JP2011026284A - Method for producing (meth)acrolein or (meth)acrylic acid - Google Patents
Method for producing (meth)acrolein or (meth)acrylic acid Download PDFInfo
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- JP2011026284A JP2011026284A JP2009176614A JP2009176614A JP2011026284A JP 2011026284 A JP2011026284 A JP 2011026284A JP 2009176614 A JP2009176614 A JP 2009176614A JP 2009176614 A JP2009176614 A JP 2009176614A JP 2011026284 A JP2011026284 A JP 2011026284A
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 199
- 239000002994 raw material Substances 0.000 claims abstract description 118
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000007789 gas Substances 0.000 claims abstract description 74
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000001301 oxygen Substances 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 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BOCQEKBKBUOBCR-UHFFFAOYSA-N 4-(2-methyliminohydrazinyl)benzoic acid Chemical compound CN=NNC1=CC=C(C(O)=O)C=C1 BOCQEKBKBUOBCR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000009828 non-uniform distribution Methods 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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 group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Chemical group 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 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 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 description 1
- 238000000691 measurement method Methods 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [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
- 239000011135 tin Substances 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
- 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
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
【課題】気相接触酸化反応をスタートアップする際のホットスポットの温度を十分に抑制し、短時間でスタートアップを行うことができる（メタ）アクロレインまたは（メタ）アクリル酸の製造方法の提供。
【解決手段】触媒が充填された反応管を備えた反応器を用い、プロピレン、イソブチレン、ＴＢＡおよびＭＴＢＥからなる群より選ばれた少なくとも１種を反応原料として含む原料ガスを反応管に供給し、酸素含有ガスとの気相接触酸化反応を行うに際して、下記条件(1)、(2)を満たすように反応原料の供給量を段階的に増やして定常運転に移行させる。反応原料の供給量が、(1)定常運転時における供給量の10〜60%のときに、プロピレンおよび／またはイソブチレンの平均転化率が100〜98%であり、(2)定常運転時における供給量の90〜100%のときに、プロピレンおよび／またはイソブチレンの平均転化率が97%以下である。
【選択図】なしThe present invention provides a method for producing (meth) acrolein or (meth) acrylic acid capable of sufficiently suppressing the temperature of a hot spot when starting up a gas phase catalytic oxidation reaction and performing startup in a short time.
Using a reactor equipped with a reaction tube filled with a catalyst, a raw material gas containing at least one selected from the group consisting of propylene, isobutylene, TBA and MTBE as a reaction raw material is supplied to the reaction tube, When performing the gas phase catalytic oxidation reaction with the oxygen-containing gas, the supply amount of the reaction raw material is increased stepwise so as to satisfy the following conditions (1) and (2), and the operation is shifted to the steady operation. When the supply amount of the reaction raw material is (1) 10 to 60% of the supply amount in steady operation, the average conversion rate of propylene and / or isobutylene is 100 to 98%, and (2) supply in steady operation When the amount is 90-100%, the average conversion of propylene and / or isobutylene is 97% or less.
[Selection figure] None
Description
本発明は、（メタ）アクロレインまたは（メタ）アクリル酸の製造方法に関する。 The present invention relates to a method for producing (meth) acrolein or (meth) acrylic acid.
（メタ）アクロレインまたは（メタ）アクリル酸は、プロピレン、イソブチレン、第三級ブチルアルコール（ＴＢＡ）、またはメチル第三級ブチルエーテル（ＭＴＢＥ）（以下、これらをまとめて「反応原料」ともいう。）の気相接触酸化反応により製造される。該気相接触酸化反応に使用される触媒について、これまで数多くの提案がなされている。これらの提案は、主として触媒を構成する元素やその比率に関するものであった。 (Meth) acrolein or (meth) acrylic acid is propylene, isobutylene, tertiary butyl alcohol (TBA), or methyl tertiary butyl ether (MTBE) (hereinafter collectively referred to as “reaction raw material”). Produced by gas phase catalytic oxidation reaction. Many proposals have been made so far for the catalyst used in the gas phase catalytic oxidation reaction. These proposals mainly relate to the elements constituting the catalyst and their ratios.
ところで、気相接触酸化反応（以下、単に「酸化反応」という。）は発熱反応であるため、触媒層で蓄熱が起こる。蓄熱の結果生じる局所的高温帯域はホットスポットと呼ばれ、この部分の温度が高すぎると過度の酸化反応を生じるので目的生成物の収率は低下する。このため、酸化反応の工業的実施において、ホットスポットの温度抑制は重大な問題である。特に生産性を上げるために原料ガス中における反応原料の濃度を高める場合や、酸化反応をスタートアップする際に、ホットスポットの温度が高くなる傾向にある。中でもスタートアップ中にホットスポットの温度が過度に上昇すると、触媒の暴走反応が起こる場合があり、反応条件やスタートアップ時間に関して大きな制約を強いられる。
従って、スタートアップ中のホットスポットの温度を抑制することは、工業的に高収率で（メタ）アタクロレインや（メタ）アクリル酸を生産する上で非常に重要である。
By the way, since the gas phase catalytic oxidation reaction (hereinafter simply referred to as “oxidation reaction”) is an exothermic reaction, heat storage occurs in the catalyst layer. The local high temperature zone resulting from the heat storage is called a hot spot, and if the temperature of this part is too high, an excessive oxidation reaction occurs and the yield of the target product is lowered. For this reason, in the industrial implementation of the oxidation reaction, the temperature control of the hot spot is a serious problem. In particular, the temperature of the hot spot tends to increase when the concentration of the reaction raw material in the raw material gas is increased in order to increase productivity or when the oxidation reaction is started up. In particular, if the hot spot temperature rises excessively during start-up, a catalyst runaway reaction may occur, which imposes great restrictions on the reaction conditions and start-up time.
Therefore, suppressing the temperature of the hot spot during start-up is very important in producing (meth) atacrolein and (meth) acrylic acid with high yield on an industrial scale.
スタートアップ中のホットスポットの温度を抑制する方法として、これまでにいくつかの提案がなされている。例えば、特許文献１には、多管式反応器を使用して、プロピレンを気相接触酸化してアクロレインを製造する方法において、反応のスタートアップに際して、反応器への原料の単位時間当たりの供給量が、原料の単位時間当たりの許容最大供給量の３０％以上に達してから、少なくとも２０時間以上原料の単位時間当たりの供給量を許容最大供給量の３０％以上８０％未満に保つ方法が開示されている。 Several proposals have been made so far for suppressing the temperature of the hot spot during startup. For example, in Patent Document 1, in a method for producing acrolein by vapor-phase catalytic oxidation of propylene using a multi-tubular reactor, the supply amount of raw material to the reactor per unit time at the start-up of the reaction However, after reaching 30% or more of the permissible maximum supply amount per unit time of the raw material, a method of keeping the supply amount per unit time of the raw material at 30% or more and less than 80% of the permissible maximum supply amount for at least 20 hours or more is disclosed Has been.
また、特許文献２には、固定酸化触媒が充填された反応器の触媒層に、イソブチレンおよび／またはＴＢＡを４〜９容量％含む原料ガスを流通させる前に、前記触媒層に、酸素、窒素および水蒸気を含み、かつイソブチレンおよびＴＢＡが０〜０．５容量％のガスを流通させながら２５０〜４００℃の範囲まで昇温し、次いでイソブチレンおよび／またはＴＢＡを１〜３．８容量％、酸素を７〜１６容量％および水蒸気を５〜５０容量％含むガスを２５０〜４００℃で１時間以上流通させる方法が開示されている。
Further, in
しかしながら、特許文献１、２に記載された方法では、スタートアップ中のホットスポットの温度を抑制する効果が必ずしも十分ではなく、加えてスタートアップに長時間を費やすことがあった。
However, the methods described in
本発明は上記事情に鑑みてなされたもので、気相接触酸化反応をスタートアップする際のホットスポットの温度を十分に抑制し、短時間でスタートアップを行うことができる（メタ）アクロレインまたは（メタ）アクリル酸の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and (meth) acrolein or (meth) capable of sufficiently suppressing the temperature of a hot spot when starting up a gas phase catalytic oxidation reaction and starting up in a short time. It aims at providing the manufacturing method of acrylic acid.
本発明の（メタ）アクロレインまたは（メタ）アクリル酸の製造方法は、少なくともモリブデンおよびビスマスを触媒成分として含む固体酸化触媒が充填され触媒層が形成された反応管を備えた固定床管型反応器を用い、プロピレン、イソブチレン、第三級ブチルアルコール、およびメチル第三級ブチルエーテルからなる群より選ばれた少なくとも１種を反応原料として含む原料ガスを前記反応管に供給し、酸素含有ガスとの気相接触酸化反応により（メタ）アクロレインまたは（メタ）アクリル酸を製造する方法において、前記原料ガスの供給開始から定常運転に移行するまでの間に、下記条件（１）および（２）を満たすように反応原料の供給量を段階的に増やし、その後、定常運転を行うことを特徴とする。
（１）反応原料の供給量が、定常運転時における供給量の１０〜６０％のときに、プロピレンおよび／またはイソブチレンの平均転化率が１００〜９８％である。
（２）反応原料の供給量が、定常運転時における供給量の９０〜１００％のときに、プロピレンおよび／またはイソブチレンの平均転化率が９７％以下である。
The method for producing (meth) acrolein or (meth) acrylic acid according to the present invention is a fixed bed tubular reactor comprising a reaction tube filled with a solid oxidation catalyst containing at least molybdenum and bismuth as catalyst components to form a catalyst layer. And supplying a raw material gas containing at least one selected from the group consisting of propylene, isobutylene, tertiary butyl alcohol, and methyl tertiary butyl ether as a reaction raw material to the reaction tube. In the method for producing (meth) acrolein or (meth) acrylic acid by the phase contact oxidation reaction, the following conditions (1) and (2) are satisfied between the start of the supply of the raw material gas and the transition to the steady operation. The supply amount of the reaction raw material is increased stepwise, and then steady operation is performed.
