WO2010038677A1 - アクロレインおよび/またはアクリル酸製造用の触媒および該触媒を用いたアクロレインおよび/またはアクリル酸の製造方法 - Google Patents
アクロレインおよび/またはアクリル酸製造用の触媒および該触媒を用いたアクロレインおよび/またはアクリル酸の製造方法 Download PDFInfo
- Publication number
- WO2010038677A1 WO2010038677A1 PCT/JP2009/066657 JP2009066657W WO2010038677A1 WO 2010038677 A1 WO2010038677 A1 WO 2010038677A1 JP 2009066657 W JP2009066657 W JP 2009066657W WO 2010038677 A1 WO2010038677 A1 WO 2010038677A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- acrylic acid
- crystallinity
- acrolein
- experimental example
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 229
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 110
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 239000012808 vapor phase Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 239000012071 phase Substances 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 49
- 239000000203 mixture Substances 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000002994 raw material Substances 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000012018 catalyst precursor Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000011000 absolute method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 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 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- -1 steatite Chemical compound 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011133 lead Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Chemical group 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07C45/33—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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
Definitions
- the present invention relates to a catalyst suitable for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene with molecular oxygen and a method for producing acrolein and / or acrylic acid using the catalyst.
- Acrylic acid is industrially important as a raw material for various synthetic resins, paints, and plasticizers, and in recent years, its importance is increasing as a raw material for water-absorbing resins.
- the most common method for producing acrylic acid is a two-stage oxidation method in which acrolein is mainly obtained by catalytic vapor phase oxidation of propylene, and acrylic acid is obtained by catalytic vapor phase oxidation of the obtained acrolein.
- Patent Document 1 discloses a catalyst that has ⁇ -X 1 MoO 4 as the main component of the crystal phase of the catalyst, Fe 2 (MoO 4 ) 3 as the second component, and does not contain MoO 3 .
- Patent Document 2 discloses a catalyst made of an oxide of cobalt, molybdenum, bismuth, and iron and having a crystal phase represented by Bi 2 Fe 2 Mo 2 O 12 in its active phase.
- Patent Document 3 discloses a method of using dry powdered iron molybdate-gel (Fe (MoO 4 ) 3 ) at the time of catalyst preparation in a catalyst containing molybdenum, bismuth and iron as essential components.
- Patent Document 4 discloses that in a catalyst containing molybdenum, bismuth, and iron as essential components, a catalyst having a reduced catalytic activity is subjected to heat treatment under specific conditions, whereby Bi 2 Fe 2 of a crystalline phase in the active component of the catalyst is disclosed. It is disclosed that the peak derived from Mo 2 O 12 decreases, the peak derived from Fe 2 (MoO 4 ) 3 is regenerated, and the catalyst performance is activated.
- JP 2000-169149 A Japanese Patent Publication No. 56-28180 JP-A-1-168344 JP-A-63-137755
- Acrylic acid is currently produced on a scale of several million tons / year worldwide, and the demand for water-absorbing resin is growing. Furthermore, if the yield of acrylic acid is improved even by 0.1% on an industrial scale due to the recent rise in the price of raw material propylene, it will be very economically significant. Even in the process of producing acrolein and / or acrylic acid from propylene, which is the first stage reaction, it is desired to improve the yield. Although all of the catalysts disclosed in Patent Documents 1 to 4 show some improvement in the catalyst performance such as the yield and life of the target acrolein and / or acrylic acid, they are still in view of the industrial scale. It leaves room for improvement.
- Patent Document 3 shows that the acrylic acid yield is improved to some extent in Examples, it is a reaction result using a laboratory level reaction tube, and the raw material propylene concentration is as low as 4.5%. It is an evaluation under conditions. Moreover, the catalyst life has not been evaluated, and there are doubts about practical catalyst performance.
- Patent Document 4 discloses a method for reactivating a catalyst using a known catalyst, and does not propose a new catalyst for the purpose of improving the catalyst performance. Further, Patent Documents 1 to 4 disclose the technical idea of increasing the yield of acrolein and / or acrylic acid over a long period by controlling the crystallinity of the catalytically active component within an appropriate range. Not.
- the present invention has been made in view of the above circumstances, and its object is to produce acrolein and / or acrylic acid from propylene, which is excellent in catalyst performance such as catalytic activity and selectivity and catalyst life and stable over a long period of time.
- the object is to provide a catalyst exhibiting performance.
- the catalyst of the present invention has excellent catalyst performance such as catalyst activity and selectivity and catalyst life, and has stable performance over a long period of time.
- the crystallinity ratio R calculated as the ratio of the crystallinity M to the crystallinity T is preferably in the range of 0.03 to 0.20.
- the method for producing acrolein and / or acrylic acid of the present invention is a method for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene with a molecular oxygen-containing gas, and the presence of the catalyst of the present invention. It is characterized by having a step of performing catalytic vapor phase oxidation below. According to the production method of the present invention, acrolein and / or acrylic acid can be produced stably in a high yield over a long period of time.
- the catalyst and the method for producing acrolein and / or acrylic acid of the present invention when acrolein and / or acrylic acid is produced by catalytic gas phase oxidation of propylene with molecular oxygen, the yield is stable over a long period of time. Acrolein and / or acrylic acid can be produced at a high rate.
- the catalyst for producing acrolein and / or acrylic acid and the method for producing acrolein and / or acrylic acid using the catalyst according to the present invention will be described in detail.
