。
除玻璃纤维和氧外,这种催化剂的组成为:
Mo12W2Bi1Fe1Co10Cs0.7Si1.35其玻璃纤维含量为2.0重量%。
使用这种催化剂进行催化剂性能试验-1和破损强度试验的结果在表2中给出。
[要堆积的催化剂2的制备]
重复制备上述催化剂1的过程,但是硝酸铯的数量改变为19.5克,以制备要堆积的催化剂2。
除玻璃纤维和氧外,这种催化剂的组成为:
Mo12W2Bi1Fe1Co10Cs0.1Si1.35玻璃纤维含量为2.0重量%。
进行催化性能试验-1和破损强度试验的结果在表2中给出。
[反应]
通过在气体入口侧填充750毫升催化剂1,在气体出口侧填充750毫升催化剂2,形成堆积的反应管,在与催化性能试验-2相同的条件下进行反应。反应30小时后的催化剂性能在表2中给出。
对比实施例7
[堆积的催化剂3的制备]
用与实施例12中的催化剂1相同的方法制备催化剂3,但是没有加入玻璃纤维。
使用这种催化剂进行催化性能试验-1和破损强度试验的结果在表2中给出。
[堆积的催化剂4的制备]
用与实施例12中的催化剂2相同的方法制备催化剂4。但是没有加入玻璃纤维。
使用这种催化剂进行催化性能试验-1和破损强度试验的结果在表2中给出。
[反应]
在堆积中,在反应管的气体入口侧填充750毫升的所述催化剂3,在气体出口侧填充750毫升催化剂4。在与催化性能试验-2相同的条件下进行。反应30小时后的催化性能在表2中给出。
表2
催化剂组成 | 无机纤维 | 无机纤维加入量(wt%) | ||
实施例12 | 催化剂1 | Mo12W2Bi1Fe1Co10Cs0.7Si1.35 | 玻璃纤维(10μmφ/500μm-长) | 2.0 |
催化剂2 | Mo12W2Bi1Fe1Co10Cs0.1Si1.35 | 玻璃纤维(10μmφ/500μm-长) | 2.0 | |
反应 | 催化剂1:750ml催化剂2:750ml | - | - | |
对比实施例7 | 催化剂3 | Mo12W2Bi1Fe1Co10Cs0.7Si1.35 | - | - |
催化剂4 | Mo12W2Bi1Fe1Co10Cs0.1Si1.35 | - | - | |
反应 | 催化剂3:750ml催化剂4:750ml | - | - |
表2(续)
催化剂形状外径×内径×长(mm) | 异丁烯转化率(mol%) | 甲基丙烯醛和甲基丙烯酸总产率(mol%) | 破损强度(%) | 反应过程压力损失(kPa) | ||
实施例12 | 催化剂1 | 5.0×3.0×6.5 | 96.0 | 88.3 | 98.4 | 13.2 |
催化剂2 | 5.0×3.0×5.5 | 99.5 | 88.1 | 98.0 | 13.0 | |
反应 | 99.5 | 91.8 | - | 12.9 | ||
对比实施例7 | 催化剂3 | 5.0×3.0×5.5 | 97.1 | 86.9 | 76.4 | 179 |
催化剂4 | 5.0×3.0×5.5 | 99.8 | 86.4 | 74.3 | 18.4 | |
反应 | 99.7 | 90.2 | - | 18.5 |
Claims (3)
1.一种用分子氧催化气相氧化异丁烯、叔丁醇或丙烯以分别生产相应的甲基丙烯醛和甲基丙烯酸或丙烯醛和丙烯酸的催化剂,其特征在于它是环状体形式的,由至少含有钼和铋作为活性成分的催化剂组合物和无机纤维组成,其中,无机纤维是选自玻璃纤维、氧化铝纤维、氧化硅纤维和碳纤维中的至少一种,并且平均纤维长度为50μm-1.5mm,平均纤维直径2μm-20μm,和其中催化剂组成由下列通式表示:
MoaBibFecAdBeOx
其中,Mo是钼;Bi是铋;Fe是铁;A是选自镍和钴中的至少一种;B是选自碱金属元素、碱土金属元素、铊、磷,碲,锑,锡,铈,铅,铌,锰,砷,锌,硅,铝,钛,锆和钨中的至少一种元素;O是氧;a、b、c、d、e和x表示Mo、Bi、Fe、A、B和O的各自的原子数,这里,a为12,b为0.1-10、c为0.1-20,d为2-20;e为0-30,x是由其它元素的氧化程度决定的数值。
2.根据权利要求1的催化剂,它含有按催化剂重量计为0.01%-30%的无机纤维。
3.根据权利要求1或2的催化剂,其中,环状体的外径为3-10mm、内径是外径的0.1-0.7倍,长度为外径的0.5-2倍。
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KR100569632B1 (ko) * | 1999-05-13 | 2006-04-10 | 가부시키가이샤 닛폰 쇼쿠바이 | 불포화 알데히드 및 불포화 카르복실산을 제조하기 위한촉매 및 이 촉매를 사용하여 불포화 알데히드 및 불포화카르복실산을 제조하기 위한 방법 |
JP4185217B2 (ja) | 1999-05-25 | 2008-11-26 | 株式会社日本触媒 | 複合酸化物触媒、並びに(メタ)アクロレインおよび(メタ)アクリル酸の製造方法 |
JP3943291B2 (ja) | 1999-08-04 | 2007-07-11 | 株式会社日本触媒 | アクロレインおよびアクリル酸の製造方法 |
JP3744750B2 (ja) * | 1999-12-08 | 2006-02-15 | 株式会社日本触媒 | 複合酸化物触媒およびアクリル酸の製造方法 |
JP3744751B2 (ja) * | 1999-12-08 | 2006-02-15 | 株式会社日本触媒 | 担体、複合酸化物触媒、およびアクリル酸の製造方法 |
JP3943311B2 (ja) * | 2000-05-19 | 2007-07-11 | 株式会社日本触媒 | 不飽和アルデヒドおよび不飽和カルボン酸の製造方法 |
US7045657B2 (en) * | 2002-04-03 | 2006-05-16 | Nippon Shokubai Co., Ltd. | Catalytic gas phase oxidation process |
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2001
- 2001-03-21 JP JP2001080081A patent/JP3892244B2/ja not_active Expired - Lifetime
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- 2002-03-19 MY MYPI20020970A patent/MY126844A/en unknown
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- 2002-03-20 TW TW091105285A patent/TWI299006B/zh not_active IP Right Cessation
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Also Published As
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US6878847B2 (en) | 2005-04-12 |
BR0200854A (pt) | 2003-03-25 |
MY126844A (en) | 2006-10-31 |
US20040199008A1 (en) | 2004-10-07 |
US20020198103A1 (en) | 2002-12-26 |
KR100709055B1 (ko) | 2007-04-18 |
BRPI0200854B1 (pt) | 2016-07-26 |
ZA200202265B (en) | 2002-10-11 |
CN1386579A (zh) | 2002-12-25 |
EP1243331B1 (en) | 2013-02-27 |
EP1243331A1 (en) | 2002-09-25 |
JP3892244B2 (ja) | 2007-03-14 |
JP2002273229A (ja) | 2002-09-24 |
US6784134B2 (en) | 2004-08-31 |
KR20020075281A (ko) | 2002-10-04 |
SG103339A1 (en) | 2004-04-29 |
TWI299006B (en) | 2008-07-21 |
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