TWI645902B - 不飽和醛之氣相接觸氧化反應用觸媒,丙烯酸之製造方法及該觸媒之製造方法 - Google Patents
不飽和醛之氣相接觸氧化反應用觸媒,丙烯酸之製造方法及該觸媒之製造方法 Download PDFInfo
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- TWI645902B TWI645902B TW106124899A TW106124899A TWI645902B TW I645902 B TWI645902 B TW I645902B TW 106124899 A TW106124899 A TW 106124899A TW 106124899 A TW106124899 A TW 106124899A TW I645902 B TWI645902 B TW I645902B
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- Prior art keywords
- catalyst
- gas
- contact oxidation
- oxidation reaction
- unsaturated
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 239000012808 vapor phase Substances 0.000 title 1
- 239000007789 gas Substances 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 62
- 150000001299 aldehydes Chemical class 0.000 claims description 36
- 230000002093 peripheral effect Effects 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000012071 phase Substances 0.000 description 20
- 239000002002 slurry Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- -1 acryl Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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 compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- 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
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- 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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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/41—Silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/53—Antimony
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/847—Nickel
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Abstract
本發明之目的在於提供一種觸媒,其於使用觸媒使不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時,可將壓力損失抑制得較低,能夠以高選擇率製造不飽和羧酸。本發明係關於一種觸媒,其係用於使不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之環形或圓柱形之觸媒,且外周緣部相對於中心線傾斜。
Description
本發明係關於一種觸媒。詳細而言,係關於一種用於使不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之觸媒。
習知,關於用於使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之觸媒之形狀,有各種提案。
例如,專利文獻1中,作為用以將(甲基)丙烯醛選擇性氧化為(甲基)丙烯酸之觸媒,記載有成形為中空圓筒體狀且該中空圓筒體狀之端面彎曲之非均相系觸媒反應用之成形觸媒。又,專利文獻2中,記載有用以使丙烯、異丁烯、第三丁醇或甲基第三丁醚氣相接觸氧化而製造對應之不飽和醛及不飽和羧酸之觸媒,其係將觸媒粉體塗覆於惰性載體而成之擔載觸媒,其特徵在於:該惰性載體具有環形,且外周緣部朝載體之長度方向彎曲。
又,專利文獻3中,記載有環狀載體之兩正面被自內向外傾斜地倒角,而圓筒外壁之長度與圓筒內壁之長度相比至少短20%之含有釩及鈦及/或鋯之用以製造鄰苯二甲酸酐之擔載觸媒。進而,專利文獻4中,記載有包含外周緣部相對於中心線傾斜60°左右之中空圓筒之非多孔質之支持體的用於甲醇向甲醛之氧化的被
覆觸媒。
專利文獻1:日本專利特開昭61-141933號公報
專利文獻2:國際公開第2009/147965號
專利文獻3:日本專利特開昭55-139834號公報
專利文獻4:美國專利申請公開第2010/0016640號說明書
然而,專利文獻1及專利文獻2中所記載之觸媒存在以下問題:於利用填充有該觸媒之反應器使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時,壓力損失較高,不飽和醛之轉化率較低,對應之不飽和羧酸之選擇率亦較低,結果產率降低。例如,環形之觸媒存在未均勻地填充至反應器之情形,有反應場於反應器內變得不均勻,導致轉化率、選擇率降低之可能性。又,中空圓筒體狀之端面彎曲之觸媒由於相對於觸媒體積之觸媒表面積較小,反應活性點較少,故而有反應之效率較低,轉化率、選擇率降低之情形。
又,於製造屬於不飽和羧酸之丙烯酸時,碳化物會附著於觸媒表面。於多管式反應器之壓力損失較高之反應管中,因氣體量減少而容易發生該碳化物向觸媒表面之附著(結焦)。一旦發生結焦,則壓力損失會變得更高,故而會產生碳化物向觸媒表面之附著進一步加速之不良循環,最終可能陷入不得不使反應停止之狀
況。
本發明係為了解決上述問題而成者。即,本發明之目的在於提供一種觸媒,其於使用觸媒使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時,可降低壓力損失而將氣體量保持為較高,藉此可抑制結焦,不飽和醛之轉化率較高,能夠以高選擇率製造對應之不飽和羧酸。
本發明者等人為了解決上述課題而反覆進行銳意研究,結果發現:藉由將用於使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之環形或圓柱形之觸媒設為外周緣部相對於中心線傾斜之觸媒,可將壓力損失抑制得較低,不飽和醛之轉化率較高,能夠以高選擇率製造不飽和羧酸,從而完成本發明。
即,本發明為以下內容。
[1]一種觸媒,其係用於使不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之環形或圓柱形之觸媒,且外周緣部相對於中心線傾斜。
[2]如[1]所記載之觸媒,其中,上述外周緣部係觸媒之兩端面。
