WO2015008814A1 - 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 - Google Patents
不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 Download PDFInfo
- Publication number
- WO2015008814A1 WO2015008814A1 PCT/JP2014/068992 JP2014068992W WO2015008814A1 WO 2015008814 A1 WO2015008814 A1 WO 2015008814A1 JP 2014068992 W JP2014068992 W JP 2014068992W WO 2015008814 A1 WO2015008814 A1 WO 2015008814A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- carboxylic acid
- temperature
- unsaturated carboxylic
- unsaturated
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 19
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 8
- 239000003054 catalyst Substances 0.000 claims abstract description 144
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 230000008859 change Effects 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 44
- 239000000843 powder Substances 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000001354 calcination Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000003570 air Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 4
- 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 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 229910000380 bismuth sulfate 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
- C07C27/14—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen wholly gaseous reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
Definitions
- the present invention relates to a method for producing a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by vapor-phase catalytic oxidation of alkene with molecular oxygen or a molecular oxygen-containing gas.
- a method for producing a corresponding unsaturated aldehyde or unsaturated carboxylic acid from an alkene or an alcohol capable of generating an alkene by an intramolecular dehydration reaction as a raw material is widely practiced industrially.
- the occurrence of a portion (hot spot) is a big problem.
- the generation of hot spots shortens the catalyst life, decreases the yield due to excessive oxidation reaction, and in the worst case leads to runaway reaction. Therefore, the activity of the catalyst that fills the hot spot generation part to suppress the hot spot temperature Several techniques have been proposed to control this.
- Patent Document 1 discloses a technique for reducing the hot spot temperature by using a catalyst whose activity is adjusted by changing the loading amount, or by using a catalyst whose activity is adjusted by changing the calcination temperature of the catalyst.
- Patent Document 2 discloses a technique of using a catalyst whose activity is adjusted by changing the ratio of the apparent density of the catalyst.
- Patent Document 3 uses a catalyst whose activity is adjusted by changing the content of the inactive component of the catalyst molded body, changing the occupied volume of the catalyst molded body, the type and / or amount of alkali metal, and the firing temperature of the catalyst. Techniques to do this are disclosed.
- Patent Document 4 discloses a technique in which a reaction zone in which the occupied volume of a catalyst molded body is changed is provided and an inert substance is mixed in at least one reaction zone.
- Patent Document 5 discloses a technique of using a catalyst whose activity is adjusted by changing the calcination temperature of the catalyst.
- Patent Document 6 discloses a technique of using a catalyst whose activity is adjusted by changing the occupied volume of the catalyst and the calcination temperature and / or the type and amount of alkali metal.
- the applicant of the present application has proposed and improved the Japanese Patent Application Laid-Open No. 2014-19675, etc., but as a result of further diligent investigation, the change Sn of the hot spot temperature relative to the change of the reaction bath temperature was specified.
- the present invention that can solve the above-mentioned problem that can be said to be unique to an industrial plant and can stably maintain a high yield over a long period of time has been completed.
- Y is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As), antimony (Sb), and tungsten (W), and Z is sodium (Na), potassium ( K), rubidium (Rb), and at least one element selected from the group consisting of cesium (Cs), wherein (a) to (g) represent the atomic ratio of each component, and h is the degree of oxidation of the catalyst component.
- a 0.80-2.0
- b 1-3
- c 3-7
- d 2-4
- e 0-10
- f 0-10
- g 0 .01 to 0.10
- h the oxidation state of other elements Is denoted by a numerical value which added together, d / a is 1.9 or more than 3.2, and d / g is at 29 or more 69 or less, and a / g is 18 or more 39 or less), About.
- the present invention in the production of a corresponding unsaturated aldehyde or unsaturated carboxylic acid using an alkene or an alcohol capable of generating an alkene by an intramolecular dehydration reaction as a raw material, it can be safely and stably produced in an industrial plant over a long period of time. The yield can be maintained.
- N splitting N Is provided with a plurality of catalyst layers formed by N ⁇ 2
- Sn hot spot temperature
- the catalyst is filled so that Sn ⁇ 6.
- the catalyst used in the present invention is not particularly limited in shape and type as long as the above conditions can be achieved, but can be prepared, for example, through the following steps.
- Molybdenum component raw materials include molybdenum oxides such as molybdenum trioxide, molybdic acid such as molybdic acid and ammonium molybdate or salts thereof, heteropoly acids containing molybdenum such as phosphomolybdic acid and silicomolybdic acid, or salts thereof, and the like. Although it can be used, a high-performance catalyst can be obtained preferably when ammonium molybdate is used.
- ammonium molybdate includes a plurality of types of compounds such as ammonium dimolybdate, ammonium tetramolybdate, and ammonium heptamolybdate. Among these, ammonium heptamolybdate is most preferable.
- bismuth component raw material bismuth salts such as bismuth nitrate, bismuth subcarbonate, bismuth sulfate, bismuth acetate, bismuth trioxide, metal bismuth, etc. can be used, but bismuth nitrate is more preferred. A high performance catalyst is obtained.
- an iron component raw material, a cobalt component raw material, and / or a nickel component raw material are dissolved and mixed in water at a desired ratio under conditions of 10 to 80 ° C., and a molybdenum component separately prepared under conditions of 20 to 90 ° C.
- aqueous solution or slurry After mixing with the raw material and the Z component raw material aqueous solution or slurry and heating and stirring for about 1 hour at 20 to 90 ° C., an aqueous solution in which the bismuth component raw material is dissolved, and the X component raw material and the Y component raw material as necessary. Addition to obtain an aqueous solution or slurry containing the catalyst component. Henceforth, both are collectively called a preparation liquid (A).
- the preparation liquid (A) does not necessarily contain all the catalyst constituent elements, and a part of the elements or a part of the amount may be added in the subsequent steps.
- the preparation liquid (A) when the preparation liquid (A) is prepared, the amount of water used to dissolve each component raw material, and when adding an acid such as sulfuric acid, nitric acid, hydrochloric acid, tartaric acid or acetic acid for dissolution, the raw material is dissolved. If the acid concentration in the aqueous solution is not suitable for preparation in the range of 5% by weight to 99% by weight, for example, the form of the preparation liquid (A) may be a clay-like lump. In this case, an excellent catalyst cannot be obtained. As the form of the preparation liquid (A), an aqueous solution or a slurry is preferable because an excellent catalyst can be obtained.
- the drying method is not particularly limited as long as the preparation liquid (A) can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness.
- spray drying that can be dried from the slurry into powder or granules in a short time is particularly preferable.
- the drying temperature of spray drying varies depending on the slurry concentration, the liquid feeding speed, etc., but the temperature at the outlet of the dryer is generally 70 to 150 ° C. Further, it is preferable to dry so that the average particle size of the dry powder obtained at this time is 10 to 700 ⁇ m. A dry powder (B) is thus obtained.
- Step c) Pre-calcination The obtained dry powder (B) is calcined at 200 ° C. to 600 ° C., preferably 300 ° C. to 600 ° C. under air flow to improve the moldability, mechanical strength, and catalyst performance of the catalyst. Tend to. The firing time is preferably 1 hour to 12 hours. Thus, the pre-fired powder (C) is obtained.