- the scope of the present invention is not limited to these descriptions.
- the present invention can be appropriately modified and implemented without departing from the spirit of the present invention.
- the acrolein and / or acrylic acid production catalyst of the present invention is a catalyst for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene with a molecular oxygen-containing gas.
- the raw material gas for producing acrolein and / or acrylic acid only needs to contain at least a molecular oxygen-containing gas and propylene.
- the molecular oxygen-containing gas is not particularly limited as long as it contains molecular oxygen. For example, a gas composed only of molecular oxygen may be used, or air may be used.
- the crystallinity T in the following range is in the range of 4% to 18%.
- the crystallinity T is preferably 7% or more and 15% or less.
- the catalyst performance and catalyst life such as catalyst activity and selectivity are excellent and the catalyst has stable performance over a long period of time.
- the reason for this is not clear, but if the crystallinity T is less than 4%, the selectivity for acrolein and / or acrylic acid decreases, and if the crystallinity T exceeds 18%, the life of the catalyst is short. As a result, deterioration of performance over time is caused at an early stage.
- the total diffracted X-ray intensity in the following range is obtained, and is calculated from the ratio of the X-ray diffracted intensity of the entire crystalline portion to the total diffracted X-ray intensity.
- T (diffracted X-ray intensity from all crystalline parts) / (total diffracted X-ray intensity) ⁇ 100 (2)
- a specific method for obtaining the crystallinity T is as follows. After removing the background from the diffraction profile obtained by X-ray diffraction analysis, the halo pattern due to the amorphous part is separated, and the resulting diffraction line of the crystalline part is separated for each peak.
- the integrated intensity (S n ) of the halo pattern due to the amorphous part and the integrated intensity (S c1 , S c2 , S c3 ...) Of each peak of the crystalline part are calculated, and each peak of the crystalline part is calculated.
- the diffracted X-ray intensity S c of the entire crystalline portion is calculated from the total sum of the integrated intensities (S c1 + S c2 + S c3 +).
- the crystallinity ratio R calculated as the ratio between the peak crystallinity M and the crystallinity T is preferably in the range of 0.03 to 0.20.
- the crystallinity ratio R is more preferably in the range of 0.05 or more and 0.13 or less.
- R M / T (1)
- the crystallinity ratio R the ratio of a specific crystalline portion in the total crystalline portion is defined, and the catalyst performance and the life of the catalyst are excellent. For acrylic acid production that exhibits stable performance over a long period of time It becomes easy to obtain a catalyst.
- the catalyst for producing acrolein and / or acrylic acid of the present invention contains a catalytically active component containing molybdenum, bismuth, and cobalt as essential components.
- acrolein and / or acrylic acid production catalyst of the present invention it is important that the crystallinity T satisfies the above range, and the present invention is a catalyst containing molybdenum, bismuth and cobalt as essential components as catalytic active components.
- various compositions and preparation methods for the catalytically active component have been proposed by various companies.
- the composition of the catalytically active component is represented by the following general formula (4).
- a catalyst represented by it is a catalyst represented by.
- the activity that is, propylene conversion rate, acrolein and / or acrylic acid yield is adjusted by adjusting the crystallinity T to an appropriate range. It becomes easy to obtain a catalyst excellent in catalyst performance such as rate and catalyst life.
- Mo molybdenum
- Bi bismuth
- Co cobalt
- X1 is at least one element selected from the group consisting of iron and nickel
- X2 is a group consisting of alkali metal, alkaline earth metal, boron, and thallium.
- X4 is phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese.
- O oxygen
- a, b, c, d, e, f, g, and z Mo, Bi, Co, X1, and X2, respectively.
- a 0.001 ⁇ e ⁇ 10,0 ⁇ f ⁇ 30,0 ⁇ g ⁇ 10, z is a numerical value determined by the oxidation state of each element.
- the catalyst of the present invention may have an inert carrier for supporting the catalytically active component in addition to the catalytically active component containing molybdenum, bismuth and cobalt as essential components.
- an inert carrier alumina, silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite and the like can be used.
- the shape of the carrier is not particularly limited, and those having a spherical shape, a cylindrical shape, a ring shape, or the like can be used.
- raw materials for the catalytically active component oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates or organic acid salts of the elements constituting the catalytically active component, aqueous solutions thereof, sols thereof
- a compound containing a plurality of elements is mixed with water to obtain an aqueous solution or an aqueous slurry (hereinafter referred to as “starting material mixture”).
- the obtained starting material mixture is dried by a method such as heating or decompression as necessary to obtain a catalyst precursor.
- a drying method by heating for example, a spray dryer, a drum dryer or the like may be used, and as a result, a powdery catalyst precursor is obtained.
- the starting raw material mixture can be heated in an air stream using a box dryer, a tunnel dryer, or the like to obtain a block or flake catalyst precursor.
- a method of further heating the solid can be employed.
- a drying method by reduced pressure for example, a block or powdery catalyst precursor may be obtained using a vacuum dryer.
- the obtained catalyst precursor is sent to a subsequent molding step through a pulverization step and a classification step for obtaining a powder having an appropriate particle size, if necessary.
- the catalyst precursor may be once calcined and then sent to the molding step.