[3]如[1]或[2]所記載之觸媒,其中,上述外周緣部相對於上述中心線傾斜之角度為45°~85°。
[4]如[1]至[3]中任一項所記載之觸媒,其中,外徑a(mm)相對於底邊部直徑b(mm)之比(a/b)為2.3以上,直體部長度H(mm)相對於底邊部直徑b(mm)之比(H/b)為1.35以上且2.5以下,直體部長度H(mm)為2mm~11mm,且外徑a(mm)為2mm~11mm。
[5]如[4]所記載之觸媒,其中,上述外徑a(mm)相對於上述直體部長度H(mm)之比(a/H)為1.47以上。
[6]一種丙烯酸之製造方法,其係使用[1]至[5]中任一項所記載之觸媒使丙烯醛與含氧氣體以氣相進行接觸氧化。
[7]一種觸媒之製造方法,其係[1]至[5]中任一項所記載之觸媒之製造方法,其包括打錠成形。
根據本發明之觸媒,於利用填充有該觸媒之反應器自丙烯醛等不飽和醛製造丙烯酸等不飽和羧酸之情形時,可降低壓力損失而將氣體量保持得較高。藉此,可抑制結焦,能夠以高轉化率將丙烯醛等不飽和醛氧化,從而以高選擇率製造丙烯酸等不飽和羧酸。
又,已發生結焦之觸媒可藉由使含氧氣體流通而再生(除焦)。但是,藉由如本發明般將環形或圓柱形之觸媒設為外周緣部相對於中心線傾斜之觸媒,而即便為已結焦之狀態,與習知之形狀之觸媒相比,亦可保持降低壓力損失之效果,可實現利用該特定組成之氣體進行之高效率之除焦。
1‧‧‧外周緣部
2‧‧‧中心線
3‧‧‧傾斜之角度
4‧‧‧底邊部直徑
5‧‧‧外徑
6‧‧‧直體部長度
圖1係本發明之環形之觸媒之橫截面圖。
圖2係本發明之環形之觸媒之另一橫截面圖。
圖3係表示本發明之環形之觸媒之一例之橫截面圖。
圖4係習知之觸媒之橫截面圖。
以下,對本發明詳細地進行說明。再者,鉬(Mo)、釩(V)、鈮(Nb)、鎢(W)、銅(Cu)、鎂(Mg)、鈣(Ca)、鍶(Sr)、鋇(Ba)、鋅(Zn)、銻(Sb)、鐵(Fe)、鈷(Co)、鎳(Ni)、鉍(Bi)、矽(Si)各元素係分別使用括號內之元素符號進行記載。
本發明之觸媒為環形或圓柱形,外周緣部相對於中心線傾斜。藉由外周緣部相對於中心線傾斜,而於將該觸媒填充至反應器中而自丙烯醛等不飽和醛製造丙烯酸等不飽和羧酸之情形時,可降低壓力損失,提高丙烯醛等不飽和醛之轉化率,以高選擇率製造丙烯酸等不飽和羧酸。再者,於在相同之體積下比較環形之外周緣部相對於中心線傾斜之觸媒與圓柱形之外周緣部相對於中心線傾斜之觸媒之情形時,就使不飽和醛與含氧氣體以氣相進行接觸氧化之觸媒表面之面積較大方面而言,較佳為環形之外周緣部相對於中心線傾斜之觸媒。
本發明之觸媒之外周緣部相對於中心線傾斜,該外周緣部較佳為觸媒之兩端面。藉由為觸媒之兩端面,而觸媒粒子之流動性變得良好,於使用漏斗等向反應器填充觸媒時,於漏斗內觸媒之架橋得到抑制,觸媒被均勻地填充至反應管內,藉此可縮短填充時間,進而,於填充至反應器後,可降低使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時之壓力損失。又,可提高不飽和醛之轉化率,以高選擇率製造對應之不飽和羧酸。
上述外周緣部相對於上述中心線傾斜之角度較佳為45°~85°,更佳為55°~80°,進而較佳為65°~75°。藉由將該角度設為上述範圍,而於填充至反應器後,可降低使丙烯醛等不飽和醛 與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時之壓力損失。又,可提高不飽和醛之轉化率,以高選擇率製造對應之不飽和羧酸。再者,所謂該外周緣部相對於該中心線傾斜之角度,可於下文進行說明。無論觸媒為環形或圓柱形,中心線均與直體部之長度方向平行。即,所謂該外周緣部相對於中心線傾斜之角度,係指該外周緣部相對於直體部之長度方向傾斜之角度。