- Step d) Molding Although there is no particular limitation on the molding method, a method using a tableting molding machine, an extrusion molding machine or the like is preferable when molding into a cylindrical shape or a ring shape. More preferably, it is a case of forming into a spherical shape, and the pre-fired powder (C) may be formed into a sphere with a molding machine, but the pre-fired powder (C) (including a molding aid and a strength improver if necessary). A method in which is supported on a carrier such as an inert ceramic is preferred.
- a supporting method a rolling granulation method, a method using a centrifugal fluid coating apparatus, a wash coating method and the like are widely known.
- the method is not particularly limited as long as the pre-calcined powder (C) can be uniformly supported on the carrier.
- the flat calcined powder (C) is flat on the bottom of the fixed cylindrical container.
- binder examples include water, ethanol, methanol, propanol, polyhydric alcohol, polyvinyl alcohol as a polymeric binder, silica sol aqueous solution of an inorganic binder, and the like.
- Ethanol, methanol, propanol, polyhydric alcohol A diol such as ethylene glycol or a triol such as glycerin is more preferable.
- an aqueous glycerin solution By using an appropriate amount of an aqueous glycerin solution, the moldability becomes good, and a high-performance catalyst with high mechanical strength is obtained. Specifically, when an aqueous solution having a glycerin concentration of 5% by weight or more is used, the performance is particularly high. A catalyst is obtained.
- the amount of these binders used is usually 2 to 80 parts by weight with respect to 100 parts by weight of the pre-fired powder (C).
- the inert carrier one having a diameter of about 2 to 8 mm is usually used, and the pre-fired powder (C) is supported thereon.
- the loading is determined in consideration of the conditions for using the catalyst, for example, the reaction conditions such as the space velocity of the reaction raw material and the concentration of the raw material, but is usually 20 to 80% by weight.
- the supporting rate is expressed by the following equation.
- Loading ratio 100 ⁇ [weight of pre-fired powder (C) used for molding / (weight of pre-fired powder (C) used for molding + weight of inert carrier used for molding)]
- a molded body (D) is obtained.
- the mechanical strength of the molded body (D) is greatly influenced by the atomic ratio of the catalyst composition, that is, the type of compound produced by adjusting the atomic ratio and the fact that the phase form of the crystal structure is different even for the same compound. Receive.
- the micro physical properties such as the strength of the compound crystals in the composite metal oxide
- it is also affected by macroscopic physical property changes such as the particle size distribution of the pre-fired powder.
- the combined physical properties including not only the preparation method of each step but also the influence of the atomic ratio determine the mechanical strength of the catalyst finally prepared.
- the molded body (D) tends to improve catalytic activity and selectivity by calcination at a temperature of 200 to 600 ° C. for about 1 to 12 hours.
- the baking temperature is preferably 400 ° C. or higher and 600 ° C. or lower, and more preferably 500 ° C. or higher and 600 ° C. or lower.
- As the gas to be circulated air is simple and preferable.
- nitrogen, carbon dioxide, nitrogen oxide-containing gas for forming a reducing atmosphere, ammonia-containing gas, hydrogen gas and mixtures thereof may be used as the inert gas. Is possible. In this way, a catalyst (E) is obtained.
- the catalyst contained in all the catalyst layers of the fixed bed multitubular reactor used in the method of the present invention is not particularly limited, but a composite metal oxide having a composition represented by the following general formula (1) is used. It is preferable that it is included.
- X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn), copper (Cu), zinc (Zn), cerium (Ce) and samarium (Sm).
- Y is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As), antimony (Sb), and tungsten (W), and Z is sodium (Na), potassium ( K), rubidium (Rb), and at least one element selected from the group consisting of cesium (Cs), wherein (a) to (g) represent the atomic ratio of each component, and h is the degree of oxidation of the catalyst component.
- b 1 to 2.5
- d 2 to 3.5
- a / g 18 or more and 35 or less.
- the catalytic gas phase oxidation reaction of alkene in the present invention is carried out by using 7 to 12% by volume alkene, 5 to 18% by volume molecular oxygen, 0 to 60% by volume water vapor and 20 to 70% by volume inert as the raw material gas composition.
- a mixed gas composed of a gas, such as nitrogen or carbon dioxide, is applied on the catalyst prepared as described above in a temperature range of 250 to 450 ° C. and a pressure of normal pressure to 10 atm, preferably normal pressure to 5 atm. More preferably, the introduction is carried out by introducing from a normal pressure to 3 atm and a contact time of 0.5 to 10 seconds.
- the alkene includes alcohols that generate alkene in the intramolecular dehydration reaction, such as tertiary butyl alcohol.
- a higher space velocity (reaction substrate supply rate (NL / hr) / catalyst filling space volume (L)) of the reaction substrate such as alkene is preferable from the viewpoint of production efficiency, but if it is too high, the target product (acrolein) + Acrylic acid) in some cases, the practical life is preferably 40 to 200 hr ⁇ 1 , more preferably 60 to 180 hr ⁇ 1 in view of the fact that the yield of (acrylic acid) may decrease and the life of the catalyst may be shortened.
- NL represents the volume of the reaction substrate in the standard state.
- the alkene conversion rate is preferably in the vicinity of the conversion rate at which an effective yield (acrolein yield + acrylic acid yield) is obtained, and is usually 90 to 99.9%, preferably 96 to 99.5%, more Preferably, it is 97.5 to 99%.
- a catalyst layer formed by dividing into a plurality of N in the raw material gas flow direction of the reaction tube is provided, and the plurality of types of catalysts are activated from the raw material inlet to the outlet in the raw gas flow direction. It is preferable to arrange them so as to be higher.
- the number of divisions N is not particularly limited, but is usually 2 to 5, preferably 2 to 3.
- the temperature of the hot spot when the temperature of the hot spot is increased, an excessive oxidation reaction proceeds, whereby the raw material, the target product and the like are decomposed and the yield is lowered. Furthermore, the temperature distribution fluctuates greatly, and even a runaway reaction can occur.
- the reaction bath temperature may slightly vary due to the influence of external factors. In such a case, the hot spot temperature of the catalyst having a large Sn is likely to change, and careful operation is required.
- the external factor include a change in the flow rate of the raw material gas due to a change in the flow rate of the heat medium supplied into the reaction bath jacket of the reactor and a change in the outside air temperature.
- the present invention is characterized in that the rate of temperature change of the hot spot of the catalyst layer is controlled within a specific range. That is, when the change in the temperature of the hot spot per 1 ° C. (° C.) in the catalyst layer is Sn, Sn ⁇ 6, preferably Sn ⁇ 3. Sn is 0 ⁇ Sn.
- the hot spot as used in the field of this invention means the maximum value of the temperature in a catalyst layer, and usually refers to the hot spot in the catalyst layer arrange
- the alkene concentration is preferably 7 to 12% by volume, but Sn tends to increase as the alkene concentration increases. Therefore, when the alkene concentration is 8% by volume or more, the effect of the present invention is more remarkably exhibited.