- the particle size of the catalyst precursor before being sent to the molding step is not particularly limited, but is preferably a particle size in which the passing particle portion of the sieve having an opening of 500 ⁇ m is 90% by mass or more from the viewpoint of excellent moldability.
- the catalyst precursor may be molded into a fixed shape by an extrusion molding method, a tableting molding method, or the like to obtain a molded body.
- a starting material mixture or catalyst precursor as a catalytically active component may be supported on an arbitrary inert carrier having a certain shape to obtain a support (supporting method).
- the shape of the molded body obtained by the extrusion molding method or tableting molding method there is no particular limitation on the shape of the molded body obtained by the extrusion molding method or tableting molding method, and any shape such as a spherical shape, a cylindrical shape, a ring shape, or an indefinite shape may be used.
- a spherical shape it does not need to be a true sphere, and may be substantially spherical, and the same applies to a cylindrical shape and a ring shape.
- an evaporative drying method in which a starting material mixed solution is applied to or adhered to an inert carrier having a certain shape as it is without being dried in an aqueous solution or an aqueous slurry while being heated and dried.
- a solid method or a granulation method in which the catalyst precursor is supported in powder form on an inert carrier can be employed.
- the centrifugal fluid coating method described in JP-A No. 63-200249, the rolling granulation method described in JP-A No. 8-2999797, or the rocking mixer method described in JP-A No. 2004-136267 are used.
- a granulation method in which the catalytically active component is supported on an inert carrier is preferred.
- the material and shape of the inert carrier that can be used in the loading method are as described above.
- a molding aid or binder for improving moldability, a pore forming agent for forming appropriate pores in the catalyst, or the like may be used.
- Specific examples thereof include organic compounds of ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol, and phenols; water; inorganic salts such as nitric acid, ammonium nitrate, and ammonium carbonate. .
- a reinforcing agent such as silica, alumina, glass fiber, silicon carbide, or silicon nitride can be used.
- the reinforcing agent may be added to the starting raw material mixture or may be blended with the catalyst precursor.
- the molded body or carrier obtained in the molding process is sent to the subsequent firing process and fired.
- the firing temperature is preferably in the range of 350 ° C. to 600 ° C., more preferably in the range of 400 ° C. to 550 ° C.
- the firing time is preferably 1 to 10 hours.
- the firing furnace used in the firing step is not particularly limited, and a generally used box-type firing furnace, tunnel-type firing furnace, or the like may be used.
- the catalyst of the present invention has a specific crystallinity T, and more preferably has a specific crystallinity ratio R.
- the following method is preferably adopted. That is, in the above catalyst preparation method, when preparing the starting raw material mixed solution, the raw materials are dividedly added, the raw material charging time and the temperature of the mixed liquid when mixing the raw materials are adjusted; The catalyst may be hydrothermally treated under specific conditions. Specifically, when preparing the starting raw material mixture, raw materials such as molybdenum, bismuth, cobalt, etc. are added in two or more times, or a solution (liquid B) containing cobalt, bismuth, etc. is added to molybdenum, etc.
- the solution B may be added over a period of 30 seconds to 10 minutes, preferably 1 minute to 5 minutes. What is necessary is just to set suitably the temperature of the liquid mixture at the time of mixing a raw material with the raw material to supply.
- the calcined catalyst is charged into the autoclave together with moisture that becomes saturated steam, and the pressure is 150 ° C. to 250 ° C., more preferably 190 ° C. to 240 ° C. under pressure.
- the treatment may be performed for 2 to 48 hours.
- the crystallinity ratio R can be changed by appropriately adjusting the composition ratio of molybdenum, bismuth and cobalt in the catalytically active component.
- the method for producing acrolein and / or acrylic acid of the present invention is a method for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene with a molecular oxygen-containing gas, in the presence of the catalyst of the present invention. It has the process of performing contact gas phase oxidation. According to the method for producing acrolein and / or acrylic acid of the present invention, acrolein and / or acrylic acid can be produced stably in a high yield over a long period of time.
- the method for producing acrolein and / or acrylic acid of the present invention is not particularly limited as long as the catalytic gas phase oxidation reaction is performed using the catalyst of the present invention.
- the reactor any of a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor can be used.
- a fixed bed reactor is used as the reactor.
- the fixed bed reactor As the fixed bed reactor, a tubular type is preferable, and a multi-tube type is more preferable.
- the fixed bed reactor has one or more reaction tubes, and the catalyst is filled in the reaction tubes.
- the reaction tubes are generally arranged vertically in a fixed bed reactor.
- the inner diameter of the reaction tube is not particularly limited as long as it can be filled with the catalyst, but is usually 15 to 50 mm, more preferably 20 to 40 mm, and further preferably 22 to 38 mm.
- the catalyst filled in the reaction tube may be a single catalyst or two or more types, but the catalyst filled in the reaction tube is divided into two layers in the tube axis direction in the catalyst layer in the reaction tube. It is preferable to fill the plurality of reaction zones divided as described above so that the crystallinity ratio R of the catalyst charged in each reaction zone is different. That is, the reaction tube preferably has a plurality of reaction zones divided in the tube axis direction, and each reaction zone is preferably filled with catalysts having different crystallinity ratios R.
- the catalyst is provided in the reaction tube so that the crystallinity ratio R of the catalyst in the plurality of reaction zones decreases sequentially from the inlet side to the outlet side of the raw material gas containing propylene and the molecular oxygen-containing gas. Fill.