本發明之觸媒較佳為外徑a(mm)相對於底邊部直徑b(mm)之比(a/b)為2.3以上,直體部長度H(mm)相對於底邊部直徑b(mm)之比(H/b)為1.35以上且2.5以下,直體部長度H(mm)為2mm~11mm,且外徑a(mm)為2mm~11mm。藉由為上述範圍,而可抑制向反應器填充時之觸媒之破裂,於使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時,可降低壓力損失。又,可提高不飽和醛之轉化率,以高選擇率製造對應之不飽和羧酸。
a/b更佳為2.35以上,進而較佳為2.4以上,尤佳為2.45以上。上限並無特別限定,就觸媒強度之觀點而言,較佳為3.5。
H/b更佳為1.4以上且2.5以下,進而較佳為1.45以上且2.5以下,尤佳為1.5以上且2.5以下。H更佳為2mm~10mm,進而較佳為2.3mm~9mm,尤佳為2.6mm~7mm,最佳為3mm~5mm。a更佳為2mm~10mm,進而較佳為3mm~9mm,尤佳為4mm~7mm,最佳為4mm~5.6mm。
進而,外徑a(mm)相對於直體部長度H(mm)之比(a/H)較佳為1.47以上,更佳為1.50以上,進而較佳為1.53以上,尤佳為1.56以上。上限並無特別限定,較佳為2.5。藉由為上述範圍內, 而於使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸之情形時,可降低壓力損失。又,可提高不飽和醛之轉化率,以高選擇率製造對應之不飽和羧酸。
利用本發明之環形之觸媒之橫截面圖(圖1、圖2)對底邊部直徑、外徑、直體部長度進行說明。本發明之觸媒係外周緣部相對於中心線傾斜之觸媒,該傾斜到達環之空體部之觸媒為圖1所示之觸媒,該傾斜未到達空體部之觸媒為圖2所示之觸媒。所謂直體部長度,係指直體部之除傾斜部分以外之長度(參照圖1、圖2)。所謂外徑,係指直體部之直徑(參照圖1、圖2)。所謂底邊部直徑,無論是該傾斜到達環之空體部之情形(參照圖1)或該傾斜未到達環之空體部之情形(參照圖2),均指傾斜結束之底邊部之直徑(參照圖1、圖2)。
作為本發明中之環形之觸媒,圖1之觸媒與圖2相比,相對於觸媒體積之觸媒表面積較大,可提高不飽和醛之轉化率,以高選擇率製造對應之不飽和羧酸,就該方面而言,較佳為傾斜到達空體部之觸媒。又,於圓柱形之觸媒之情形時,由於無空體部,故而若將圖1與圖2變換為圓柱形之觸媒之圖,則成為相同之圖。再者,圖1及圖2之例中之本發明之觸媒於橫截面圖中相對於中心線傾斜之外周緣部為直線狀。
本發明之觸媒係用於使丙烯醛等不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之觸媒,較佳為至少包含鉬及釩之觸媒。若為包含該2種成分之觸媒,則可用於本發明之觸媒,尤其,可較佳地應用下述通式(1)所表示之觸媒。
MoaVbCucSbdSieXfYgZhOi (1)
(式中,X係自Nb及W所組成之群選擇之至少1種元素,Y係自Mg、Ca、Sr、Ba及Zn所組成之群選擇之至少1種元素,Z係自Fe、Co、Ni及Bi所組成之群選擇之至少1種元素;又,a~h表示各元素之原子數之比,a=12時,為0<b≦12、0<c≦12、0≦d≦500、0≦e≦500、0≦f≦12、0≦g≦8、0≦h≦500之範圍,又,i為滿足其他元素之氧化狀態之數值)。
本發明之觸媒係例如以如下方式進行製造。使視所製造之組成而必需之所需量之含有上述觸媒之各元素成分之原料化合物適當地溶解或分散於水性介質中,藉此製造包含觸媒成分之混合溶液或其水性漿體。各觸媒成分之原料係使用包含各元素之硝酸鹽、銨鹽、氫氧化物、氧化物、硫酸鹽、碳酸鹽、鹵化物、乙酸鹽等。例如,作為鉬,係使用仲鉬酸銨、三氧化鉬、氯化鉬等。作為釩,係使用釩酸銨、五氧化釩、草酸釩、硫酸釩等。
為了防止各成分之不均勻,較佳為將上述包含觸媒成分之混合溶液或水性漿體充分地攪拌、混合。繼而,將包含觸媒成分之混合溶液或水性漿體進行乾燥而製成粉體,該乾燥可藉由各種方法實施。例如,可列舉利用通常之噴霧乾燥機、漿體乾燥機、轉筒乾燥機等進行之乾燥,尤佳為利用噴霧乾燥機進行之乾燥。