(1) When the supply amount of the reaction raw material is 10 to 60% of the supply amount in the steady operation, the average conversion rate of propylene and / or isobutylene is 100 to 98%.
(2) When the supply amount of the reaction raw material is 90 to 100% of the supply amount in the steady operation, the average conversion rate of propylene and / or isobutylene is 97% or less.
また、前記原料ガスの供給開始から定常運転に移行するまでの間に、さらに下記条件（３）を満たすように反応原料の供給量を段階的に増やすことが好ましい。
（３）反応原料の供給量が、定常運転時における供給量の６０％超、９０％未満のときに、プロピレンおよび／またはイソブチレンの平均転化率が９９〜９７％である。
Moreover, it is preferable to increase the supply amount of the reaction raw material stepwise so as to satisfy the following condition (3) between the start of the supply of the raw material gas and the transition to the steady operation.
(3) When the supply amount of the reaction raw material is more than 60% and less than 90% of the supply amount in steady operation, the average conversion rate of propylene and / or isobutylene is 99 to 97%.
さらに、前記原料ガスは酸素含有ガスとして酸素および水蒸気を含み、定常運転時における当該原料ガス中の反応原料の濃度が４〜１０容量％、酸素の濃度が７〜１６容量％、水蒸気の濃度が５〜５０容量％であることが好ましい。
また、前記固定床管型反応器は反応管の外側に熱媒浴を備え、反応管に形成された触媒層と、熱媒浴との温度差（触媒層の温度−熱媒浴の温度）が最大となる位置から、触媒層の原料ガス入口側の端部までの距離が、当該触媒層の全長の０．５倍以下であることが好ましい。
Further, the raw material gas contains oxygen and water vapor as an oxygen-containing gas, the concentration of the reaction raw material in the raw material gas during steady operation is 4 to 10% by volume, the concentration of oxygen is 7 to 16% by volume, and the concentration of water vapor is It is preferably 5 to 50% by volume.
The fixed bed tubular reactor includes a heat medium bath outside the reaction tube, and a temperature difference between the catalyst layer formed in the reaction tube and the heat medium bath (temperature of the catalyst layer−temperature of the heat medium bath). It is preferable that the distance from the position where the maximum is to the end of the catalyst layer on the raw material gas inlet side is 0.5 times or less the total length of the catalyst layer.
本発明の（メタ）アクロレインまたは（メタ）アクリル酸の製造方法によれば、気相接触酸化反応をスタートアップする際のホットスポットの温度を十分に抑制し、短時間でスタートアップを行うことができる。 According to the method for producing (meth) acrolein or (meth) acrylic acid of the present invention, it is possible to sufficiently suppress the temperature of the hot spot when starting up the gas phase catalytic oxidation reaction, and to start up in a short time.
本発明において、（メタ）アクロレインおよび（メタ）アクリル酸を合成する反応は、固定床管型反応器（以下、単に「反応器」という。）を用いて実施される。反応器としては特に限定されないが、工業的には内径１０〜４０ｍｍの反応管を数千〜数万本備えた多管式反応器が好ましい。反応管には、固体酸化触媒が充填され、触媒層が形成される。
また、反応器は、反応管の外側に該反応管を加熱または除熱するための熱媒浴を備えることが好ましい。熱媒としては特に限定されないが、例えば、硝酸カリウムおよび亜硝酸ナトリウムを含む塩溶融物が挙げられる。
なお、本発明において「（メタ）アクロレイン」はメタクロレインとアクロレインの両方を示し、「（メタ）アクリル酸」はメタクリル酸とアクリル酸の両方を示す。
In the present invention, the reaction for synthesizing (meth) acrolein and (meth) acrylic acid is carried out using a fixed bed tubular reactor (hereinafter simply referred to as “reactor”). Although it does not specifically limit as a reactor, Industrially the multitubular reactor provided with several thousand to several tens of thousands of reaction tubes with an internal diameter of 10-40 mm is preferable. The reaction tube is filled with a solid oxidation catalyst to form a catalyst layer.
Moreover, it is preferable that a reactor equips the outer side of a reaction tube with the heat-medium bath for heating or removing this reaction tube. Although it does not specifically limit as a heat medium, For example, the salt melt containing potassium nitrate and sodium nitrite is mentioned.
In the present invention, “(meth) acrolein” indicates both methacrolein and acrolein, and “(meth) acrylic acid” indicates both methacrylic acid and acrylic acid.
本発明に用いる固体酸化触媒（以下、単に「触媒」という。）としては、少なくともモリブデンおよびビスマスを触媒成分として含み、気相接触酸化反応（以下、単に「酸化反応」という。）に用いられる固体触媒であれば特に限定されない。例えば、従来から知られているモリブデンおよびビスマスを含む複合酸化物等を用いることができるが、下記の式（Ｉ）で表される複合酸化物が好ましい。
ＭｏａＢｉｂＦｅｃＡｄＸｅＹｆＺｇＯｈ ・・・（Ｉ）
The solid oxidation catalyst (hereinafter simply referred to as “catalyst”) used in the present invention contains at least molybdenum and bismuth as catalyst components and is used in a gas phase catalytic oxidation reaction (hereinafter simply referred to as “oxidation reaction”). If it is a catalyst, it will not specifically limit. For example, a conventionally known composite oxide containing molybdenum and bismuth can be used, but a composite oxide represented by the following formula (I) is preferable.
Mo a Bi b Fe c A d X e Y f Z g O h ··· (I)
式（Ｉ）において、Ｍｏ、Ｂｉ、ＦｅおよびＯはそれぞれモリブデン、ビスマス、鉄および酸素を表し、Ａはニッケルおよび／またはコバルト、Ｘはマグネシウム、亜鉛、クロム、マンガン、スズおよび鉛からなる群より選ばれる少なくとも１種の元素、Ｙはリン、ホウ素、イオウ、テルル、ケイ素、ゲルマニウム、セリウム、ニオブ、チタン、ジルコニウム、タングステンおよびアンチモンからなる群より選ばれる少なくとも１種の元素、Ｚはカリウム、ナトリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれる少なくとも１種の元素を表す。
ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇおよびｈは各元素の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦５、０．１≦ｃ≦５、１≦ｄ≦１２、０≦ｅ≦１０、０≦ｆ≦１０、０．０１≦ｇ≦３であり、ｈは前記各元素の原子価を満足するのに必要な酸素の原子比である。特に好ましい各元素の原子比は、ａ＝１２のとき、０．２≦ｂ≦３、０．５≦ｃ≦４、２≦ｄ≦１０、０．１≦ｇ≦２である。
In the formula (I), Mo, Bi, Fe and O represent molybdenum, bismuth, iron and oxygen, respectively, A is nickel and / or cobalt, X is magnesium, zinc, chromium, manganese, tin and lead. At least one element selected, Y is at least one element selected from the group consisting of phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium, niobium, titanium, zirconium, tungsten and antimony, Z is potassium, sodium And at least one element selected from the group consisting of rubidium, cesium and thallium.
However, a, b, c, d, e, f, g, and h represent the atomic ratio of each element. When a = 12, 0.1 ≦ b ≦ 5, 0.1 ≦ c ≦ 5, 1 ≦ d ≦ 12, 0 ≦ e ≦ 10, 0 ≦ f ≦ 10, 0.01 ≦ g ≦ 3, and h is an atomic ratio of oxygen necessary to satisfy the valence of each element. Particularly preferable atomic ratios of each element are 0.2 ≦ b ≦ 3, 0.5 ≦ c ≦ 4, 2 ≦ d ≦ 10, and 0.1 ≦ g ≦ 2 when a = 12.
触媒の調製方法としては特に限定されず、成分の著しい偏在を伴わない限り、従来からよく知られている種々の方法を用いることができる。
また、触媒の調製に用いる原料としては特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を組み合わせて使用することができる。例えばモリブデンの原料化合物としてはパラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等が挙げられる。ビスマスの原料化合物としては、硝酸ビスマス、酸化ビスマス、酢酸ビスマス、水酸化ビスマス等が挙げられる。触媒成分の原料化合物は、触媒成分を構成する各元素に対して１種を用いてもよく、２種以上を組み合わせて用いてもよい。
The method for preparing the catalyst is not particularly limited, and various well-known methods can be used as long as the components are not significantly unevenly distributed.