- the catalyst charged in any of the reaction zones preferably has a crystallinity ratio R in the range of 0.03 to 0.20.
- the above-mentioned catalyst filling method is combined with a method for filling the catalyst so that the volume occupied by the catalyst decreases from the inlet side to the outlet side of the raw material gas, a method for diluting a part of the catalyst with an inert carrier, etc. May be.
- the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor. However, if the number of reaction zones is too large, problems such as complicated packing operation of the catalyst occur. Therefore, the number of reaction zones is preferably about 2 to 6 industrially.
- the reaction conditions of the method for producing acrolein and / or acrylic acid of the present invention are not particularly limited, and any conditions can be used as long as they are generally used for this kind of reaction.
- the source gas may be 1 to 15% by volume (preferably 4 to 12% by volume) propylene, 0.5 to 25% by volume (preferably 2 to 20% by volume) molecular oxygen, 0 to 30% by volume.
- a gas mixture (preferably 0 to 25% by volume) of water vapor and the balance of an inert gas such as nitrogen may be used.
- the raw material gas may be brought into contact with the catalyst at a space velocity of 300 to 5,000 h ⁇ 1 (STP) under a pressure of 0.1 to 1.0 MPa in a temperature range of 280 to 450 ° C.
- the propylene conversion rate and the total yield of acrolein and acrylic acid were determined by the following formula.
- Propylene conversion (mol%) (mol number of reacted propylene) / (mol number of supplied propylene) ⁇ 100
- Acrolein + acrylic acid yield (mol%) (moles of produced acrolein and acrylic acid) / (moles of supplied propylene) ⁇ 100
- X-ray diffraction measurement was performed using Spectris Co., Ltd. X'PertPro.
- a sample for X-ray diffraction measurement was prepared by sieving the catalytically active component, and compressing and molding about 0.5 g of the powder having an opening of 150 ⁇ m into a tablet with a diameter of 16 mm and a thickness of 2 mm.
- the diffraction intensity was measured. From the obtained X-ray diffraction profile, the crystallinity T and the crystallinity ratio R were calculated according to the method described in JIS ⁇ K0131 (absolute method).
- a silica-alumina spherical carrier having an average particle diameter of 4.5 mm 500 parts of a silica-alumina spherical carrier having an average particle diameter of 4.5 mm is put into a rolling granulator, and then a catalyst precursor is put together with a 15% by mass aqueous ammonium nitrate solution as a binder to be carried on the carrier, and then air
- the catalyst 1 was obtained by calcination at 470 ° C. for 6 hours in an atmosphere.
- the supported rate of the catalyst 1 was 100% by mass, and the metal element composition excluding oxygen was as follows.
- the loading rate was determined by the following formula.
- Support rate (mass%) (mass of catalyst (g) ⁇ mass of carrier used (g)) / mass of carrier used (g) ⁇ 100
- the crystallinity T in the range of 2 ⁇ 5 ° to 90 ° by X-ray diffraction measurement of the catalytically active component of catalyst 1 was 7.1%, and the crystallinity ratio R of catalyst 1 was 0.10. .
- Table 1 The results of propylene conversion and acrolein + acrylic acid yield are shown in Table 1. Table 1 also shows the results of continuing the reaction for 4000 hours while appropriately changing the reaction temperature. In Experimental Example 1, the initial yield was as high as 92.8 mol%, and the decrease in yield was suppressed to only 0.2 mol% after 4000 hours. In Experimental Example 1, acrolein and acrylic acid could be produced stably and with high yield over a long period of time.
- the obtained catalyst 2 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions. The results are shown in Table 1. Table 1 also shows the results of continuing the reaction for 4000 hours while appropriately changing the reaction temperature.
- the crystallinity T of the catalyst 2 exceeded 18% and the crystallinity ratio R was a low value of 0.02, so the initial yield was as low as 90.7 mol%. After 4000 hours, the yield further decreased, and the yield decreased by 1.5 mol% compared to the initial stage.
- the obtained catalyst 3 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the initial yield was as high as 93.0 mol%.
- the obtained catalyst 4 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions. The results are shown in Table 1. Table 1 also shows the results of continuing the reaction for 4000 hours while appropriately changing the reaction temperature.
- the crystallinity T of the catalyst 4 was slightly low as 4.5%, and the crystallinity ratio R was as high as 0.21, so the yield was lower than in Experimental Examples 1 and 3.
- the initial value was 91.7 mol%, and it was 90.9 mol% after 4000 hours.
- Experimental example 5 In Experimental Example 4, the amount of ammonium paramolybdate added to the liquid A and the suspension was changed to 0 parts and 500 parts, respectively, and the time when the liquid B was added to the liquid A was changed to 20 minutes.
- the catalyst 5 was prepared in the same manner as in Experimental Example 4 except for the above.
- the supporting rate of the catalyst 5 was 100% by mass, and the metal element composition excluding oxygen was the same as in Experimental Example 4.
- the crystallinity T of the catalyst 5 was 3.4%, and the crystallinity ratio R was 0.22.
- the obtained catalyst 5 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions. The results are shown in Table 1. Table 1 also shows the results of continuing the reaction for 4000 hours while appropriately changing the reaction temperature.
- the crystallinity T of the catalyst 5 was less than 4% and the crystallinity ratio R was a high value of 0.22, so the initial yield was as low as 89.6 mol%. .