- the temperature sensitivity can be reduced by carrying out the manufacturing method as described above, enabling a stable operation of the industrial plant over a long period of time and obtaining a stable yield.
- This effect is due to the fact that by reducing the temperature sensitivity, the amount of hot spot change with respect to the change in the reaction bath temperature can be kept small, so that the load caused by thermal degradation on the catalyst is reduced.
- acrolein yield (Number of moles of acrolein produced / number of moles of propylene supplied) ⁇ 100
- Acrylic acid yield (mol%) (Number of moles of acrylic acid produced / number of moles of supplied propylene) ⁇ 100
- Effective yield (mol%) acrolein yield + acrylic acid yield
- Sn in the present invention refers to the rate of change of the hot spot temperature of the catalyst layer with respect to the reaction bath, and in particular, the definition in this case refers to the change (° C.) of the hot spot temperature of the catalyst with respect to the change of the reaction bath temperature of 1 ° C. . Since this index can be regarded as the sensitivity of the hot spot temperature to changes in the reaction bath temperature, the inventors called it temperature sensitivity, and is an index of the stability of the catalyst in the operation of an industrial plant using this catalyst. Can be used as Sn can be determined from the hot spot temperature at two or more reaction bath temperatures selected from any reaction bath temperature as described above. The reaction bath temperature for obtaining Sn is generally 250 ° C. or higher and 400 ° C.
- reaction bath temperatures should be the reaction bath temperature that results in the conversion of the raw alkene suitable for producing the unsaturated aldehyde and also the unsaturated carboxylic acid.
- the reaction bath temperature for obtaining Sn is set in the range of 90% to 99.9% for propylene conversion. It is preferable to use the actually measured temperature rather than the set value as the reaction bath temperature required for obtaining Sn. Similarly, the measured value is used for the hot spot temperature.
- thermocouple In the hot spot temperature measurement, a thermocouple is installed in the reaction tube in the gas flow direction, the temperature is measured at intervals of about 5 cm to 10 cm, and the maximum temperature in the obtained catalyst layer is set as the hot spot temperature. The smaller the temperature measurement interval is, the better. If it is larger than 10 cm, accurate data may not be obtained.
- Production Example 1 (Preparation of catalyst) While heating and stirring 3000 parts by weight of distilled water, 423.7 parts by weight of ammonium molybdate and 0.73 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A1). Separately, 378.4 parts by weight of cobalt nitrate, 139.6 parts by weight of nickel nitrate, and 161.6 parts by weight of ferric nitrate were dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B1), and 81 parts by weight of concentrated nitric acid. An aqueous solution (C1) was prepared by dissolving 97.1 parts by weight of bismuth nitrate in 200 parts by weight of distilled water made acidic by adding.
- the powder obtained by mixing 100 parts by weight of the pre-fired powder with 5 parts by weight of crystalline cellulose is defined by the above formula (2) as an inert carrier (spherical substance having a diameter of 4.5 mm mainly composed of alumina and silica).
- the weight of the carrier used for molding and the weight of the pre-fired powder were adjusted so that the loading ratio accounted for 50% by weight.
- a 20 wt% aqueous glycerin solution was used as a binder and supported and molded into a spherical shape having a diameter of 5.2 mm to obtain a supported catalyst (E2).
- the supported catalyst (E2) was calcined in an air atmosphere at a calcining temperature of 530 ° C. for 4 hours to obtain a catalyst (F2).
- the supported catalyst (E2) was calcined at a calcining temperature of 520 ° C. for 4 hours to obtain a catalyst (F3).
- pre-calcined powder (D1) was obtained using cesium nitrate instead of potassium nitrate.
- the pre-fired powder (D1) was supported and molded in the same manner as described above to obtain a supported catalyst (E1).
- the supported catalyst (E1) was calcined in an air atmosphere at a calcining temperature of 530 ° C. for 4 hours to obtain a catalyst (F1).
- Comparative production example 1 While heating and stirring 3000 parts by weight of distilled water, 423.7 parts by weight of ammonium molybdate and 1.64 parts by weight of potassium nitrate were dissolved to obtain an aqueous solution (A2). Separately, 302.7 parts by weight of cobalt nitrate, 162.9 parts by weight of nickel nitrate, and 145.5 parts by weight of ferric nitrate are dissolved in 1000 parts by weight of distilled water to prepare an aqueous solution (B2), and 42 parts by weight of concentrated nitric acid. An aqueous solution (C2) was prepared by dissolving 164.9 parts by weight of bismuth nitrate in 200 parts by weight of distilled water acidified by adding.
- the pre-fired powder (D3) was supported and molded in the same manner as the pre-fired powder (D2) of Production Example 1 to obtain a supported catalyst (E3).
- the supported catalyst (E3) was calcined in an air atmosphere at a calcining temperature of 530 ° C. for 4 hours to obtain a catalyst (F4).
- the supported catalyst (E3) obtained in Comparative Production Example 1 was calcined in an air atmosphere at a calcining temperature of 520 ° C. for 4 hours to obtain a catalyst (F5).
- Example 1 The propylene oxidation reaction was carried out using the catalysts (F1) to (F5) prepared as described above.
- the composition is different between the catalyst (F1) on the reaction tube raw material gas inlet side and the reaction tube raw material gas outlet side catalyst (F2) or (F3) used in the examples, both are described in the general formula (1). Included in the composition range.
- a jacket for circulating molten salt as a heating medium and a thermocouple for measuring the temperature of the catalyst layer are installed on the tube axis, and a silica alumina sphere having a diameter of 5.2 mm is 20 cm from the raw material gas inlet side of a stainless steel reactor having an inner diameter of 25 mm.
- a diluted catalyst obtained by mixing the catalyst (F1) and the silica alumina mixture inert spherical carrier at a weight ratio of 85:15 as the first layer of the oxidation catalyst (raw material gas inlet side) sequentially toward the raw material gas outlet.
- the catalyst layer (F1) was 80 cm as the oxidation catalyst second layer and the catalyst (F2) was 190 cm as the oxidation catalyst third layer, thereby forming a three-layer catalyst layer, and the reaction bath temperature was 330 ° C.
- the pressure of the reaction tube outlet side during the entire gas circulation when 300 hours passed after the start of the reaction as 50 kPaG, by changing the reaction bath temperature was an oxidation reaction of propylene.
- the hot spot temperature of the oxidation catalyst first layer, Sn of the catalyst layer, and the effective yield were obtained. The results are shown in Table 1.
- Sn in Table 1 a value calculated by linear approximation was used.
- the temperature of the hot spot in Table 1 was described for the hot spot showing the highest temperature among the hot spots of each catalyst layer.
- Example 2 The oxidation reaction of propylene was carried out in the same manner as in Example 1 except that 190 cm of the oxidation catalyst (F3) was filled as the oxidation catalyst third layer (gas outlet side) under the oxidation reaction conditions of Example 1. As the values at the reaction bath temperatures of 316 ° C. and 328 ° C., the hot spot temperature of the catalyst layer on the raw material gas inlet side, Sn of the catalyst layer, and the effective yield were obtained. The results are shown in Table 1.