Moreover, it does not specifically limit as a raw material used for preparation of a catalyst, Nitrate, carbonate, acetate, ammonium salt, an oxide, a halide, etc. of each element can be used in combination. For example, the molybdenum source compound includes ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, and the like. Examples of bismuth raw material compounds include bismuth nitrate, bismuth oxide, bismuth acetate, and bismuth hydroxide. As the raw material compound of the catalyst component, one kind may be used for each element constituting the catalyst component, or two or more kinds may be used in combination.
本発明に用いる触媒は無担体でもよいが、シリカ、アルミナ、シリカ・アルミナ、シリコンカーバイト等の不活性担体に担持させた担持触媒や、あるいはこれら不活性担体で希釈した触媒を用いることもできる。 The catalyst used in the present invention may be non-supported, but a supported catalyst supported on an inert carrier such as silica, alumina, silica-alumina, silicon carbide, or a catalyst diluted with these inert carriers can also be used. .
上述した触媒を反応器に備わる反応管に充填し、触媒層を形成させる。
なお、本発明において「触媒層」とは、反応管内において少なくとも触媒が含まれている領域を指す。すなわち、触媒だけが充填されている領域だけでなく、触媒が不活性担体等で希釈されている領域も触媒層とする。ただし、反応管の両端部など、何も充填されていない空間部分や不活性担体等だけが充填されている領域は、触媒が実質的に含まれないので触媒層には含まない。
The catalyst described above is filled in a reaction tube provided in the reactor to form a catalyst layer.
In the present invention, the “catalyst layer” refers to a region containing at least a catalyst in the reaction tube. That is, not only the region filled with only the catalyst but also the region where the catalyst is diluted with an inert carrier or the like is used as the catalyst layer. However, spaces that are not filled with anything, such as both ends of the reaction tube, or regions that are filled only with an inert carrier or the like are not included in the catalyst layer because the catalyst is not substantially included.
本発明においては、触媒層が形成された反応管を備えた反応器を用い、反応原料を含む原料ガスを反応管に供給し、酸素含有ガスとの酸化反応により、（メタ）アクロレインまたは（メタ）アクリル酸を製造する。
反応原料としては、プロピレン、イソブチレン、第三級ブチルアルコール（ＴＢＡ）、およびメチル第三級ブチルエーテル（ＭＴＢＥ）からなる群より選ばれた少なくとも１種を用いる。
In the present invention, using a reactor equipped with a reaction tube in which a catalyst layer is formed, a raw material gas containing a reaction raw material is supplied to the reaction tube, and (meth) acrolein or (meta ) Manufacture acrylic acid.
As the reaction raw material, at least one selected from the group consisting of propylene, isobutylene, tertiary butyl alcohol (TBA), and methyl tertiary butyl ether (MTBE) is used.
ところで、酸化反応により（メタ）アクロレインおよび（メタ）アクリル酸を製造する際は、通常、２５０〜４００℃の範囲の反応温度で実施される。しかし、２５０〜４００℃の範囲の反応温度に保たれた触媒層に、反応開始当初から多量の反応原料を供給すると、触媒層に最大温度の高いホットスポットが生じやすい。その結果、触媒の暴走反応が起こりやすくなり、反応を継続するのが困難となる。そのため、酸化反応を行う際は、反応原料の供給量を段階的に増やして定常運転に移行する操作（以下、「スタートアップ」という。）を行うのが一般的であるが、ホットスポットの温度上昇を抑え、目標の反応原料の供給量に達するまで（すなわち、定常状態に移行するまで）には長時間を費やす必要があった。 By the way, when manufacturing (meth) acrolein and (meth) acrylic acid by oxidation reaction, it is normally implemented at the reaction temperature of the range of 250-400 degreeC. However, if a large amount of reaction raw material is supplied to the catalyst layer maintained at a reaction temperature in the range of 250 to 400 ° C. from the beginning of the reaction, a hot spot having a high maximum temperature is likely to be generated in the catalyst layer. As a result, a runaway reaction of the catalyst easily occurs, and it is difficult to continue the reaction. For this reason, when performing an oxidation reaction, it is common to perform an operation (hereinafter referred to as “start-up”) in which the supply amount of the reaction raw material is increased step by step, and the temperature of the hot spot increases. It is necessary to spend a long time until the target amount of reaction raw material is supplied (that is, until the steady reaction state is reached).
本発明者らはこの問題を解決すべく鋭意検討した結果、ホットスポットの温度を抑制するには、反応原料の転化率を下げることで反応熱を抑制するのが一般的であるところ、本発明では逆に反応原料の転化率を高め、ホットスポットの位置を制御することでホットスポットの温度を抑制できることを見出した。そして、酸化反応においてスタートアップを行う際の条件を規定することで、スタートアップ中のホットスポットの温度を十分に抑制でき、短時間でスタートアップを行うことができ、結果として（メタ）アクロレインおよび（メタ）アクリル酸を高い収率で製造できることを見出した。 As a result of intensive studies to solve this problem, the present inventors have generally suppressed the heat of reaction by reducing the conversion rate of the reaction raw material in order to suppress the temperature of the hot spot. Then, on the contrary, it was found that the temperature of the hot spot can be suppressed by increasing the conversion rate of the reaction raw material and controlling the position of the hot spot. By defining the conditions for starting up in the oxidation reaction, the temperature of the hot spot during startup can be sufficiently suppressed, and startup can be performed in a short time. As a result, (meth) acrolein and (meta) It has been found that acrylic acid can be produced in high yield.
すなわち、本発明は原料ガスの供給開始から定常運転に移行するまでの間に、下記条件（１）および（２）を満たすようにスタートアップすることを特徴とする。
（１）反応原料の供給量が、定常運転時における供給量の１０〜６０％のとき（以下、この間を「供給期間１０〜６０％」という。）に、プロピレンおよび／またはイソブチレンの平均転化率が１００〜９８％である。
（２）反応原料の供給量が、定常運転時における供給量の９０〜１００％のとき（以下、この間を「供給期間９０〜１００％」という。）に、プロピレンおよび／またはイソブチレンの平均転化率が９７％以下である。
That is, the present invention is characterized by starting up so as to satisfy the following conditions (1) and (2) during the period from the start of the supply of the raw material gas to the transition to the steady operation.
(1) When the supply amount of the reaction raw material is 10 to 60% of the supply amount in the steady operation (hereinafter referred to as “
(2) The average conversion rate of propylene and / or isobutylene when the supply amount of the reaction raw material is 90 to 100% of the supply amount in steady operation (hereinafter, this period is referred to as “supply period 90 to 100%”). Is 97% or less.
なお、本発明において「定常運転」とは、反応原料が目標の供給量に達し、一定で運転している状態のことである。また、「定常運転時における反応原料の供給量」とは、反応原料の供給量を増加させる工程を終了してから、酸化反応を停止するまでの間に供給される反応原料の供給量の平均値のことである。 In the present invention, “steady operation” refers to a state where the reaction raw material reaches a target supply amount and is operating at a constant level. The “reaction raw material supply amount in steady operation” means the average of the supply amount of the reaction raw material supplied from the end of the step of increasing the reaction raw material supply amount until the oxidation reaction is stopped. It is a value.
また、本発明において「平均転化率」とは、指定された範囲の量の反応原料を供給する期間中のプロピレンおよび／またはイソブチレンの転化率の平均値のことである。すなわち、例えば条件（１）の場合は、供給期間１０〜６０％のときの、プロピレンおよび／またはイソブチレンの転化率の平均値のことである。 In the present invention, the “average conversion rate” is an average value of the conversion rate of propylene and / or isobutylene during a period in which a reaction raw material in a specified range is supplied. That is, for example, in the case of condition (1), it is the average value of the conversion rate of propylene and / or isobutylene when the supply period is 10 to 60%.
プロピレンおよび／またはイソブチレンの転化率は、熱媒浴の温度、反応圧力、反応原料の供給量など、反応条件を変更したときに測定するのが一般的であり、自動ガスクロマトグラフィー等で随時測定することが好ましい。そして、下記式（ｉ）より転化率を求めることができる。
転化率（％）＝Ａ／Ｂ×１００ ・・・（ｉ）
ここで、「Ａ」は反応したプロピレンおよび／またはイソブチレンのモル数、「Ｂ」は供給したプロピレンおよび／またはイソブチレンのモル数である。
The conversion rate of propylene and / or isobutylene is generally measured when the reaction conditions such as the temperature of the heat medium bath, reaction pressure, and supply amount of reaction raw materials are changed. It is preferable to do. And a conversion rate can be calculated | required from following formula (i).
Conversion rate (%) = A / B × 100 (i)
Here, “A” is the number of moles of propylene and / or isobutylene reacted, and “B” is the number of moles of propylene and / or isobutylene supplied.
なお、転化率は反応条件を変更する際にその値が大きく変化することがあるが、後述するΔＴｍａｘの上昇を抑制する観点から、反応条件を変更する前の転化率から±１０％以内の変化に留めることが好ましく、より好ましくは±５％である。また、反応条件の変更により一時的に変化した転化率は、反応条件を変更した後２時間以内に、反応条件を変更する前の転化率の±５％以内に戻ることが好ましい。このように転化率の変化を制御するには、例えば熱媒浴の温度を調整したり、反応圧力を調整したりすればよい。 The value of the conversion rate may change greatly when the reaction conditions are changed. From the viewpoint of suppressing the increase in ΔT max described later, the conversion rate is within ± 10% from the conversion rate before changing the reaction conditions. It is preferable to keep the change, more preferably ± 5%. Moreover, it is preferable that the conversion rate temporarily changed by changing the reaction conditions returns to within ± 5% of the conversion rate before changing the reaction conditions within 2 hours after changing the reaction conditions. In order to control the change in the conversion rate in this way, for example, the temperature of the heat medium bath may be adjusted, or the reaction pressure may be adjusted.