- the yield further decreased, and the yield decreased by 1.9 mol% compared to the initial stage.
- the obtained catalyst 6 was filled in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the crystallinity T of the catalyst 6 was slightly high at 17.1% and the crystallinity ratio R was a low value of 0.02, so the yield was lower than in Experimental Examples 1 and 3.
- the initial amount was 91.4 mol%.
- Experimental example 7 In Experimental Example 6, the holding temperature of liquid A and liquid B was changed to 50 ° C., the amount of ammonium paramolybdate added to liquid A and the suspension was changed to 0 parts and 500 parts, respectively, liquid B was prepared in the same manner as in Experimental Example 6 except that the catalyst 7 was obtained.
- the supporting rate of the catalyst 7 was 100% by mass, and the metal element composition excluding oxygen was the same as in Experimental Example 6.
- the crystallinity T of the catalyst 7 was 3.4%, and the crystallinity ratio R was 0.01.
- the obtained catalyst 7 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the crystallinity T of the catalyst 7 was less than 4%, and the crystallinity ratio R was as low as 0.01, so the initial yield was as low as 90.4 mol%. .
- Experimental Example 8 In Experimental Example 4, the holding temperature of the liquid A and the liquid B was changed to 70 ° C., the amount of ammonium paramolybdate added to the liquid A and the suspension was 400 parts and 100 parts, respectively, and the amount of bismuth nitrate was changed. 145 parts, the amount of iron nitrate was changed to 95.4 parts, nickel nitrate was not added, the time when adding B liquid to A liquid was changed to 30 seconds, rolling granulator A catalyst 8 was obtained in the same manner as in Experimental Example 4 except that the amount of the silica-alumina spherical support charged in was changed to 430 parts. The supporting rate of the catalyst 8 was 100% by mass, and the metal element composition excluding oxygen was as follows. Catalyst 8: Mo 12 Bi 1.3 Co 5 Fe 1 K 0.05 The crystallinity T of the catalyst 8 was 9.7%, and the crystallinity ratio R was 0.04.
- the obtained catalyst 8 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the initial yield was as high as 92.6 mol%.
- the obtained catalyst 9 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions. The results are shown in Table 1. In Experimental Example 9, the initial yield was as high as 93.0 mol%.
- the obtained catalyst 10 was charged in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the initial yield was 92.2 mol%, which was a relatively high value.
- the obtained catalyst 11 was filled in the same manner as in Experimental Example 1, and a propylene oxidation reaction was performed under the same conditions.
- the results are shown in Table 1.
- the initial yield was 92.2 mol%, which was a relatively high value.
- reaction temperature Maintaining the heat medium temperature (reaction temperature) at 315 ° C., from the bottom of the reaction tube filled with the catalyst, a mixed gas consisting of 8% by volume of propylene, 15% by volume of oxygen, 8% by volume of water vapor, and the balance of an inert gas such as nitrogen Introduced at a space velocity of 1950 hr ⁇ 1 (STP), propylene oxidation reaction was carried out.
- the catalyst 12 was arranged on the inlet side of the reaction tube and the catalyst 3 was arranged on the outlet side of the reaction tube with respect to the flow of the mixed gas. The reaction was continued for 4000 hours while appropriately changing the reaction temperature. The results are shown in Table 2.
- Experimental Example 13 A catalyst 13 was obtained in the same manner as in Experimental Example 3 except that the average particle diameter of the silica-alumina spherical carrier used in Experimental Example 3 was changed to 6.5 mm.
- the supported rate of the catalyst 13 was 100% by mass, and the metal element composition excluding oxygen, the crystallinity T, and the crystallinity ratio R were the same as those of the catalyst 3.
- the catalyst 13 and the catalyst 1 are sequentially dropped from the upper part of the reaction tube into the same reaction tube as in the experimental example 12, and filled so that the layer length of the catalyst 13 is 800 mm and the layer length of the catalyst 1 is 2100 mm, respectively.
- Propylene oxidation reaction was carried out under the same conditions as in No. 12.
- the catalyst 13 was disposed on the inlet side of the reaction tube and the catalyst 1 was disposed on the outlet side of the reaction tube with respect to the mixed gas flow.
- the results are shown in Table 2.
- two types of catalyst 1 and catalyst 13 having a crystallinity ratio R in the range of 0.03 to 0.20 are filled in a reaction tube, and a catalyst 13 having a low crystallinity ratio R is provided on the inlet side.
- the catalyst 1 having a high crystallinity ratio R was disposed on the outlet side.
- a high yield was maintained both at the initial stage and after the lapse of 4000 hours, but the performance was lower than in Experimental Example 12.
- Experimental Example 14 A catalyst 14 was obtained in the same manner as in Experimental Example 2, except that the average particle diameter of the silica-alumina spherical carrier used in Experimental Example 2 was changed to 6.5 mm.
- the supported rate of the catalyst 14 was 100% by mass, and the metal element composition excluding oxygen, the crystallinity T, and the crystallinity ratio R were the same as those of the catalyst 2.
- the catalyst 14 and the catalyst 2 are dropped sequentially from the upper part of the reaction tube and filled so that the layer length of the catalyst 14 is 800 mm and the layer length of the catalyst 2 is 2100 mm, respectively.
- Propylene oxidation reaction was carried out under the same conditions as in No. 12.