- Example 3 In the oxidation reaction conditions of Example 1, 120 cm of catalyst (F1) was filled as the oxidation catalyst first layer (raw material gas inlet side), and the catalyst (F2) was sequentially formed as the second catalyst layer (gas outlet side) toward the raw material gas outlet. ) was charged in the same manner as in Example 1 except that the catalyst layer had a two-layer structure by filling 230 cm. As the values at the reaction bath temperatures of 314 ° C. and 324 ° C., the hot spot temperature of the catalyst layer on the raw material gas inlet side, Sn of the catalyst layer, and the effective yield were obtained. The results are shown in Table 1.
- Example 5 The same method as in Example 4 except that the space velocity of propylene is 150 h ⁇ 1 under the oxidation reaction conditions in Example 4 and the pressure on the outlet side of the reaction tube is 80 kPaG when all the gases are supplied.
- the propylene oxidation reaction was carried out.
- the values at the reaction bath temperatures of 314 ° C. and 326 ° C. the hot spot temperature of the catalyst layer on the raw material gas inlet side, Sn of the catalyst layer, and the effective yield were obtained. The results are shown in Table 1.
- the present invention is useful in industrial plants that produce unsaturated aldehydes and unsaturated carboxylic acids.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
A)固定床多管型反応器を用いて、アルケンを部分酸化して対応する不飽和アルデヒドおよび/または不飽和カルボン酸を製造する方法であって、
反応管のガス流れ方向に対しN分割(NはN≧2)して形成される複数の触媒層を設け、触媒層における反応浴温度変化1℃当たりのホットスポット温度の変化(℃)をSnとしたとき、複数の触媒層の少なくともいずれかにおいてSn ≦6とする不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法、
B)複数の触媒層の少なくともいずれかにおいてSn≦3とするA)記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法、
C)N=2または3であるA)またはB)に記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法、
D)原料中のアルケンの濃度が7~12容量%以下であるA)からC)のいずれか1項記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法、
E)全触媒層が、下記一般式(1)で表される組成を有する複合金属酸化物を含むA)からD)のいずれか1項に記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法、
一般式(1)
Mo12BiaFebCocNidXeYfZgOh
(Xはマグネシウム(Mg)、カルシウム(Ca)、マンガン(Mn)、銅(Cu)、亜鉛(Zn)、セリウム(Ce)及びサマリウム(Sm)からなる群から選ばれる少なくとも1種の元素であり、Yはホウ素(B)、リン(P)、砒素(As)、アンチモン(Sb)及びタングステン(W)からなる群から選ばれる少なくとも1種の元素であり、Zはナトリウム(Na)、カリウム(K)、ルビジウム(Rb)、セシウム(Cs)からなる群より選ばれる少なくとも1種の元素であり、(a)から(g)は各成分の原子比率を表し、hは触媒成分の酸化度で決定される数値を表し、a=0.80~2.0、b=1~3、c=3~7、d=2~4、e=0~10、f=0~10、g=0.01~0.10であり、hは他の元素の酸化状態を満足させる数値で表記され、d/aが1.9以上3.2以下であり、かつd/gが29以上69以下であり、かつa/gが18以上39以下である)、
に関する。
一般に触媒を構成する各元素の出発原料は特に制限されるものではない。モリブデン成分原料としては三酸化モリブデンのようなモリブデン酸化物、モリブデン酸、モリブデン酸アンモニウムのようなモリブデン酸又はその塩、リンモリブデン酸、ケイモリブデン酸のようなモリブデンを含むヘテロポリ酸又はその塩などを用いることができるが、好ましくはモリブデン酸アンモニウムを使用した場合で、高性能な触媒を得ることができる。特にモリブデン酸アンモニウムには、ジモリブデン酸アンモニウム、テトラモリブデン酸アンモニウム、ヘプタモリブデン酸アンモニウム等、複数種類の化合物が存在するが、その中でもヘプタモリブデン酸アンモニウムを使用した場合が最も好ましい。ビスマス成分原料としては硝酸ビスマス、次炭酸ビスマス、硫酸ビスマス、酢酸ビスマスなどのビスマス塩、三酸化ビスマス、金属ビスマスなどを用いることができるが、より好ましくは硝酸ビスマスであり、これを使用した場合に高性能な触媒が得られる。鉄、コバルト、ニッケル及びその他の元素の原料としては通常は酸化物あるいは強熱することにより酸化物になり得る硝酸塩、炭酸塩、有機酸塩、水酸化物等又はそれらの混合物を用いることができる。例えば、鉄成分原料とコバルト成分原料及び/又はニッケル成分原料を所望の比率で10~80℃の条件下にて水に溶解混合し、20~90℃の条件下にて別途調合されたモリブデン成分原料およびZ成分原料水溶液もしくはスラリーと混合し、20~90℃の条件下にて1時間程度加熱撹拌した後、ビスマス成分原料を溶解した水溶液と、必要に応じX成分原料、Y成分原料とを添加して触媒成分を含有する水溶液またはスラリーを得る。以降、両者をまとめて調合液(A)と称する。ここで、調合液(A)は必ずしもすべての触媒構成元素を含有する必要は無く、その一部の元素または一部の量を以降の工程で添加してもよい。また、調合液(A)を調合する際に各成分原料を溶解する水の量や、溶解のために硫酸や硝酸、塩酸、酒石酸、酢酸などの酸を加える場合には、原料が溶解するのに十分な水溶液中の酸濃度が、例えば5重量%~99重量%の範囲で調合に適していないと、調合液(A)の形態が粘土状の塊となる場合がある。この場合では、優れた触媒が得られない。調合液(A)の形態としては水溶液またはスラリーが、優れた触媒が得られるため、好ましい。
次いで上記で得られた調合液(A)を乾燥し、乾燥粉体とする。乾燥方法は、調合液(A)を完全に乾燥できる方法であれば特に制限はないが、例えばドラム乾燥、凍結乾燥、噴霧乾燥、蒸発乾固等が挙げられる。これらのうち本発明においては、スラリーから短時間に粉体又は顆粒に乾燥することができる噴霧乾燥が特に好ましい。噴霧乾燥の乾燥温度はスラリーの濃度、送液速度等によって異なるが概ね乾燥機の出口における温度が70~150℃である。また、この際得られる乾燥紛体の平均粒径が10~700μmとなるよう乾燥するのが好ましい。こうして乾燥粉体(B)を得る。
得られた乾燥紛体(B)は空気流通下で200℃から600℃で、好ましくは300℃から600℃で焼成することで触媒の成型性、機械的強度、触媒性能が向上する傾向がある。焼成時間は1時間から12時間が好ましい。こうして予備焼成紛体(C)を得る。