条件（１）について、供給期間１０〜６０％のときのプロピレンおよび／またはイソブチレンの平均転化率が９８％未満であると、ホットスポットの温度が原料ガス出口側で局所的に上昇し、触媒の暴走反応が起こりやすくなるため、短時間でのスタートアップが困難となる。プロピレンおよび／またはイソブチレンの平均転化率は、９９．５〜９８．１％が好ましい。
また、条件（１）において、供給期間１０〜６０％のときのプロピレンおよび／またはイソブチレンの転化率の下限値は、９５％以上が好ましい。
With respect to the condition (1), when the average conversion rate of propylene and / or isobutylene when the supply period is 10 to 60% is less than 98%, the temperature of the hot spot rises locally on the raw material gas outlet side, A runaway reaction is likely to occur, making startup in a short time difficult. The average conversion rate of propylene and / or isobutylene is preferably 99.5 to 98.1%.
In the condition (1), the lower limit of the conversion rate of propylene and / or isobutylene when the supply period is 10 to 60% is preferably 95% or more.
条件（２）について、供給期間９０〜１００％のときのプロピレンおよび／またはイソブチレンの平均転化率が９７％を超えると、ホットスポットの温度が上昇し、触媒の暴走反応が起こりやすくなるため、安定した運転が困難となる。プロピレンおよび／またはイソブチレンの平均転化率は、９６．８％以下が好ましい。なお、平均転化率の下限値については、９３％以上が好ましい。
また、条件（２）において、供給期間９０〜１００％のときのプロピレンおよび／またはイソブチレンの転化率の上限値は、９８％以下が好ましく、下限値は、９０％以上が好ましい。
With respect to condition (2), when the average conversion rate of propylene and / or isobutylene in the supply period of 90 to 100% exceeds 97%, the hot spot temperature rises and the catalyst runaway reaction is likely to occur. Driving becomes difficult. The average conversion rate of propylene and / or isobutylene is preferably 96.8% or less. In addition, about the lower limit of average conversion rate, 93% or more is preferable.
In the condition (2), the upper limit value of the conversion rate of propylene and / or isobutylene when the supply period is 90 to 100% is preferably 98% or less, and the lower limit value is preferably 90% or more.
このように、原料ガスの供給開始から定常運転に移行するまでの間に、上記条件（１）および（２）を満たすようにスタートアップすることで、反応原料の転化率を高め、ホットスポットの位置を制御することができる。
「反応原料の転化率を高める」とは、触媒層の原料ガス入口側の反応を促進することを意味する。逆に、反応原料の転化率が低い場合は、触媒層の原料ガス出口側で主に酸化反応が進行することとなる。そのため、ホットスポットの発生位置が触媒層の原料ガス出口側に移動しやすくなる。ホットスポットの発生位置が触媒層の原料ガス出口側に移動すると、該ホットスポットで局所的に発熱する傾向があり、触媒の暴走反応が起こりやすくなる。そのため、ホットスポットの温度が下がるまで反応原料の供給量を増やすことができないので、スタートアップが完了するまでに長時間を費やすこととなる。
Thus, by starting up so as to satisfy the above conditions (1) and (2) during the period from the start of the supply of the raw material gas to the transition to the steady operation, the conversion rate of the reaction raw material is increased, and the position of the hot spot Can be controlled.
“Increasing the conversion rate of the reaction raw material” means promoting the reaction on the raw material gas inlet side of the catalyst layer. Conversely, when the conversion rate of the reaction raw material is low, the oxidation reaction proceeds mainly on the raw material gas outlet side of the catalyst layer. For this reason, the hot spot generation position easily moves to the source gas outlet side of the catalyst layer. When the hot spot generation position moves to the source gas outlet side of the catalyst layer, the hot spot tends to generate heat locally, and the catalyst runaway reaction is likely to occur. Therefore, since the supply amount of the reaction raw material cannot be increased until the temperature of the hot spot is lowered, it takes a long time to complete the start-up.
しかし、本発明であれば、スタートアップ中の反応原料の転化率を高めるので、ホットスポットが原料ガス出口側に発生することを抑制できる（すなわち、触媒層の長さ方向においてホットスポットの発生位置を制御できる）。従って、触媒層の長さ方向の発熱を均一化でき、ホットスポットの温度が局所的に上昇することを抑制できる。そのため、反応原料の供給量を減らしたり供給量の上昇を止めたりする必要がなく、短時間でスタートアップできる。 However, according to the present invention, since the conversion rate of the reaction raw material during start-up is increased, it is possible to suppress the generation of hot spots on the raw material gas outlet side (that is, the hot spot generation position in the length direction of the catalyst layer). Can be controlled). Therefore, the heat generation in the length direction of the catalyst layer can be made uniform, and the hot spot temperature can be prevented from rising locally. Therefore, it is not necessary to reduce the supply amount of the reaction raw material or stop the increase in the supply amount, and the startup can be performed in a short time.
本発明においては、原料ガスの供給開始から定常運転に移行するまでの間に、下記条件（３）を満たすようにスタートアップするのが好ましい。
（３）反応原料の供給量が、定常運転時における供給量の６０％超、９０％未満のとき（以下、この間を「供給期間６０％超〜９０％未満」という。）に、プロピレンおよび／またはイソブチレンの平均転化率が９９〜９７％である。
In the present invention, it is preferable to start up so as to satisfy the following condition (3) between the start of supply of the raw material gas and the transition to the steady operation.
(3) When the supply amount of the reaction raw material is more than 60% and less than 90% of the supply amount in the steady operation (hereinafter referred to as “more than 60% to less than 90% supply period”), propylene and / or Or the average conversion of isobutylene is 99 to 97%.
条件（３）について、供給期間６０％超〜９０％未満のときのプロピレンおよび／またはイソブチレンの平均転化率が９７％未満であると、ホットスポットの温度が原料ガス出口側で局所的に上昇し、触媒の暴走反応が起こりやすくなるため、短時間でのスタートアップが困難となる。一方、プロピレンおよび／またはイソブチレンの平均転化率が９９％を超えると、ホットスポットの温度が上昇し、触媒の暴走反応が起こりやすくなるため、安定した運転が困難となる。プロピレンおよび／またはイソブチレンの平均転化率は、９８．５〜９７．１％が好ましい。
また、条件（３）において、供給期間６０％超〜９０％未満のときのプロピレンおよび／またはイソブチレンの転化率の上限値は、９９．５％以下が好ましく、下限値は、９４％以上が好ましい。
Regarding condition (3), if the average conversion rate of propylene and / or isobutylene is less than 97% when the supply period is more than 60% and less than 90%, the temperature of the hot spot rises locally on the raw material gas outlet side. Since the catalyst runaway reaction is likely to occur, start-up in a short time becomes difficult. On the other hand, when the average conversion rate of propylene and / or isobutylene exceeds 99%, the temperature of the hot spot rises and the runaway reaction of the catalyst tends to occur, so that stable operation becomes difficult. The average conversion rate of propylene and / or isobutylene is preferably 98.5 to 97.1%.
In the condition (3), the upper limit value of the conversion rate of propylene and / or isobutylene when the supply period is more than 60% to less than 90% is preferably 99.5% or less, and the lower limit value is preferably 94% or more. .
なお、ＴＢＡやＭＴＢＡは、反応器に供給されると速やかに脱水されてイソブチレンに変換される。従って、反応原料としてＴＢＡやＭＴＢＡを用いた場合は、イソブチレンを用いた場合と同様の結果が得られると予想される。 When TBA and MTBA are supplied to the reactor, they are quickly dehydrated and converted to isobutylene. Therefore, when TBA or MTBA is used as a reaction raw material, it is expected that the same result as that obtained when isobutylene is used will be obtained.
各供給期間におけるプロピレンおよび／またはイソブチレンの転化率は、例えば熱媒浴の温度を調整したり、反応圧力を調整したりすることで制御できるが、これらの方法に限定されない。
熱媒浴の温度は、２８０〜４５０℃が好ましく、３００〜４００℃がより好ましい。
反応圧力は、常圧から数気圧程度が好ましい。
熱媒浴の温度や反応圧力が高くなるに連れて、プロピレンおよび／またはイソブチレンの転化率は上がる傾向にある。
The conversion rate of propylene and / or isobutylene in each supply period can be controlled by adjusting the temperature of the heat medium bath or adjusting the reaction pressure, but is not limited to these methods.
The temperature of the heat medium bath is preferably 280 to 450 ° C, more preferably 300 to 400 ° C.
The reaction pressure is preferably about normal pressure to several atmospheres.
As the temperature of the heat medium bath and the reaction pressure increase, the conversion of propylene and / or isobutylene tends to increase.