- the catalyst 14 was disposed on the inlet side of the reaction tube and the catalyst 2 was disposed on the outlet side of the reaction tube with respect to the mixed gas flow.
- the results are shown in Table 2.
- the catalyst 2 and the catalyst 14 having the same crystallinity ratio R when the crystallinity ratio R was outside the range of 0.03 to 0.20 were charged in the reaction tube.
- the yield was lower than in Experimental Examples 12 and 13.
- Experimental Example 15 A catalyst 15 was obtained in the same manner as in Experimental Example 5 except that the average particle size of the silica-alumina spherical carrier used in Experimental Example 5 was changed to 6.5 mm.
- the supported rate of the catalyst 15 was 100% by mass, and the metal element composition excluding oxygen, the crystallinity T, and the crystallinity ratio R were the same as those of the catalyst 5.
- the catalyst 15 and the catalyst 2 are dropped sequentially from the upper part of the reaction tube and filled so that the layer length of the catalyst 15 is 800 mm and the layer length of the catalyst 2 is 2100 mm, respectively.
- Propylene oxidation reaction was carried out under the same conditions as in No. 12.
- the catalyst 15 was disposed on the inlet side of the reaction tube and the catalyst 2 was disposed on the outlet side of the reaction tube with respect to the flow of the mixed gas.
- the results are shown in Table 2.
- two types of catalyst 2 and catalyst 15 having a crystallinity ratio R outside the range of 0.03 to 0.20 are filled in the reaction tube, and the catalyst 15 having a high crystallinity ratio R on the inlet side.
- a catalyst 3 having a low crystallinity ratio R was arranged on the outlet side.
- the yield was lower than in Experimental Examples 12 and 13.
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Abstract
Description
R=M/T (1)
T=(全結晶性部分からの回折X線強度)/(全体の回折X線強度)×100 (2)
R=M/T (1)
M=(ピークの結晶性部分からの回折X線強度)/(全体の回折X線強度)×100 (3)
MoaBibCocX1dX2eX3fX4gOz (4)
(ここで、Moはモリブデン、Biはビスマス、Coはコバルト、X1は鉄およびニッケルからなる群より選ばれる少なくとも1種の元素、X2はアルカリ金属、アルカリ土類金属、ホウ素、およびタリウムからなる群より選ばれる少なくとも1種の元素、X3はタングステン、ケイ素、アルミニウム、ジルコニウム、およびチタンからなる群より選ばれる少なくとも1種の元素、X4はリン、テルル、アンチモン、スズ、セリウム、鉛、ニオブ、マンガン、砒素、および亜鉛からなる群より選ばれる少なくとも1種の元素、Oは酸素を表し、またa、b、c、d、e、f、gおよびzはそれぞれMo、Bi、Co、X1、X2、X3、X4およびOの原子比を表し、a=12のとき、0.1≦b≦10、0.1≦c≦20、0.1≦d≦20、0.001≦e≦10、0≦f≦30、0≦g≦10であり、zは各元素の酸化状態によって定まる数値である。)
プロピレン転化率(モル%)=(反応したプロピレンのモル数)/(供給したプロピレンのモル数)×100
アクロレイン+アクリル酸収率(モル%)=(生成したアクロレインおよびアクリル酸のモル数)/(供給したプロピレンのモル数)×100
(1-1)触媒の調製
蒸留水3000部を60℃に維持しながら攪拌し、そこにパラモリブデン酸アンモニウム300部、硝酸カリウム1.7部を溶解して、A液を調製した。別に蒸留水300部を60℃に維持しながら攪拌し、65質量%硝酸50部、硝酸ビスマス137部、硝酸コバルト412部、硝酸鉄114部、および硝酸ニッケル206部を添加して、B液を調製した。得られたB液を、質量比で1:1になるように2つに分け、B液-1とB液-2とを得た。A液を撹拌しながら、A液にB液-1を2分間かけて添加し、さらに30分攪拌し続けた。その後、B液-2を同様に2分間かけて添加し、30分攪拌し続け懸濁液を得た。得られた懸濁液に再度パラモリブデン酸アンモニウム200部を添加し、30分攪拌し続け出発原料混合液を得た。この出発原料混合液を蒸発乾固して、ケーキ状の固形物とし、得られた固形物を空気雰囲気下200℃で約5時間乾燥を行った。乾燥後の固形物を250μm以下に粉砕し、粉体の触媒前駆体を得た。転動造粒装置に平均粒径4.5mmのシリカ-アルミナ球形担体500部を投入し、次いで結合剤として15質量%の硝酸アンモニウム水溶液と共に触媒前駆体を投入して担体に担持させた後、空気雰囲気下470℃で6時間焼成して触媒1を得た。この触媒1の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒1:Mo12Bi1.2Co6Fe1.2Ni3K0.07