繼而,使藉由上述乾燥而獲得之粉體成形為環形或圓柱形。成形為環形或圓柱形之方法未必受限制,可較佳係可列舉打錠成形、擠出成形等。尤其,由於容易控制外周緣部之傾斜程度,故而較佳為打錠成形。於成形時,亦可使用成形助劑。較佳之成形助劑為二氧化矽、石墨、晶質纖維素、纖維素、澱粉、聚乙烯醇、硬脂酸或硬脂酸鹽。成形助劑相對於粉體100重量份通常可使用0.1 重量份~50重量份左右。又,視需要亦可使用陶瓷纖維、鬚晶等無機纖維作為觸媒之機械強度提高材料。該等纖維之使用量相對於粉體100重量份通常為1重量份~30重量份。
以下,列舉實施例更加具體地說明本發明,但本發明只要不超出其主旨,則不受以下實施例任何限定。
以如下方式製造氧以外之構成成分為表1所示之組成之觸媒。再者,所使用之各供給源化合物之量係表1所示之量。使鹼性碳酸鎳分散於純水350ml中,向其中添加二氧化矽及三氧化銻並充分地進行攪拌,獲得漿狀液。對該漿狀液進行加熱而進行濃縮、乾燥。利用蒙烰爐將所獲得之乾燥固體於800℃下焙燒3小時,將生成固體進行粉碎而獲得通過60目篩網之粉體。(Sb-Ni-Si-O粉末)。
另一方面,將純水加熱至80℃,一面攪拌一面依次使仲鉬酸銨、偏釩酸銨溶解。向其中添加使硫酸銅溶解於純水100ml而成之硫酸銅水溶液,進而添加氫氧化鈮並進行攪拌,獲得漿體液。
向該漿體液中一面攪拌一面緩慢地添加上述Sb-Ni-Si-O粉末並充分地進行攪拌混合,獲得漿狀液。於150℃下對該漿狀液進行噴霧乾燥而獲得前驅化合物。向其中添加混合1.5重量%之石墨,利用小型打錠成形機成形為密度2.93g/cm3之環形。將所獲得之成形體於1%氧氣流中且380℃下進行焙燒,製造觸 媒。環形之觸媒係如圖3之橫截面圖所示,為外徑:5mm、底邊部直徑:2mm、直體部長度:3mm,外周緣部與兩端面一併相對於中心線傾斜,相對於中心線傾斜之角度均為72°。又,藉由下述方法測定觸媒之壓力損失。將結果示於表2。
使內徑26mm、長度1000mm之丙烯酸系樹脂製直管直立,填充上述環形之觸媒至900mm之高度,於室溫下自安裝於該丙烯酸系樹脂製直管之上部之內徑6mm之不鏽鋼(SUS,Steel Use Stainless)製配管使乾燥空氣以50NL/分鐘之流量流通,利用安裝於自SUS製配管分支之配管之數位差壓計testo 506-3測定差壓(差壓A)。繼而,將該環形之觸媒粒子自丙烯酸系樹脂製直管抽出而設為空筒,以相同之方式測定差壓,設為空白值。壓力損失係以(差壓A)-空白值之形式求出。
繼而,使用上述觸媒,一面維持下述條件一面進行丙烯醛之氣相接觸氧化反應。丙烯醛轉化率、丙烯酸選擇率、丙烯酸產率係以下述式(1)~(3)之方式定義。
(1)丙烯醛轉化率(莫耳%)=100×(反應之丙烯醛之莫耳數)/(供給之丙烯醛之莫耳數)
(2)丙烯酸選擇率(莫耳%)=100×(生成之丙烯酸莫耳數)/(轉化之丙烯醛之莫耳數)
(3)丙烯酸產率(莫耳%)=100×(生成之丙烯酸莫耳數)/(供給之 丙烯醛之莫耳數)
向裝有硝石之附有套管之反應管(內徑21mm)中填充上述觸媒33ml,對反應管進行加熱,導入組成氣體(丙烯醛6體積%、氧氣8體積%、蒸汽22體積%、氮氣64體積%),將空間速度(SV,Space Velocity;每單位時間之原料氣體之流量/所填充之觸媒之視體積)設為1550/hr而實施丙烯醛之氣相接觸氧化反應。將結果彙總於表3。
上述所謂硝石,係包含鹼金屬之硝酸鹽之熱介質,該熱介質於200℃以上熔融,可於高達400℃下使用且除熱效率良好,故而適合發熱量較大之氧化反應。
環形之觸媒係外徑:5mm、底邊部直徑:2mm、直體部長度:2mm,除此以外,以與實施例1相同之方式獲得觸媒。又,藉由與實施例1相同之方法測定壓力損失。將結果示於表2。繼而,以與實施例1相同之方式實施丙烯醛之氣相接觸氧化反應。將結果彙總於表3。