また、プロピレンおよび／またはイソブチレンの転化率は、原料ガス中の反応原料と酸素のモル比を調整することでも制御できる。
本発明に用いる原料ガスは、上述した反応原料と、酸素源として酸素含有ガスを含む。酸素含有ガスには、通常、酸素と水蒸気が含まれる。
特に、反応原料としてイソブチレンおよび／またはＴＢＡを用いる場合、原料ガス中の酸素の濃度は、反応原料１モルに対して０．３〜４．０モルが好ましく、０．４〜３．０モルが好ましい。反応原料１モルに対する酸素の濃度が大きくなるに連れて、プロピレンおよび／またはイソブチレンの転化率は上がる傾向にある。
The conversion rate of propylene and / or isobutylene can also be controlled by adjusting the molar ratio of the reaction raw material and oxygen in the raw material gas.
The raw material gas used in the present invention includes the reaction raw material described above and an oxygen-containing gas as an oxygen source. The oxygen-containing gas usually contains oxygen and water vapor.
In particular, when isobutylene and / or TBA is used as a reaction raw material, the concentration of oxygen in the raw material gas is preferably 0.3 to 4.0 mol, and 0.4 to 3.0 mol per mol of the reaction raw material. preferable. As the concentration of oxygen with respect to 1 mol of the reaction raw material increases, the conversion of propylene and / or isobutylene tends to increase.
原料ガス中の酸素としては、分子状酸素として空気を用いるのが経済的に有利であるが、必要に応じて純酸素で富化した空気を用いてもよい。
また、原料ガスには、本反応に対して実質的に影響を与えない低級アルデヒド等の不純物を少量含んでいてもよいし、原料ガスを窒素、水蒸気、二酸化炭素等の不活性ガスを加えて希釈してもよい。
As the oxygen in the raw material gas, it is economically advantageous to use air as molecular oxygen, but air enriched with pure oxygen may be used as necessary.
In addition, the source gas may contain a small amount of impurities such as lower aldehydes that do not substantially affect the present reaction, or an inert gas such as nitrogen, water vapor or carbon dioxide is added to the source gas. It may be diluted.
定常運転時における原料ガスの濃度は、反応原料の濃度が４〜１０容量％、酸素の濃度が７〜１６容量％、水蒸気の濃度が５〜５０容量％であることが好ましく、反応原料の濃度が６〜８容量％、酸素の濃度が９〜１５容量％、水蒸気の濃度が６〜４０容量％であることがより好ましい。 The concentration of the raw material gas during steady operation is preferably 4 to 10% by volume of the reaction raw material, 7 to 16% by volume of oxygen, and 5 to 50% by volume of water vapor. Is more preferably 6 to 8% by volume, oxygen concentration is 9 to 15% by volume, and water vapor concentration is 6 to 40% by volume.
定常運転時に供給される反応原料の供給量は、通常、反応原料の反応器への上限供給量の７０％以上であり、（メタ）アクロレインまたは（メタ）アクリル酸の生産性を高めるためには、反応原料の供給量を増やすのが好ましい。
また、定常運転時に供給される原料ガスの流量は、反応管１本あたり、空間速度が３００〜３０００ｈｒ−１となるような流量が好ましく、より好ましくは５００〜２０００ｈｒ−１である。なお、スタートアップ中の原料ガスの流量は、反応原料の供給量が上述した条件（１）および（２）を満たせば、特に制限されない。
In order to increase the productivity of (meth) acrolein or (meth) acrylic acid, the supply amount of the reaction raw material supplied during steady operation is usually 70% or more of the upper limit supply amount of the reaction raw material to the reactor. It is preferable to increase the supply amount of the reaction raw material.
The flow rate of the raw material gas supplied during steady operation is preferably such that the space velocity is 300 to 3000 hr −1 per reaction tube, more preferably 500 to 2000 hr −1 . Note that the flow rate of the raw material gas during start-up is not particularly limited as long as the supply amount of the reaction raw material satisfies the conditions (1) and (2) described above.
上述したように、本発明はスタートアップ中の反応原料の転化率を高めることで、触媒層の長さ方向においてホットスポットの発生位置を制御することが可能となる。具体的には、触媒層と熱媒浴との温度差（ΔＴ：触媒層−熱媒浴の温度）が最大となる位置（すなわち、ホットスポットの発生位置）から、触媒層の原料ガス入口側の端部までの距離（ｄ）が、当該触媒層の全長の０．５倍以下となるような位置に、ホットスポットの発生位置を制御できる。距離（ｄ）は、触媒層の全長の０．４倍以下が特に好ましい。距離（ｄ）の下限値については特に制限されない。
距離（ｄ）が触媒層の全長の０．５倍以下であれば、触媒層の長さ方向の発熱を均一化でき、ホットスポットの温度が局所的に上昇することをより効果的に抑制できる。そのため、反応原料の供給量を減らしたり供給量の上昇を止めたりする必要がなく、短時間でスタートアップできる。
As described above, according to the present invention, it is possible to control the hot spot generation position in the length direction of the catalyst layer by increasing the conversion rate of the reaction raw material during start-up. Specifically, from the position at which the temperature difference between the catalyst layer and the heat medium bath (ΔT: temperature of the catalyst layer-heat medium bath) becomes maximum (that is, the hot spot generation position), the raw material gas inlet side of the catalyst layer. The position where the hot spot is generated can be controlled to a position where the distance (d) to the end of the catalyst layer becomes 0.5 times or less of the total length of the catalyst layer. The distance (d) is particularly preferably not more than 0.4 times the total length of the catalyst layer. The lower limit value of the distance (d) is not particularly limited.
If the distance (d) is 0.5 times or less of the total length of the catalyst layer, the heat generation in the length direction of the catalyst layer can be made uniform, and the hot spot temperature can be more effectively suppressed from rising locally. . Therefore, it is not necessary to reduce the supply amount of the reaction raw material or stop the increase in the supply amount, and the startup can be performed in a short time.
なお、熱媒浴中の熱媒は、反応器の形態、反応条件、熱媒の流動状態によって温度に若干の不均一分布が生じる場合がある。この不均一分布の度合いが小さい場合は、熱媒浴の平均温度を「熱媒浴の温度」として採用してもよい。ただし、不均一分布の度合いが大きい場合は、触媒層の位置に応じて触媒層近傍の熱媒浴の温度を測定し、ΔＴを求める。 Note that the heat medium in the heat medium bath may have a slightly uneven distribution in temperature depending on the form of the reactor, reaction conditions, and the flow state of the heat medium. When the degree of this non-uniform distribution is small, the average temperature of the heat medium bath may be adopted as the “temperature of the heat medium bath”. However, when the degree of non-uniform distribution is large, the temperature of the heat medium bath in the vicinity of the catalyst layer is measured according to the position of the catalyst layer to obtain ΔT.
触媒層の温度を測定する方法としては、例えば反応管に触媒を充填するに先立ち、反応管内に保護管を設置し、該保護間内に熱電対を挿入して、酸化反応中の各場所における触媒層の温度を測定する方法が挙げられる。この測定方法において、保護管の設置位置は、反応管の管軸方向に対して垂直な断面の中心付近が好ましい。また、保護管の長さは触媒層を超える長さが必要である。この測定方法によれば、触媒層のあらゆる位置の温度を簡便に測定できるので好ましい。
なお、工業的に用いられる多管式反応器の場合には、全ての反応管内の触媒層の温度を測定することは実際上困難であるため、実質的に反応器全体を代表する反応管を複数選択し、選択された反応管内の触媒層について温度を測定すればよい。
As a method for measuring the temperature of the catalyst layer, for example, prior to filling the reaction tube with the catalyst, a protective tube is installed in the reaction tube, a thermocouple is inserted between the protection tubes, and at each location during the oxidation reaction. The method of measuring the temperature of a catalyst layer is mentioned. In this measurement method, the protective tube is preferably installed near the center of the cross section perpendicular to the tube axis direction of the reaction tube. The length of the protective tube needs to exceed the catalyst layer. This measuring method is preferable because the temperature at any position of the catalyst layer can be easily measured.
In the case of a multi-tubular reactor used industrially, it is practically difficult to measure the temperature of the catalyst layer in all the reaction tubes. Therefore, a reaction tube that substantially represents the entire reactor is used. A plurality may be selected, and the temperature may be measured for the catalyst layers in the selected reaction tube.
以上説明したように、本発明によれば、原料ガスの供給開始から定常運転に移行するまでの間に、上記条件（１）および（２）を満たすようにスタートアップするので、反応原料の転化率を高め、ホットスポットの位置を制御することができる。その結果、ホットスポットの温度が上昇するのを抑制できる。具体的には、上述した触媒層と熱媒浴との温度差（ΔＴ）の最大値（ΔＴｍａｘ）を５０℃以下程度に抑制できる。
従って、本発明の（メタ）アクロレインまたは（メタ）アクリル酸の製造方法は、スタートアップ中に反応原料の供給量を減らしたり供給量の上昇を止めたりする必要がなく、短時間でスタートアップでき、結果として（メタ）アクロレインおよび（メタ）アクリル酸を高い収率で製造できる。
As described above, according to the present invention, since the start-up is performed so as to satisfy the above conditions (1) and (2) from the start of the supply of the raw material gas to the transition to the steady operation, the conversion rate of the reaction raw material And the position of the hot spot can be controlled. As a result, an increase in the temperature of the hot spot can be suppressed. Specifically, the maximum value (ΔT max ) of the temperature difference (ΔT) between the catalyst layer and the heat medium bath described above can be suppressed to about 50 ° C. or less.