成型方法に特に制限はないが円柱状、リング状に成型する際には打錠成型機、押し出し成型機などを用いた方法が好ましい。さらに好ましくは、球状に成型する場合であり、成型機で予備焼成紛体(C)を球形に成型しても良いが、予備焼成紛体(C)(必要により成型助剤、強度向上剤を含む)を不活性なセラミック等の担体に担持させる方法が好ましい。ここで担持方法としては転動造粒法、遠心流動コーティング装置を用いる方法、ウォッシュコート方法等が広く知られている。予備焼成紛体(C)が担体に均一に担持できる方法で有れば特に限定されないが、触媒の製造効率や調製される触媒の性能を考慮した場合、より好ましくは固定円筒容器の底部に、平らな、あるいは凹凸のある円盤を有する装置で、円盤を高速で回転させることにより、容器内にチャージされた担体を、担体自体の自転運動と公転運動の繰り返しにより激しく撹拌させ、ここに予備焼成紛体(C)並びに必要により、成型助剤及び/または強度向上剤を添加することにより粉体成分を担体に担持させる方法が好ましい。尚、担持に際して、バインダーを使用するのが好ましい。用いうるバインダーの具体例としては、水やエタノール、メタノール、プロパノール、多価アルコール、高分子系バインダーのポリビニルアルコール、無機系バインダーのシリカゾル水溶液等が挙げられるが、エタノール、メタノール、プロパノール、多価アルコールが好ましく、エチレングリコール等のジオールやグリセリン等のトリオール等がより好ましい。グリセリン水溶液を適量使用することにより成型性が良好となり、機械的強度の高い、高性能な触媒が得られ、具体的にはグリセリンの濃度5重量%以上の水溶液を使用した場合に特に高性能な触媒が得られる。これらバインダーの使用量は、予備焼成紛体(C)100重量部に対して通常2~80重量部である。不活性担体は、通常、直径2~8mm程度のものを使用し、これに予備焼成紛体(C)を担持させる。その担持率は触媒使用条件、たとえば反応原料の空間速度、原料濃度などの反応条件を考慮して決定されるものであるが、通常20重量%から80重量%である。ここで担持率は以下の式で表記される。
100×〔成型に使用した予備焼成紛体(C)の重量/(成型に使用した予備焼成紛体(C)の重量+成型に使用した不活性担体の重量)〕 式(2)
成型体(D)は200~600℃の温度で1~12時間程度焼成することで触媒活性、選択性が向上する傾向にある。焼成温度は400℃以上600℃以下が好ましく、500℃以上600℃以下がより好ましい。流通させるガスとしては空気が簡便で好ましいが、その他に不活性ガスとして窒素、二酸化炭素、還元雰囲気にするための窒素酸化物含有ガス、アンモニア含有ガス、水素ガスおよびそれらの混合物を使用することも可能である。こうして触媒(E)を得る。
Snが大きくなる場合は、反応浴温度の変化に対してホットスポット温度が大きく変動することになるため、多くのデメリットが生じる。まずは触媒層のホットスポットの温度が過度に高くなることは触媒の局所的な劣化を引き起こす。また、ホットスポットの温度が高くなることによって過度な酸化反応が進行することにより原料および目的生成物等が分解され収率が低下する。さらには、温度分布が大きく変動し、暴走反応さえ起こしかねない。
また、工業プラントにおいては反応浴温度を意図的に変化させていない場合でも、外部因子の影響で反応浴温度がわずかに変動する場合がある。このような場合、Snが大きい触媒はホットスポット温度が変化しやすく、運転に細心の注意を要する。外部因子とは、例えば反応器の反応浴ジャケット内に供給される熱媒体の流速の変化や外気温の変化による原料ガス流量の変動などが挙げられる。
なお、本発明でいうホットスポットとは触媒層内温度の極大値のことを意味し、通常は最も原料ガス入口側に配置された触媒層内のホットスポットを指す。たとえば最も原料ガス入口側に配置された触媒層に温度の極大値が存在しない場合、次層以降の最も原料ガス入口側に配置された触媒層内の温度の極大値をホットスポットとして、Snを定義する。
アクロレイン収率(モル%)
=(生成したアクロレインのモル数/供給したプロピレンのモル数)×100
アクリル酸収率(モル%)
=(生成したアクリル酸のモル数/供給したプロピレンのモル数)×100
有効収率(モル%)=アクロレイン収率+アクリル酸収率
Snは上記のように任意の反応浴温度から選ばれる2点以上の反応浴温度におけるホットスポット温度から求めることが出来る。Snを求めるための反応浴温度は、一般的には250℃以上400℃以下であり、270℃以上380℃以下であることが好ましく、290℃以上360℃以下である事が更に好ましい。当然のことながら、これらの反応浴温度は、不飽和アルデヒドおよびまた不飽和カルボン酸を製造するにあたって好適な原料アルケンの転化率となる反応浴温度であるべきである。原料がプロピレンである場合、Snを求めるための反応浴温度はプロピレン転化率が90%から99.9%の範囲で設定される。
Snを求める際に必要な反応浴温度は設定値ではなく実測温度を用いるのが好ましい。同様にホットスポット温度も実測値を使用する。ホットスポット温度測定は、反応管内にガス流れ方向に熱電対を設置し、5cmないし10cm間隔程度で温度測定を行い、得られた触媒層内の最高温度をホットスポット温度とする。温度測定の間隔は小さいほど好ましく、10cmより大きいと正確なデータが得られない場合があり好ましくない。
(触媒の調製)
蒸留水3000重量部を加熱攪拌しながらモリブデン酸アンモニウム423.7重量部と硝酸カリウム0.73重量部を溶解して水溶液(A1)を得た。別に、硝酸コバルト378.4重量部、硝酸ニッケル139.6重量部、硝酸第二鉄161.6重量部を蒸留水1000重量部に溶解して水溶液(B1)を、また、濃硝酸81重量部を加えて酸性にした蒸留水200重量部に硝酸ビスマス97.1重量部を溶解して水溶液(C1)をそれぞれ調製した。上記水溶液(A1)に(B1)、(C1)を順次、激しく攪拌しながら混合し、生成した懸濁液を、スプレードライヤーを用いて乾燥し440℃で6時間焼成し予備焼成粉末(D2)を得た。このときの触媒活性成分の酸素を除いた組成比は原子比でMo=12、Bi=1.0、Ni=3.0、Fe=2.0、Co=6.5、K=0.05であった。
その後、予備焼成粉末100重量部に結晶セルロース5重量部を混合した粉末を不活性担体(アルミナ、シリカを主成分とする直径4.5mmの球状物質)に、上記式(2)で定義される担持率が、50重量%を占める割合になるように、成型に使用する担体重量および予備焼成粉末重量を調整した。20重量%グリセリン水溶液をバインダーとして使用し、直径5.2mmの球状に担持成型して担持触媒(E2)を得た。この担持触媒(E2)を、焼成温度530℃で、4時間空気雰囲気下で焼成することで触媒(F2)を得た。同様にして担持触媒(E2)を焼成温度520℃で4時間焼成することで触媒(F3)を得た。
同様にして硝酸カリウムの代わりに硝酸セシウムを用いて予備焼成粉末(D1)を得た。得られた予備焼成粉末(D1)の触媒活性成分の酸素を除いた組成比は原子比でMo=12、Bi=1.0、Ni=3.0、Fe=2.0、Co=6.5、Cs=0.03であった。この予備焼成粉末(D1)を上記と同様に担持成型して担持触媒(E1)を得た。この担持触媒(E1)を、焼成温度530℃で4時間、空気雰囲気下で焼成することで触媒(F1)を得た。
蒸留水3000重量部を加熱攪拌しながらモリブデン酸アンモニウム423.7重量部と硝酸カリウム1.64重量部を溶解して水溶液(A2)を得た。別に、硝酸コバルト302.7重量部、硝酸ニッケル162.9重量部、硝酸第二鉄145.5重量部を蒸留水1000重量部に溶解して水溶液(B2)を、また、濃硝酸42重量部を加えて酸性にした蒸留水200重量部に硝酸ビスマス164.9重量部を溶解して水溶液(C2)をそれぞれ調製した。上記水溶液(A2)に(B2)、(C2)を順次、激しく攪拌しながら混合し、生成した懸濁液をスプレードライヤーを用いて乾燥し440℃で6時間焼成し予備焼成粉末(D3)を得た。このときの触媒活性成分の酸素を除いた組成比は原子比でMo=12、Bi=1.7、Ni=2.8、Fe=1.8、Co=5.2、K=0.15であった。
担持触媒(E3)を、焼成温度530℃で4時間、空気雰囲気下で焼成することで触媒(F4)を得た。
また、比較製造例1で得られた担持触媒(E3)を、焼成温度520℃で4時間、空気雰囲気下で焼成することで触媒(F5)を得た。
上記のようにして調製した触媒(F1)から触媒(F5)を使用して、プロピレンの酸化反応を実施した。なお、実施例にて使用する、反応管原料ガス入口側の触媒(F1)と反応管原料ガス出口側触媒(F2)または(F3)では組成が異なるが、ともに一般式(1)に記載の組成範囲に含まれる。
熱媒体として溶融塩を循環させるジャケット及び触媒層温度を測定するための熱電対を管軸に設置した、内径25mmのステンレス製反応器の原料ガス入口側より直径5.2mmのシリカアルミナ球を20cm充填し、順次原料ガス出口へ向かって、酸化触媒第一層(原料ガス入口側)として、触媒(F1)とシリカアルミナ混合物不活性球状担体を重量比85:15で混合した希釈触媒を80cm、酸化触媒第二層として触媒(F1)を80cm、酸化触媒第三層として触媒(F2)を190cmそれぞれ充填することにより触媒層を3層構成とし、反応浴温度を330℃にした。ここに原料モル比率が、プロピレン:酸素:水:窒素=1:1.7:8.8:1となるようにプロピレン、空気、水、窒素の供給量を設定し、プロピレンの空間速度が100h-1となるよう流通させ、その全ガス流通時における反応管出口側の圧力が50kPaGとして反応開始後300時間経過したとき、反応浴温度を変化させて、プロピレンの酸化反応を実施した。反応浴温度318℃と328℃における値として、酸化触媒第一層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。なお、表1におけるSnについては、線形近似により算出した値を用いた。また、表1におけるホットスポットの温度は、各触媒層のホットスポットのうち、最高温度を示すホットスポットにつき記載した。
実施例1の酸化反応条件において、酸化触媒第三層(ガス出口側)として酸化触媒(F3)を190cm充填したこと以外は、実施例1と同様の方法でプロピレンの酸化反応を実施した。反応浴温度316℃と328℃における値として、原料ガス入口側の触媒層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。
実施例1の酸化反応条件において、酸化触媒第一層(原料ガス入口側)として触媒(F1)を120cm充填し、順次原料ガス出口へ向かって触媒第二層(ガス出口側)として触媒(F2)を230cm充填することにより触媒層を2層構成としたこと以外は、実施例1と同様の方法でプロピレンの酸化反応を実施した。反応浴温度314℃と324℃における値として、原料ガス入口側の触媒層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。