担持率は、下記式により求めた。
担持率(質量%)=(触媒の質量(g)-用いた担体の質量(g))/用いた担体の質量(g)×100
触媒1の触媒活性成分のX線回折測定による2θ=5°以上90°以下の範囲の結晶化度Tは7.1%であり、触媒1の結晶化度割合Rは0.10であった。
全長3000mm、内径25mmのSUS製反応管、およびこれを覆う熱媒体を流すためのシェルからなる反応器を鉛直方向に用意した。反応管上部より得られた触媒1を落下させて、層長が2900mmとなるように充填した。熱媒体温度(反応温度)を310℃に保ち、触媒を充填した反応管下部より、プロピレン6容量%、酸素11容量%、水蒸気15容量%、残部が窒素等の不活性ガスからなる混合ガスを、空間速度1650hr-1(STP)で導入し、プロピレン酸化反応を行った。プロピレン転化率およびアクロレイン+アクリル酸収率の結果を表1に示す。また、反応温度を適宜変更しながら4000時間反応を継続した結果も表1に示す。実験例1では、初期の収率が92.8mol%と高い値を示し、4000時間経過後も収率の低下はわずか0.2mol%に抑えられた。実験例1では、長期間にわたり安定して高収率でアクロレインとアクリル酸を製造できた。
実験例1において、A液およびB液の保持温度を70℃に変更したこと、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ500部、0部に変更したこと、B液を2つに分けなかったこと、A液にB液を添加する際10秒以内に添加したこと以外は、実験例1と同様に調製し、触媒2を得た。この触媒2の担持率は100質量%であり、酸素を除く金属元素組成は実験例1と同じであった。触媒2の結晶化度Tは18.9%であり、結晶化度割合Rは0.02であった。
実験例1において、A液およびB液の保持温度を70℃に変更したこと、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ500部、0部に、硝酸ビスマスの量を206部に、硝酸コバルトの量を481部に、硝酸鉄の量を191部に、硝酸ニッケルの量を103部に変更したこと、A液にB液-1およびB液-2をそれぞれ添加する際の時間を1分に変更したこと以外は、実験例1と同様に調製し、触媒3を得た。この触媒3の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒3:Mo12Bi1.8Co7Fe2Ni1.5K0.07
触媒3の結晶化度Tは14.3%であり、結晶化度割合Rは0.06であった。
実験例1において、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ100部、400部に、硝酸ビスマスの量を172部に、硝酸コバルトの量を343部に、硝酸ニッケルの量を137部に、硝酸カリウムの量を1.2部に変更したこと、B液を2つに分けなかったこと、A液にB液を添加する際の時間を12分に変更したこと、転動造粒装置に投入するシリカ-アルミナ球形担体の量を450部に変更したこと以外は、実験例1と同様に調製し、触媒4を得た。この触媒4の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒4:Mo12Bi1.5Co5Fe1.2Ni2K0.05
触媒4の結晶化度Tは4.5%であり、結晶化度割合Rは0.21であった。
実験例4において、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ0部、500部に変更したこと、A液にB液を添加する際の時間を20分に変更したこと以外は、実験例4と同様に調製し、触媒5を得た。この触媒5の担持率は100質量%であり、酸素を除く金属元素組成は実験例4と同じであった。触媒5の結晶化度Tは3.4%であり、結晶化度割合Rは0.22であった。
実験例3において、硝酸ビスマスの量を183部に、硝酸鉄の量を114部に変更したこと、A液にB液-1およびB液-2をそれぞれ添加する際10秒以内に添加したこと以外は、実験例3と同様に調製し、触媒6を得た。この触媒6の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒6:Mo12Bi1.6Co7Fe1.2Ni1.5K0.07
触媒6の結晶化度Tは17.1%であり、結晶化度割合Rは0.02であった。
実験例6において、A液およびB液の保持温度を50℃に変更したこと、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ0部、500部に変更したこと、B液を2つに分けなかったこと以外は、実験例6と同様に調製し、触媒7を得た。この触媒7の担持率は100質量%であり、酸素を除く金属元素組成は実験例6と同様であった。触媒7の結晶化度Tは3.4%であり、結晶化度割合Rは0.01であった。
実験例4において、A液およびB液の保持温度を70℃に変更したこと、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ400部、100部に、硝酸ビスマスの量を145部に、硝酸鉄の量を95.4部に変更し、硝酸ニッケルを添加しなかったこと、A液にB液を添加する際の時間を30秒に変更したこと、転動造粒装置に投入するシリカ-アルミナ球形担体の量を430部に変更したこと以外は、実験例4と同様に調製し、触媒8を得た。この触媒8の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒8:Mo12Bi1.3Co5Fe1K0.05
触媒8の結晶化度Tは9.7%であり、結晶化度割合Rは0.04であった。
実験例1において、A液およびB液の保持温度を70℃に変更したこと、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ350部、150部に、硝酸ビスマスの量を229部に、硝酸コバルトの量を481部に、硝酸鉄の量を143部に変更し、硝酸ニッケルを添加しなかったこと、A液にB液-1およびB液-2をそれぞれ添加する際の時間を1分に変更したこと以外は、実験例1と同様に調製し、触媒9を得た。この触媒9の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒9:Mo12Bi2Co7Fe1.5K0.07