Therefore, the method for producing (meth) acrolein or (meth) acrylic acid according to the present invention does not require reducing the supply amount of the reaction raw material or stopping the increase in the supply amount during start-up, and can start up in a short time. (Meth) acrolein and (meth) acrylic acid can be produced in a high yield.
以下、本発明について実施例を挙げて具体的に説明する。ただし、本発明はこれらに限定されるものではない。
なお、実施例および比較例中の「部」は「質量部」を意味する。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
In the examples and comparative examples, “part” means “part by mass”.
＜ΔＴｍａｘの定義＞
ΔＴｍａｘは、以下のように定義される。
触媒層の温度は、反応管の管軸方向に対して垂直な断面の中心に設置した保護管に挿入した熱電対により測定した。なお、保護管は反応系と隔離されており、温度を測定する位置は挿入する熱電対の長さを調節して変えることができる。このとき測定した触媒層の温度と熱媒浴の温度との差（ΔＴ＝触媒層の温度−熱媒浴の温度）を測定することでホットスポットを検出した。このとき検出されたΔＴ分布のうち、最も高温のΔＴをΔＴｍａｘとして示した。
また、ΔＴｍａｘの位置は、触媒層の原料ガス入口側の端部から測定した距離（ｄ）として示した。
<Definition of ΔT max >
ΔT max is defined as follows.
The temperature of the catalyst layer was measured by a thermocouple inserted in a protective tube installed at the center of the cross section perpendicular to the tube axis direction of the reaction tube. The protective tube is isolated from the reaction system, and the temperature measurement position can be changed by adjusting the length of the thermocouple to be inserted. A hot spot was detected by measuring the difference between the temperature of the catalyst layer measured at this time and the temperature of the heat medium bath (ΔT = temperature of the catalyst layer−temperature of the heat medium bath). Of the ΔT distribution detected at this time, the highest temperature ΔT is indicated as ΔT max .
Further, the position of ΔT max is shown as a distance (d) measured from the end of the catalyst layer on the raw material gas inlet side.
＜スタートアップの手順＞
実施例および比較例におけるスタートアップは以下のように行った。
スタートアップ中はΔＴｍａｘが高温になると触媒が暴走反応を起こすことがあるため、ΔＴｍａｘが５０℃を超えた場合は反応原料の供給量を上昇させず、ΔＴｍａｘが５０℃以下に下がったのを確認した後、反応原料の供給量を上昇させることとした。また、ΔＴｍａｘの管理上限値を６０℃とし、上限値を超える場合は直ちに反応原料の供給を止め、反応を停止することとした。
反応原料の供給量は、０％から定常運転時における供給量まで１０％ずつ段階的に上昇させた。また、反応原料の供給量はΔＴｍａｘが一定になった後、上昇させた。ここで「ΔＴｍａｘが一定になる」とは、ΔＴｍａｘの温度変化が、３０分以上にわたり±１．０℃の範囲の状態を意味する。
なお、反応原料の供給量が定常運転時の供給量に達し、ΔＴｍａｘが一定に後を定常運転とした。
<Startup procedure>
Startup in Examples and Comparative Examples was performed as follows.
During startup, if ΔT max becomes high, the catalyst may cause a runaway reaction. Therefore, when ΔT max exceeds 50 ° C., the supply amount of the reaction raw material is not increased, and ΔT max decreases to 50 ° C. or less. After confirming this, the supply amount of the reaction raw material was increased. Further, the control upper limit value of ΔT max was set to 60 ° C., and when the upper limit value was exceeded, the supply of the reaction raw material was stopped immediately and the reaction was stopped.
The supply amount of the reaction raw material was increased stepwise by 10% from 0% to the supply amount in steady operation. Further, the supply amount of the reaction raw material was increased after ΔT max became constant. Here, “ΔT max becomes constant” means that the temperature change of ΔT max is in the range of ± 1.0 ° C. over 30 minutes.
The supply amount of the reaction raw material reached the supply amount at the time of steady operation, and after that ΔT max was constant, the steady operation was performed.
＜転化率の算出方法＞
原料ガス及び反応生成ガスは、ガスクロマトグラフィーにより分析した。実施例および比較例の反応原料（イソブチレン）の転化率は、下記式（ｉ）により算出した。
イソブチレンの転化率（％）＝Ａ／Ｂ×１００ ・・・（ｉ）
ここで、「Ａ」は反応したイソブチレンのモル数、「Ｂ」は供給したイソブチレンのモル数である。
<Calculation method of conversion>
The raw material gas and the reaction product gas were analyzed by gas chromatography. The conversion rates of the reaction raw materials (isobutylene) in Examples and Comparative Examples were calculated by the following formula (i).
Conversion of isobutylene (%) = A / B × 100 (i)
Here, “A” is the number of moles of reacted isobutylene, and “B” is the number of moles of isobutylene supplied.
＜触媒の調製＞
純水１０００部に、パラモリブデン酸アンモニウム５００部、パラタングステン酸アンモニウム６．２部、硝酸セシウム２３．０部、三酸化アンチモン３４．３部および三酸化ビスマス２８．５部を加え、加熱攪拌した（Ａ液）。
別途、純水１０００部に、硝酸第二鉄２０９．８部、硝酸ニッケル１０２．９部、硝酸コバルト４１２．１部、硝酸鉛１５．７部および８５％リン酸２．８部を順次加え、溶解した（Ｂ液）。
ついで、Ａ液にＢ液を加えて水性スラリーとした後、この水性スラリーをスプレー乾燥機にて乾燥させ、平均粒径６０μｍの乾燥球状粒子とした。この乾燥球状粒子を３００℃で１時間、５１０℃で３時間焼成を行い、球状粒子形状の触媒材料を製造した。
この触媒材料５０００部に対して、ヒドロキシプロピルメチルセルロース１５０部およびカードラン５０部を加え、乾式混合した。ここに純水１９００部を混合し、混練り機で粘土状物質になるまで混合（混練り）した後、得られた混練物をピストン式押出し成形機を用いて外径５ｍｍ、内径２ｍｍ、高さ５ｍｍのリング状に押出成形し、粒状の固体酸化触媒とした。
得られた固体酸化触媒の酸素以外の元素組成は、次の通りであった。なお、元素組成は触媒原料の仕込み量から求めた。
Ｍｏ１２Ｗ０．１Ｂｉ０．７Ｆｅ２．２Ｓｂ１．０Ｎｉ１．５Ｃｏ６．０Ｐｂ０．２Ｐ０．１Ｃｓ０．５
<Preparation of catalyst>
To 1000 parts of pure water, 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 34.3 parts of antimony trioxide and 28.5 parts of bismuth trioxide were added and stirred with heating. (Liquid A).
Separately, ferric nitrate 209.8 parts, nickel nitrate 102.9 parts, cobalt nitrate 412.1 parts, lead nitrate 15.7 parts and 85% phosphoric acid 2.8 parts were sequentially added to 1000 parts of pure water. Dissolved (Liquid B).
Next, liquid B was added to liquid A to form an aqueous slurry, and then the aqueous slurry was dried with a spray dryer to obtain dry spherical particles having an average particle diameter of 60 μm. The dried spherical particles were calcined at 300 ° C. for 1 hour and at 510 ° C. for 3 hours to produce a spherical particle-shaped catalyst material.
To 5000 parts of the catalyst material, 150 parts of hydroxypropyl methylcellulose and 50 parts of curdlan were added and dry mixed. 1900 parts of pure water was mixed here and mixed (kneaded) until it became a clay-like substance with a kneader, and then the obtained kneaded material was
The elemental composition other than oxygen of the obtained solid oxidation catalyst was as follows. The elemental composition was obtained from the charged amount of the catalyst raw material.
Mo 12 W 0.1 Bi 0.7 Fe 2.2 Sb 1.0 Ni 1.5 Co 6.0 Pb 0.2 P 0.1 Cs 0.5
［実施例１］
＜触媒の充填＞
気相接触酸化反応には、内径２６．５ｍｍ、長さ６ｍの反応管を１本備え、該反応管の外側に熱媒浴を有する固定床管型反応器を用いた。熱媒としては、硝酸カリウム５０質量％および亜硝酸ナトリウム５０質量％からなる塩溶融物を用い、熱媒浴の温度を１８０℃に設定した。
反応管の原料ガス入口側に、先に調製した固体酸化触媒５００ｇと、ＳＵＳ３０４製のラシヒリング（外径５ｍｍ、外径と内径の差０．４ｍｍ、長さ５ｍｍ）４００ｇとを混合したものを充填した。さらにその上から固体酸化触媒８００ｇを充填し、全長４０８５ｍｍの触媒層を形成した。
この触媒層に、酸素９容量％、水蒸気１０容量％、および窒素８１容量％からなる酸素含有ガスを、空間速度２４０ｈｒ−１で流通させながら、熱媒浴の温度を３５０℃まで５０℃／時間で昇温した。
[Example 1]
<Packing of catalyst>
For the gas phase catalytic oxidation reaction, a fixed bed tubular reactor having one reaction tube having an inner diameter of 26.5 mm and a length of 6 m and having a heat medium bath outside the reaction tube was used. As the heat medium, a salt melt composed of 50% by mass of potassium nitrate and 50% by mass of sodium nitrite was used, and the temperature of the heat medium bath was set to 180 ° C.