実施例1の酸化反応条件において、酸化触媒第一層(原料ガス入口側)として触媒(F1)を135cm充填し、順次原料ガス出口へ向かって触媒第二層(ガス出口側)として酸化触媒(F2)を165cm充填することにより触媒層を2層構成とし、原料モル比率が、プロピレン:酸素:水:窒素=1:1.7:2:7.6となるようにプロピレン、空気、水、窒素の供給量を設定し、プロピレンの空間速度が110h-1となるよう流通させ、その全ガス流通時における反応管出口側の圧力が50kPaGとすること以外は、実施例1と同様の方法でプロピレンの酸化反応を実施した。反応浴温度310℃と321℃における値として、原料ガス入口側の触媒層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。
実施例4の酸化反応条件において、プロピレンの空間速度が150h-1となるよう流通させ、その全ガス流通時における反応管出口側の圧力が80kPaGとすること以外は、実施例4と同様の方法でプロピレンの酸化反応を実施した。反応浴温度314℃と326℃における値として、原料ガス入口側の触媒層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。
実施例1の酸化反応条件において、酸化触媒第一層(原料ガス入口側)として触媒(F4)とシリカアルミナ混合物不活性球状担体を重量比70:30で混合した希釈触媒を120cm充填し、順次原料ガス出口へ向かって酸化触媒第二層(原料ガス入口側)として触媒(F5)を230cm充填することにより触媒層を2層構成とし、プロピレンの空間速度が100h-1となるよう流通させたこと以外は、実施例1と同様の方法でプロピレンの酸化反応を実施した。反応浴温度322℃と330℃における値として、原料ガス入口側の触媒層のホットスポット温度、同触媒層のSn、有効収率を得た。結果を表1に示す。
なお、本出願は、2013年7月18日付で出願された日本国特許出願(特願2013-149333)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
Claims (5)
- 固定床多管型反応器を用いて、アルケンを部分酸化して対応する不飽和アルデヒドおよび/または不飽和カルボン酸を製造する方法であって、
反応管のガス流れ方向に対しN分割(NはN≧2)して形成される複数の触媒層を設け、触媒層における反応浴温度変化1℃当たりのホットスポット温度の変化(℃)をSnとしたとき、複数の触媒層の少なくともいずれかにおいてSn ≦6とする不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。 - 複数の触媒層の少なくともいずれかにおいてSn≦3とする請求項1記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。
- N=2または3である請求項1または2に記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。
- 原料中のアルケンの濃度が7~12容量%以下である請求項1から3のいずれか1項に記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。
- 全触媒層が、下記一般式(1)で表される組成を有する複合金属酸化物を含む請求項1から4のいずれか1項に記載の不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法。
一般式(1)
Mo12BiaFebCocNidXeYfZgOh
(Xはマグネシウム(Mg)、カルシウム(Ca)、マンガン(Mn)、銅(Cu)、亜鉛(Zn)、セリウム(Ce)及びサマリウム(Sm)からなる群から選ばれる少なくとも1種の元素であり、Yはホウ素(B)、リン(P)、砒素(As)、アンチモン(Sb)及びタングステン(W)からなる群から選ばれる少なくとも1種の元素であり、Zはナトリウム(Na)、カリウム(K)、ルビジウム(Rb)、セシウム(Cs)からなる群より選ばれる少なくとも1種の元素であり、(a)から(g)は各成分の原子比率を表し、hは触媒成分の酸化度で決定される数値を表し、a=0.80~2.0、b=1~3、c=3~7、d=2~4、e=0~10、f=0~10、g=0.01~0.10であり、hは他の元素の酸化状態を満足させる数値で表記され、d/aが1.9以上3.2以下であり、かつd/gが29以上69以下であり、かつa/gが18以上39以下である。)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG11201600350RA SG11201600350RA (en) | 2013-07-18 | 2014-07-17 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
MYPI2016700119A MY182262A (en) | 2013-07-18 | 2014-07-17 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
CN201480040828.8A CN105392761A (zh) | 2013-07-18 | 2014-07-17 | 不饱和醛和/或不饱和羧酸的制造方法 |
JP2015527327A JP6199972B2 (ja) | 2013-07-18 | 2014-07-17 | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
KR1020157036349A KR101819465B1 (ko) | 2013-07-18 | 2014-07-17 | 불포화 알데히드 및/또는 불포화 카본산의 제조 방법 |
US14/903,410 US9580376B2 (en) | 2013-07-18 | 2014-07-17 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
MX2016000550A MX2016000550A (es) | 2013-07-18 | 2014-07-17 | Metodo para fabricar aldehido insaturado y/o acido carboxilico insaturado. |
EP14825697.7A EP3023405A4 (en) | 2013-07-18 | 2014-07-17 | PROCESS FOR PRODUCING UNSATURATED ALDEHYDE AND / OR UNSATURATED CARBOXYLIC ACID |
RU2016105244A RU2654063C2 (ru) | 2013-07-18 | 2014-07-17 | Способ получения ненасыщенного альдегида и/или ненасыщенной карбоновой кислоты |
SA516370412A SA516370412B1 (ar) | 2013-07-18 | 2016-01-17 | طريقة لإنتاج ألدهيد غير مشبع و/أو حمض كربوكسيلى غير مشبع |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013149333 | 2013-07-18 | ||
JP2013-149333 | 2013-07-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015008814A1 true WO2015008814A1 (ja) | 2015-01-22 |
Family
ID=52346257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/068992 WO2015008814A1 (ja) | 2013-07-18 | 2014-07-17 | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US9580376B2 (ja) |
EP (1) | EP3023405A4 (ja) |
JP (1) | JP6199972B2 (ja) |
KR (1) | KR101819465B1 (ja) |
CN (1) | CN105392761A (ja) |
MX (1) | MX2016000550A (ja) |
MY (1) | MY182262A (ja) |
RU (1) | RU2654063C2 (ja) |
SA (1) | SA516370412B1 (ja) |
SG (1) | SG11201600350RA (ja) |
TW (1) | TWI585075B (ja) |
WO (1) | WO2015008814A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017010159A1 (ja) * | 2015-07-10 | 2017-01-19 | 日本化薬株式会社 | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
JP2017178817A (ja) * | 2016-03-29 | 2017-10-05 | 日本化薬株式会社 | 再スタートアップ方法 |