触媒9の結晶化度Tは7.9%であり、結晶化度割合Rは0.12であった。
実験例1において、A液および懸濁液に添加するパラモリブデン酸アンモニウムの量をそれぞれ0部、500部に、硝酸ビスマスの量を80.1部に、硝酸コバルトの量を378部に、硝酸鉄の量を143部に、硝酸カリウムの量を1.2部に変更し、硝酸ニッケルを添加しなかったこと、A液にB液-1およびB液-2をそれぞれ添加する際の時間を4分に変更したこと、転動造粒装置に投入するシリカ-アルミナ球形担体の量を430部に変更したこと以外は、実験例1と同様に調製し、触媒10を得た。この触媒10の担持率は100質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒10:Mo12Bi0.7Co5.5Fe1.5K0.05
触媒10の結晶化度Tは5.9%であり、結晶化度割合Rは0.14であった。
実験例6において、硝酸ビスマスの量を229部に、硝酸コバルトの量を412部に、硝酸鉄の量を172部に、硝酸ニッケルの量を137部に変更したこと、A液にB液-1およびB液-2をそれぞれ添加する際の時間を30秒に変更したこと以外は、実験例6と同様に調製し、触媒11を得た。この触媒11の担持率は104質量%であり、酸素を除く金属元素組成は次のとおりであった。
触媒11:Mo12Bi2Co6Fe1.8Ni2K0.07
触媒11の結晶化度Tは16.2%であり、結晶化度割合Rは0.03であった。
(12-1)触媒の調製
実験例1において用いたシリカ-アルミナ球状担体の平均粒径を6.5mmのものに変更した以外は、実験例1と同様に調製し、触媒12を得た。この触媒12の担持率は100質量%であり、酸素を除く金属元素組成、結晶化度Tおよび結晶化度割合Rは触媒1と同じであった。
全長3000mm、内径25mmのSUS製反応管、およびこれを覆う熱媒体を流すためのシェルからなる反応器を鉛直方向に用意した。反応管上部より触媒12、触媒3を順次落下させて、それぞれ触媒12の層長が800mm、触媒3の層長が2100mmとなるように充填した。
実験例3において用いたシリカ-アルミナ球状担体の平均粒径を6.5mmのものに変更した以外は、実験例3と同様に調製し、触媒13を得た。この触媒13の担持率は100質量%であり、酸素を除く金属元素組成、結晶化度Tおよび結晶化度割合Rは触媒3と同じであった。
実験例2において用いたシリカ-アルミナ球状担体の平均粒径を6.5mmのものに変更した以外は、実験例2と同様に調製し、触媒14を得た。この触媒14の担持率は100質量%であり、酸素を除く金属元素組成、結晶化度Tおよび結晶化度割合Rは触媒2と同じであった。
実験例5において用いたシリカ-アルミナ球状担体の平均粒径を6.5mmのものに変更した以外は、実験例5と同様に調製し、触媒15を得た。この触媒15の担持率は100質量%であり、酸素を除く金属元素組成、結晶化度Tおよび結晶化度割合Rは触媒5と同じであった。
Claims (7)
- プロピレンを分子状酸素含有ガスにより接触気相酸化してアクロレインおよび/またはアクリル酸を製造するための触媒であって、
モリブデン、ビスマス、およびコバルトを必須成分として含む触媒活性成分を含有し、
触媒活性成分のCu-Kα線を用いたX線回折分析によって測定される2θ=5°以上90°以下の範囲の結晶化度Tが4%以上18%以下の範囲であることを特徴とするアクロレインおよび/またはアクリル酸製造用の触媒。 - 下記式(1)で表される触媒の結晶化度割合Rが0.03以上0.20以下の範囲であることを特徴とするアクロレインおよび/またはアクリル酸製造用の触媒。
R=M/T (1)
(Mは、触媒活性成分のCu-Kα線を用いたX線回折分析によって測定される2θ=26.5±0.5°におけるピークの結晶化度を表す。) - 前記触媒は、さらに、前記触媒活性成分を担持するための不活性担体を有する請求項1または2に記載のアクロレインおよび/またはアクリル酸製造用の触媒。
- プロピレンを分子状酸素含有ガスにより接触気相酸化してアクロレインおよび/またはアクリル酸を製造する方法であって、
請求項1~3のいずれか1項に記載の触媒の存在下に接触気相酸化を行う工程を有することを特徴とするアクロレインおよび/またはアクリル酸の製造方法。 - 前記触媒が充填された反応管を有する固定床反応器を用いる請求項4に記載のアクロレインおよび/またはアクリル酸の製造方法。
- 前記反応管は、管軸方向に分割された複数個の反応帯を有し、
各反応帯は、前記結晶化度割合Rが互いに異なる触媒が充填されている請求項5に記載のアクロレインおよび/またはアクリル酸の製造方法。 - 前記複数個の反応帯の結晶化度割合Rは、プロピレンと分子状酸素含有ガスとを含む原料ガスの入口側から出口側に向かって順次小さくなる請求項6に記載のアクロレインおよび/またはアクリル酸の製造方法。
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- 2009-09-25 EP EP09817710.8A patent/EP2329880B1/en active Active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021141133A1 (ja) | 2020-01-10 | 2021-07-15 | 日本化薬株式会社 | 触媒、触媒の充填方法、および触媒を用いた化合物の製造方法 |
WO2021141134A1 (ja) | 2020-01-10 | 2021-07-15 | 日本化薬株式会社 | 触媒、それを用いた化合物の製造方法及び化合物 |
Also Published As
Publication number | Publication date |
---|---|
EP2329880B1 (en) | 2016-08-31 |
JPWO2010038677A1 (ja) | 2012-03-01 |
US20110112325A1 (en) | 2011-05-12 |
CN102076411B (zh) | 2013-02-13 |
EP2329880A1 (en) | 2011-06-08 |
CN102076411A (zh) | 2011-05-25 |
JP5420556B2 (ja) | 2014-02-19 |
EP2329880A4 (en) | 2013-08-14 |
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