Filled with the raw material gas inlet side of the reaction tube with a mixture of 500 g of the previously prepared solid oxidation catalyst and 400 g of SUS304 Raschig rings (
Through this catalyst layer, an oxygen-containing gas consisting of 9% by volume of oxygen, 10% by volume of water vapor, and 81% by volume of nitrogen was circulated at a space velocity of 240 hr −1 , while the temperature of the heat medium bath was increased to 350 ° C. at 50 ° C./hour. The temperature was raised.
＜第１工程：供給期間１０〜６０％＞
熱媒浴の温度を３２５℃に設定した。
反応原料としてイソブチレンと、酸素、水蒸気および窒素からなる酸素含有ガスとを含む原料ガスを反応管に供給し、イソブチレンの供給量を定常運転時における供給量の０〜６０％まで増やした。供給期間１０〜６０％（すなわち、定常運転時における反応原料の供給量に対するスタートアップ中の反応原料の供給量の割合が１０〜６０％）のときのイソブチレン、酸素、水蒸気および窒素の濃度と、原料ガスの空間速度を表１に示す。
供給期間１０〜６０％のとき、イソブチレンの平均転化率９９．４％であった。
また、供給期間１０〜６０％のときのΔＴｍａｘ、ΔＴｍａｘの位置、第１工程の所要時間を表２に示す。
<First step: 10 to 60% of supply period>
The temperature of the heat medium bath was set to 325 ° C.
A raw material gas containing isobutylene as a reaction raw material and an oxygen-containing gas composed of oxygen, water vapor, and nitrogen was supplied to the reaction tube, and the supply amount of isobutylene was increased to 0 to 60% of the supply amount in steady operation. Concentrations of isobutylene, oxygen, water vapor and nitrogen when the supply period is 10 to 60% (that is, the ratio of the supply amount of the reaction raw material during start-up to the supply amount of the reaction raw material during steady operation is 10 to 60%), and the raw material Table 1 shows the space velocity of the gas.
When the feed period was 10 to 60%, the average conversion of isobutylene was 99.4%.
Table 2 shows the positions of ΔT max and ΔT max when the supply period is 10 to 60% and the time required for the first step.
＜第２工程：供給期間６０％超〜９０％未満＞
第１工程に引き続き、イソブチレンの供給量を定常運転時における供給量の６０％超〜９０％未満まで増やした。なお、熱媒浴の温度は３２５℃に設定した。供給期間６０％超〜９０％未満のときのイソブチレン、酸素、水蒸気および窒素の濃度と、原料ガスの空間速度を表１に示す。
供給期間６０％超〜９０％未満のとき、イソブチレンの平均転化率９８．０％であった。
供給期間６０％超〜９０％未満のときのΔＴｍａｘ、ΔＴｍａｘの位置、第２工程の所要時間を表２に示す。
<Second step: More than 60% to less than 90% supply period>
Following the first step, the supply amount of isobutylene was increased from more than 60% to less than 90% of the supply amount during steady operation. The temperature of the heat medium bath was set to 325 ° C. Table 1 shows the concentrations of isobutylene, oxygen, water vapor and nitrogen, and the space velocity of the raw material gas when the supply period exceeds 60% to less than 90%.
When the feed period was more than 60% and less than 90%, the average conversion of isobutylene was 98.0%.
Table 2 shows the positions of ΔT max and ΔT max when the supply period is over 60% to less than 90% and the time required for the second step.
＜第３工程：供給期間９０〜１００％＞
第２工程に引き続き、イソブチレンの供給量を定常運転時における供給量の９０〜１００％まで増やした。なお、熱媒浴の温度は３２５℃に設定した。供給期間９０〜１００％のときのイソブチレン、酸素、水蒸気および窒素の濃度と、原料ガスの空間速度を表１に示す。
供給期間９０〜１００％のとき、イソブチレンの平均転化率９６．８％であった。
供給期間９０〜１００％のときのΔＴｍａｘ、ΔＴｍａｘの位置、第３工程の所要時間を表２に示す。
また、各供給期間における、熱媒浴の温度、イソブチレンの供給量、イソブチレンの転化率、およびΔＴｍａｘと、時間（原料ガスの供給開始からの経過時間）とのそれぞれ関係（推移）を図１に示す。
<Third step: 90 to 100% of supply period>
Following the second step, the supply amount of isobutylene was increased to 90 to 100% of the supply amount during steady operation. The temperature of the heat medium bath was set to 325 ° C. Table 1 shows the concentration of isobutylene, oxygen, water vapor and nitrogen and the space velocity of the raw material gas when the supply period is 90 to 100%.
When the feed period was 90 to 100%, the average conversion of isobutylene was 96.8%.
Table 2 shows the positions of ΔT max and ΔT max when the supply period is 90 to 100% and the time required for the third step.
FIG. 1 shows the relationship (transition) of the temperature of the heat medium bath, the supply amount of isobutylene, the conversion rate of isobutylene, and ΔT max in each supply period, and time (elapsed time from the start of supply of raw material gas). Shown in
［実施例２］
第１工程〜第３工程において、熱媒浴の温度を３２２℃に設定した以外は、実施例１と同様にして第１工程〜第３工程を行った。
各供給期間におけるイソブチレンの平均転化率、ΔＴｍａｘ、ΔＴｍａｘの位置、および第１工程〜第３工程の所要時間を表２に示す。
また、各供給期間における、熱媒浴の温度、イソブチレンの供給量、イソブチレンの転化率、およびΔＴｍａｘと、時間とのそれぞれ関係を図２に示す。
[Example 2]
In the first step to the third step, the first step to the third step were performed in the same manner as in Example 1 except that the temperature of the heat medium bath was set to 322 ° C.
Table 2 shows the average conversion of isobutylene in each supply period, the positions of ΔT max and ΔT max , and the time required for the first to third steps.
FIG. 2 shows the relationship between the temperature of the heat medium bath, the supply amount of isobutylene, the conversion rate of isobutylene, ΔT max and time in each supply period.
［比較例１］
熱媒浴の温度を３０８℃に設定し、供給期間１０〜６０％のときのイソブチレンの転化率が９５％で一定になるように、イソブチレンの供給量を増やした際に熱媒浴の温度を調節した以外は、実施例１と同様にして第１工程を行った。
ついで、供給期間６０％超〜９０％未満のときのイソブチレンの転化率が９５％で一定になるように、イソブチレンの供給量を増やした際に熱媒浴の温度を調節した以外は、実施例１と同様にして第２工程を行った。
ついで、供給期間９０〜１００％のときのイソブチレンの転化率が９５％で一定になるように、イソブチレンの供給量を増やした際に熱媒浴の温度を調節した以外は、実施例１と同様にして第３工程を行った。
[Comparative Example 1]
When the temperature of the heat medium bath is set to 308 ° C. and the amount of isobutylene supplied is increased so that the conversion of isobutylene is constant at 95% when the supply period is 10 to 60%, the temperature of the heat medium bath is set to The first step was performed in the same manner as in Example 1 except that the adjustment was performed.
Then, except that the temperature of the heat medium bath was adjusted when the supply amount of isobutylene was increased so that the conversion of isobutylene when the supply period was more than 60% to less than 90% was constant at 95%. The second step was performed in the same manner as in 1.
Next, except that the temperature of the heat medium bath was adjusted when the amount of isobutylene supplied was increased so that the conversion of isobutylene during the supply period of 90 to 100% was constant at 95%. Then, the third step was performed.
各工程終了時の熱媒浴の温度、各供給期間におけるイソブチレンの平均転化率、ΔＴｍａｘ、ΔＴｍａｘの位置、および第１反応〜第３反応の所要時間を表２に示す。
また、各供給期間における、熱媒浴の温度、イソブチレンの供給量、イソブチレンの転化率、およびΔＴｍａｘと、時間とのそれぞれ関係を図３に示す。
Table 2 shows the temperature of the heat medium bath at the end of each step, the average conversion of isobutylene during each supply period, the positions of ΔT max and ΔT max , and the time required for the first to third reactions.
FIG. 3 shows the relationship between the temperature of the heat medium bath, the supply amount of isobutylene, the conversion rate of isobutylene, and ΔT max in each supply period, and time.
［比較例２］
比較例１と同様にして第１工程を行った。
ついで、ΔＴｍａｘが５０℃を超えてもイソブチレンの供給量の上昇を続けた以外は、比較例１と同様にして第２工程、第３工程を行った。
その結果、イソブチレンの供給量が定常運転時の供給量の９０％に達したときに、ΔＴｍａｘが６０℃を超えたため、原料ガスの供給を止め、反応器を停止した。反応器を開放して触媒を確認したところ、触媒の一部が変色し、失活していた。
[Comparative Example 2]
The first step was performed in the same manner as in Comparative Example 1.
Subsequently, the second step and the third step were performed in the same manner as in Comparative Example 1 except that the increase in the amount of isobutylene continued even when ΔT max exceeded 50 ° C.