WO2019198763A1 (ja) | 2018-04-10 | 2019-10-17 | 日本化薬株式会社 | 不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造方法並びに不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造用触媒 |
JP2020152727A (ja) * | 2020-06-01 | 2020-09-24 | 日本化薬株式会社 | 再スタートアップ方法 |
WO2020203606A1 (ja) * | 2019-03-29 | 2020-10-08 | 日本化薬株式会社 | 触媒製造用乾燥顆粒、触媒、及び化合物の製造方法 |
WO2021141133A1 (ja) | 2020-01-10 | 2021-07-15 | 日本化薬株式会社 | 触媒、触媒の充填方法、および触媒を用いた化合物の製造方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019182089A1 (ja) * | 2018-03-23 | 2019-09-26 | 三菱ケミカル株式会社 | 触媒 |
CN113573811B (zh) * | 2019-03-29 | 2023-12-08 | 日本化药株式会社 | 不饱和醛的制造方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH083093A (ja) | 1994-06-20 | 1996-01-09 | Sumitomo Chem Co Ltd | アクロレインおよびアクリル酸の製造方法 |
JPH08336298A (ja) | 1995-06-06 | 1996-12-17 | Nippondenso Co Ltd | 車両用交流発電機の制御装置 |
JP2001226302A (ja) | 2000-02-16 | 2001-08-21 | Nippon Shokubai Co Ltd | アクロレインおよびアクリル酸の製造方法 |
JP2001328951A (ja) | 2000-05-19 | 2001-11-27 | Nippon Shokubai Co Ltd | 不飽和アルデヒドおよび不飽和カルボン酸の製造方法 |
JP2004002209A (ja) | 2002-03-29 | 2004-01-08 | Nippon Shokubai Co Ltd | 不飽和アルデヒドの製造方法 |
JP2005320315A (ja) | 2003-10-22 | 2005-11-17 | Nippon Shokubai Co Ltd | 接触気相酸化反応 |
JP2007326787A (ja) * | 2006-06-06 | 2007-12-20 | Sumitomo Chemical Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 |
JP2012176938A (ja) * | 2011-02-02 | 2012-09-13 | Nippon Kayaku Co Ltd | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
JP2014019675A (ja) | 2012-07-20 | 2014-02-03 | Nippon Kayaku Co Ltd | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5731689A (en) | 1995-06-06 | 1998-03-24 | Nippondenso Co., Ltd. | Control system for A.C. generator |
CN1093417C (zh) * | 1999-11-01 | 2002-10-30 | 何国顺 | 一种毛孔缩小的药物及其制备方法 |
US6620968B1 (en) * | 1999-11-23 | 2003-09-16 | Rohm And Haas Company | High hydrocarbon space velocity process for preparing unsaturated aldehydes and acids |
CN1170555C (zh) * | 2000-04-11 | 2004-10-13 | 隋锡梅 | 一种治疗溃疡病的中成药 |
US6960684B2 (en) | 2002-03-29 | 2005-11-01 | Nippon Shokubai Co., Ltd. | Production process for unsaturated aldehyde |
US7161044B2 (en) * | 2003-10-22 | 2007-01-09 | Nippon Shokubai Co., Ltd. | Catalytic gas phase oxidation reaction |
JP4677527B2 (ja) * | 2003-10-29 | 2011-04-27 | ビーエーエスエフ ソシエタス・ヨーロピア | プロペンからアクロレインを生じさせる不均一系触媒による気相部分酸化の長期稼働を行う方法 |
JP2005162744A (ja) * | 2003-11-14 | 2005-06-23 | Mitsubishi Chemicals Corp | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 |
US7326389B2 (en) * | 2003-12-26 | 2008-02-05 | Lg Chem, Ltd. | Method of producing unsaturated aldehyde and/or unsaturated acid |
JP2005213179A (ja) * | 2004-01-29 | 2005-08-11 | Mitsubishi Rayon Co Ltd | 触媒層およびその形成方法、固定床管型反応器、メタクロレインまたはメタクリル酸の製造方法 |
CN101657408B (zh) * | 2007-04-03 | 2012-10-03 | Lg化学株式会社 | 使用固定床催化部分氧化反应器制备不饱和醛和/或不饱和脂肪酸的方法 |
RU2609023C2 (ru) | 2011-07-12 | 2017-01-30 | Басф Се | Полиметаллические оксидные массы, содержащие молибден, висмут и железо |
-
2014
- 2014-07-17 SG SG11201600350RA patent/SG11201600350RA/en unknown
- 2014-07-17 JP JP2015527327A patent/JP6199972B2/ja active Active
- 2014-07-17 CN CN201480040828.8A patent/CN105392761A/zh active Pending
- 2014-07-17 US US14/903,410 patent/US9580376B2/en active Active
- 2014-07-17 KR KR1020157036349A patent/KR101819465B1/ko active IP Right Grant
- 2014-07-17 RU RU2016105244A patent/RU2654063C2/ru active
- 2014-07-17 WO PCT/JP2014/068992 patent/WO2015008814A1/ja active Application Filing
- 2014-07-17 EP EP14825697.7A patent/EP3023405A4/en not_active Withdrawn
- 2014-07-17 MX MX2016000550A patent/MX2016000550A/es unknown
- 2014-07-17 MY MYPI2016700119A patent/MY182262A/en unknown
- 2014-07-18 TW TW103124805A patent/TWI585075B/zh active
-
2016
- 2016-01-17 SA SA516370412A patent/SA516370412B1/ar unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH083093A (ja) | 1994-06-20 | 1996-01-09 | Sumitomo Chem Co Ltd | アクロレインおよびアクリル酸の製造方法 |
JPH08336298A (ja) | 1995-06-06 | 1996-12-17 | Nippondenso Co Ltd | 車両用交流発電機の制御装置 |
JP2001226302A (ja) | 2000-02-16 | 2001-08-21 | Nippon Shokubai Co Ltd | アクロレインおよびアクリル酸の製造方法 |
JP2001328951A (ja) | 2000-05-19 | 2001-11-27 | Nippon Shokubai Co Ltd | 不飽和アルデヒドおよび不飽和カルボン酸の製造方法 |
JP2004002209A (ja) | 2002-03-29 | 2004-01-08 | Nippon Shokubai Co Ltd | 不飽和アルデヒドの製造方法 |
JP2005320315A (ja) | 2003-10-22 | 2005-11-17 | Nippon Shokubai Co Ltd | 接触気相酸化反応 |