環形之觸媒係外徑:5mm、底邊部直徑:2mm、直體部長度:5.1mm,除此以外,以與實施例1相同之方式獲得觸媒。又,藉由與實施例1相同之方法測定壓力損失。將結果示於表2。繼而,以與實施例1相同之方式實施丙烯醛之氣相接觸氧化反應。將結果彙總於表3。
環形之觸媒係外徑:5mm、底邊部直徑:2mm、直體部長度:3mm,外周緣部與兩端部一併相對於中心線不傾斜,除此以外,以與實施例1相同之方式獲得觸媒。又,藉由與實施例1相同之方法測定壓力損失。將結果示於表2。繼而,以與實施例1相同之方式實施丙烯醛之氣相接觸氧化反應。將結果彙總於表3。
本發明之觸媒係如上述所示般,於利用填充有該觸媒之反應器使作為不飽和醛之丙烯醛進行氣相接觸氧化反應而製造屬於對應之不飽和羧酸之丙烯酸之情形時,可將壓力損失抑制得較低,且不使溫度上升地以高轉化率將丙烯醛氧化,能夠以高選擇率製造丙烯酸。再者,實施例1至3中之壓力損失藉由簡單地使乾燥空氣流通而測定,顯示出相對於習知技術之優勢,且可知,即便於使包含丙烯醛等不飽和醛與含氧氣體之原料混合氣體流通之情形時,亦可保持本發明之優勢。
已詳細地且參照特定之實施態樣對本發明進行了說明,但熟悉本技藝者知悉可於不脫離本發明之精神與範圍之情況下加以各種變更或修正。本申請係基於2017年5月17日提出申請之日本專利申請案(日本專利特願2017-098451)、2017年5月17日提出申請之日本專利申請案(日本專利特願2017-098452)、2017年4月27日提出申請之日本專利申請案(日本專利特願2017-088647)及2016年7月25日提出申請之日本專利申請案(日本專利特願2016-145419),並將其內容以參照之形式引入本文中。
Claims (8)
- 一種不飽和醛之氣相接觸氧化反應用觸媒,其係用於使不飽和醛與含氧氣體以氣相進行接觸氧化而製造對應之不飽和羧酸時之環形或圓柱形之觸媒;該觸媒係如下述通式(1)所表示:MoaVbCucSbdSieXfYgZhOi (1)(式中,X係自Nb及W所組成之群選擇之至少1種元素,Y係自Mg、Ca、Sr、Ba及Zn所組成之群選擇之至少1種元素,Z係自Fe、Co、Ni及Bi所組成之群選擇之至少1種元素;又,a~h表示各元素之原子數之比,a=12時,為0<b≦12、0<c≦12、0≦d≦500、0≦e≦500、0≦f≦12、0≦g≦8、0≦h≦500之範圍,又,i為滿足其他元素之氧化狀態之數值);且外周緣部相對於中心線傾斜。
- 如請求項1之不飽和醛之氣相接觸氧化反應用觸媒,其中,上述外周緣部為觸媒之兩端面。
- 如請求項1或2之不飽和醛之氣相接觸氧化反應用觸媒,其中,上述外周緣部相對於上述中心線傾斜之角度為45°~85°。
- 如請求項1或2之不飽和醛之氣相接觸氧化反應用觸媒,其中,外徑a(mm)相對於底邊部直徑b(mm)之比(a/b)為2.3以上,直體部長度H(mm)相對於底邊部直徑b(mm)之比(H/b)為1.35以上且2.5以下,直體部長度H(mm)為2mm~11mm,且外徑a(mm)為2mm~11mm。
- 如請求項3項之不飽和醛之氣相接觸氧化反應用觸媒,其中,外徑a(mm)相對於底邊部直徑b(mm)之比(a/b)為2.3以上,直體部長度H(mm)相對於底邊部直徑b(mm)之比(H/b)為1.35以上且2.5以下,直體部長度H(mm)為2mm~11mm,且外徑a(mm)為2mm~11mm。
- 如請求項4之不飽和醛之氣相接觸氧化反應用觸媒,其中,上述外徑a(mm)相對於上述直體部長度H(mm)之比(a/H)為1.47以上。
- 如請求項5之不飽和醛之氣相接觸氧化反應用觸媒,其中,上述外徑a(mm)相對於上述直體部長度H(mm)之比(a/H)為1.47以上。
- 一種丙烯酸之製造方法,其係使用請求項1至7中任一項之不飽和醛之氣相接觸氧化反應用觸媒,使丙烯醛與含氧氣體以氣相進行接觸氧化。
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