As a result, when the supply amount of isobutylene reached 90% of the supply amount during steady operation, ΔT max exceeded 60 ° C., so the supply of the raw material gas was stopped and the reactor was stopped. When the reactor was opened and the catalyst was confirmed, a part of the catalyst was discolored and deactivated.
［比較例３］
各供給期間におけるイソブチレンの転化率が９７％で一定になるように、イソブチレンの供給量を増やした際に熱媒浴の温度を調節した以外は、比較例１と同様にして第１工程〜第３工程を行った。
各工程終了時の熱媒浴の温度、各供給期間におけるイソブチレンの平均転化率、ΔＴｍａｘ、ΔＴｍａｘの位置、および第１工程〜第３工程の所要時間を表２に示す。
また、各供給期間における、熱媒浴の温度、イソブチレンの供給量、イソブチレンの転化率、およびΔＴｍａｘと、時間とのそれぞれ関係を図４に示す。
[Comparative Example 3]
The first step to the second step are the same as in Comparative Example 1 except that the temperature of the heat medium bath is adjusted when the supply amount of isobutylene is increased so that the conversion of isobutylene is constant at 97% in each supply period. Three steps were performed.
Table 2 shows the temperature of the heat medium bath at the end of each step, the average conversion of isobutylene during each supply period, the positions of ΔT max and ΔT max , and the time required for the first to third steps.
FIG. 4 shows the relationship between the temperature of the heat medium bath, the supply amount of isobutylene, the conversion rate of isobutylene, ΔT max , and time in each supply period.
［比較例４］
比較例３と同様にして第１工程を行った。
ついで、ΔＴｍａｘが５０℃を超えてもイソブチレンの供給量の上昇を続けた以外は、比較例３と同様にして第２工程、第３工程を行った。
その結果、イソブチレンの供給量が定常運転時の供給量の９０％に達したときに、ΔＴｍａｘが６０℃を超えたため、原料ガスの供給を止め、反応器を停止した。反応器を開放して触媒を確認したところ、触媒の一部が変色し、失活していた。
[Comparative Example 4]
The first step was performed in the same manner as in Comparative Example 3.
Subsequently, the second step and the third step were performed in the same manner as in Comparative Example 3 except that the increase in the amount of isobutylene continued even when ΔT max exceeded 50 ° C.
As a result, when the supply amount of isobutylene reached 90% of the supply amount during steady operation, ΔT max exceeded 60 ° C., so the supply of the raw material gas was stopped and the reactor was stopped. When the reactor was opened and the catalyst was confirmed, a part of the catalyst was discolored and deactivated.
［比較例５］
第１工程を行わなかった以外は、実施例１と同様にして第２工程を行った。なお、「第１工程を行わない」とは、定常運転時におけるイソブチレンの供給量の６０％に相当する量にて、原料ガスの供給を開始したことを意味する。
その結果、イソブチレンの供給量が定常運転時の供給量の９０％に達したときに、ΔＴｍａｘが６０℃を超えたため、原料ガスの供給を止め、反応器を停止した。反応器を開放して触媒を確認したところ、触媒の一部が変色し、失活していた。
[Comparative Example 5]
The second step was performed in the same manner as in Example 1 except that the first step was not performed. Note that “not performing the first step” means that the supply of the raw material gas is started in an amount corresponding to 60% of the supply amount of isobutylene in the steady operation.
As a result, when the supply amount of isobutylene reached 90% of the supply amount during steady operation, ΔT max exceeded 60 ° C., so the supply of the raw material gas was stopped and the reactor was stopped. When the reactor was opened and the catalyst was confirmed, a part of the catalyst was discolored and deactivated.
表２中、実施例１、２の「熱媒浴の温度」は、各工程において設定した熱媒浴の温度を示した。一方、比較例１、２の「熱媒浴の温度」は、各工程終了時の熱媒浴の温度を示した。 In Table 2, “temperature of the heat medium bath” in Examples 1 and 2 indicates the temperature of the heat medium bath set in each step. On the other hand, “temperature of the heat medium bath” in Comparative Examples 1 and 2 indicates the temperature of the heat medium bath at the end of each step.
表２、および図１、２から明らかなように、実施例１、２の場合、ホットスポットの温度を十分に抑制でき、短時間でスタートアップを行うことができた。また、第３工程が終了した後、反応器を開放して触媒を確認したところ、異常は認められなかった。 As is clear from Table 2 and FIGS. 1 and 2, in the case of Examples 1 and 2, the temperature of the hot spot could be sufficiently suppressed, and start-up could be performed in a short time. Moreover, after the 3rd process was complete | finished, when the reactor was open | released and the catalyst was confirmed, abnormality was not recognized.
一方、比較例１の場合、表２、および図３から明らかなように、第２工程においてイソブチレンの供給量が定常運転時における供給量の８０％に達したときに、ΔＴｍａｘが５０℃を越えたため、ΔＴｍａｘが５０℃以下に下がるまでイソブチレンの供給量の上昇をやめざるをえず、第２工程の所要時間が２３時間と大幅に長くなった。その結果、スタートアップが完了するまでに３０時間も要した。なお、ΔＴｍａｘの位置は、原料ガスの供給開始から２０時間目に、その位置が原料ガス入口側に大きく移動した。
比較例３の場合、表２、および図４から明らかなように、第２工程においてイソブチレンの供給量が定常運転時における供給量の８０％に達したときに、ΔＴｍａｘが５０℃を越えたため、ΔＴｍａｘが５０℃以下に下がるまでイソブチレンの供給量の上昇をやめざるをえず、第２工程の所要時間が１８時間と大幅に長くなった。その結果、スタートアップが完了するまでに２５時間も要した。なお、ΔＴｍａｘの位置は、原料ガスの供給開始から２１時間目に、その位置が原料ガス入口側に大きく移動した。
なお、比較例１、３において第３工程が終了した後、反応器を開放して触媒を確認したところ、異常は認められなかった。
On the other hand, in the case of Comparative Example 1, as is clear from Table 2 and FIG. 3, when the isobutylene supply amount reaches 80% of the supply amount in the steady operation in the second step, ΔT max becomes 50 ° C. Therefore, the increase in isobutylene supply amount had to be stopped until ΔT max dropped to 50 ° C. or less, and the time required for the second step was significantly increased to 23 hours. As a result, it took 30 hours to complete the startup. Note that the position of ΔT max greatly moved to the source
In the case of Comparative Example 3, as apparent from Table 2 and FIG. 4, ΔT max exceeded 50 ° C. when the amount of isobutylene supplied in the second step reached 80% of the amount supplied in steady operation. Until the ΔT max decreased to 50 ° C. or less, the supply amount of isobutylene had to be stopped, and the time required for the second step was significantly increased to 18 hours. As a result, it took 25 hours to complete the startup. Note that the position of ΔT max greatly moved to the source gas inlet side at 21 hours from the start of the supply of the source gas.
In Comparative Examples 1 and 3, after completion of the third step, the reactor was opened and the catalyst was confirmed. No abnormality was observed.
Claims (4)
前記原料ガスの供給開始から定常運転に移行するまでの間に、下記条件（１）および（２）を満たすように反応原料の供給量を段階的に増やし、その後、定常運転を行うことを特徴とする（メタ）アクロレインまたは（メタ）アクリル酸の製造方法。
（１）反応原料の供給量が、定常運転時における供給量の１０〜６０％のときに、プロピレンおよび／またはイソブチレンの平均転化率が１００〜９８％である。
（２）反応原料の供給量が、定常運転時における供給量の９０〜１００％のときに、プロピレンおよび／またはイソブチレンの平均転化率が９７％以下である。 Using a fixed bed tubular reactor equipped with a reaction tube filled with a solid oxidation catalyst containing at least molybdenum and bismuth as catalyst components to form a catalyst layer, propylene, isobutylene, tertiary butyl alcohol, and methyl tertiary A raw material gas containing at least one selected from the group consisting of butyl ether as a reaction raw material is supplied to the reaction tube, and (meth) acrolein or (meth) acrylic acid is produced by a gas phase catalytic oxidation reaction with an oxygen-containing gas. In the method
Between the start of the supply of the raw material gas and the transition to the steady operation, the supply amount of the reaction raw material is increased stepwise so as to satisfy the following conditions (1) and (2), and then the steady operation is performed. A method for producing (meth) acrolein or (meth) acrylic acid.
(1) When the supply amount of the reaction raw material is 10 to 60% of the supply amount in the steady operation, the average conversion rate of propylene and / or isobutylene is 100 to 98%.
(2) When the supply amount of the reaction raw material is 90 to 100% of the supply amount in the steady operation, the average conversion rate of propylene and / or isobutylene is 97% or less.
（３）反応原料の供給量が、定常運転時における供給量の６０％超、９０％未満のときに、プロピレンおよび／またはイソブチレンの平均転化率が９９〜９７％である。 2. The (meta) supply according to claim 1, wherein the supply amount of the reaction raw material is increased stepwise so that the following condition (3) is further satisfied from the start of supply of the raw material gas to the transition to steady operation. ) A process for producing acrolein or (meth) acrylic acid.
(3) When the supply amount of the reaction raw material is more than 60% and less than 90% of the supply amount in steady operation, the average conversion rate of propylene and / or isobutylene is 99 to 97%.
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