JP2007326787A (ja) * | 2006-06-06 | 2007-12-20 | Sumitomo Chemical Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 |
JP2012176938A (ja) * | 2011-02-02 | 2012-09-13 | Nippon Kayaku Co Ltd | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
JP2014019675A (ja) | 2012-07-20 | 2014-02-03 | Nippon Kayaku Co Ltd | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3023405A4 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017010159A1 (ja) * | 2015-07-10 | 2017-01-19 | 日本化薬株式会社 | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
JPWO2017010159A1 (ja) * | 2015-07-10 | 2018-04-19 | 日本化薬株式会社 | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
JP2017178817A (ja) * | 2016-03-29 | 2017-10-05 | 日本化薬株式会社 | 再スタートアップ方法 |
WO2017170721A1 (ja) * | 2016-03-29 | 2017-10-05 | 日本化薬株式会社 | 再スタートアップ方法 |
US10851040B2 (en) | 2016-03-29 | 2020-12-01 | Nippon Kayaku Kabushiki Kaisha | Restarting method |
US20200048175A1 (en) * | 2016-03-29 | 2020-02-13 | Nippon Kayaku Kabushiki Kaisha | Restarting method |
JPWO2019198763A1 (ja) * | 2018-04-10 | 2020-04-30 | 日本化薬株式会社 | 不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造方法並びに不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造用触媒 |
WO2019198763A1 (ja) | 2018-04-10 | 2019-10-17 | 日本化薬株式会社 | 不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造方法並びに不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造用触媒 |
US11254634B2 (en) | 2018-04-10 | 2022-02-22 | Nippon Kayaku Kabushiki Kaisha | Method for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid and catalyst for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid |
WO2020203606A1 (ja) * | 2019-03-29 | 2020-10-08 | 日本化薬株式会社 | 触媒製造用乾燥顆粒、触媒、及び化合物の製造方法 |
JP6792744B1 (ja) * | 2019-03-29 | 2020-11-25 | 日本化薬株式会社 | 触媒製造用乾燥顆粒、触媒、及び化合物の製造方法 |
WO2021141133A1 (ja) | 2020-01-10 | 2021-07-15 | 日本化薬株式会社 | 触媒、触媒の充填方法、および触媒を用いた化合物の製造方法 |
JP2020152727A (ja) * | 2020-06-01 | 2020-09-24 | 日本化薬株式会社 | 再スタートアップ方法 |
Also Published As
Publication number | Publication date |
---|---|
US20160145180A1 (en) | 2016-05-26 |
JP6199972B2 (ja) | 2017-09-20 |
RU2016105244A (ru) | 2017-08-23 |
TW201512164A (zh) | 2015-04-01 |
KR101819465B1 (ko) | 2018-01-17 |
EP3023405A4 (en) | 2016-12-28 |
MX2016000550A (es) | 2016-04-20 |
EP3023405A1 (en) | 2016-05-25 |
US9580376B2 (en) | 2017-02-28 |
SA516370412B1 (ar) | 2017-11-21 |
KR20160014666A (ko) | 2016-02-11 |
TWI585075B (zh) | 2017-06-01 |
SG11201600350RA (en) | 2016-02-26 |
CN105392761A (zh) | 2016-03-09 |
RU2654063C2 (ru) | 2018-05-16 |
JPWO2015008814A1 (ja) | 2017-03-02 |
MY182262A (en) | 2021-01-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6199972B2 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JP6294883B2 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JP2018140993A (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JP5951121B2 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒、その製造方法及び不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
WO2016136882A1 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒及びその製造方法並びに不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JPH1028877A (ja) | 触媒及び不飽和アルデヒドおよび不飽和酸の製造方法 | |
JP7506031B2 (ja) | 不飽和アルデヒドの製造方法 | |
KR102612311B1 (ko) | 아크롤레인, 메타크롤레인, 아크릴산, 또는 메타크릴산의 제조 방법 | |
WO2014014041A1 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
WO2019198763A1 (ja) | 不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造方法並びに不飽和アルデヒド及び不飽和カルボン酸の少なくとも一方の製造用触媒 | |
JP6238354B2 (ja) | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒およびその製造方法ならびに不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480040828.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14825697 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015527327 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157036349 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14903410 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2016/000550 Country of ref document: MX Ref document number: 2014825697 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: IDP00201600265 Country of ref document: ID |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112016000251 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 2016105244 Country of ref document: RU Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 112016000251 Country of ref document: BR Kind code of ref document: A2 Effective date: 20160106 |