JP6579010B2 - Composite oxide catalyst and method for producing conjugated diene - Google Patents
Composite oxide catalyst and method for producing conjugated diene Download PDFInfo
- Publication number
- JP6579010B2 JP6579010B2 JP2016058927A JP2016058927A JP6579010B2 JP 6579010 B2 JP6579010 B2 JP 6579010B2 JP 2016058927 A JP2016058927 A JP 2016058927A JP 2016058927 A JP2016058927 A JP 2016058927A JP 6579010 B2 JP6579010 B2 JP 6579010B2
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- JP
- Japan
- Prior art keywords
- composite oxide
- oxide catalyst
- conjugated diene
- butene
- pore volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 139
- 239000002131 composite material Substances 0.000 title claims description 102
- 150000001993 dienes Chemical class 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011148 porous material Substances 0.000 claims description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 27
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 26
- 238000009826 distribution Methods 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000005673 monoalkenes Chemical class 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 229910052710 silicon Inorganic materials 0.000 description 29
- 239000010703 silicon Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000012071 phase Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 229910021485 fumed silica Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000000227 grinding Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000010354 integration Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 ammonium carboxylates Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 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 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 5
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 4
- 229940036358 bismuth subcarbonate Drugs 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 150000001622 bismuth compounds Chemical class 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000021615 conjugation Effects 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- HQOJMTATBXYHNR-UHFFFAOYSA-M thallium(I) acetate Chemical compound [Tl+].CC([O-])=O HQOJMTATBXYHNR-UHFFFAOYSA-M 0.000 description 1
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Description
本発明は、炭素数４以上のモノオレフィンを酸素含有ガスにより気相接触酸化脱水素反応させて対応する共役ジエンを製造する際に用いる複合酸化物触媒と、この複合酸化物触媒を用いた共役ジエンの製造方法に関する。 The present invention relates to a composite oxide catalyst used for producing a corresponding conjugated diene by subjecting a monoolefin having 4 or more carbon atoms to a gas phase catalytic oxidative dehydrogenation reaction with an oxygen-containing gas, and a conjugate using the composite oxide catalyst. The present invention relates to a method for producing dienes.
従来、炭素数４以上のモノオレフィンを酸素含有ガスとの気相接触酸化脱水素反応により共役ジエンを製造するために用いる触媒については種々提案されている。 Conventionally, various catalysts for producing conjugated dienes by a gas phase catalytic oxidative dehydrogenation reaction of monoolefins having 4 or more carbon atoms with oxygen-containing gas have been proposed.
例えば、特許文献１には、モリブデン、鉄、ニッケル又はコバルトの少なくとも一つ、及びシリカを含む複合金属酸化物触媒の製造方法が開示され、当該触媒はブテンからブタジエンを製造する反応に用い得ることが記載されている。特許文献２には、モリブデン、ビスマスを主成分とする、ブタジエン製造用の複合金属酸化物触媒が開示されている。特許文献３には、マクロ孔の細孔容積が全体の細孔容積の８０％以上を占め、モリブデンを必須成分とする、ブタジエン製造用の複合金属酸化物成型触媒が開示されている。 For example, Patent Document 1 discloses a method for producing a composite metal oxide catalyst containing at least one of molybdenum, iron, nickel, or cobalt and silica, and the catalyst can be used in a reaction for producing butadiene from butene. Is described. Patent Document 2 discloses a composite metal oxide catalyst for producing butadiene, which contains molybdenum and bismuth as main components. Patent Document 3 discloses a composite metal oxide molded catalyst for producing butadiene, in which the pore volume of macropores accounts for 80% or more of the total pore volume, and molybdenum is an essential component.
しかし、従来知られた複合酸化物触媒は、炭素数４以上のモノオレフィンの気相接触酸化脱水素反応で共役ジエンを製造するための工業触媒として必ずしも反応効率が十分ではなく、さらなる改良が望まれていた。 However, conventionally known composite oxide catalysts are not necessarily efficient as industrial catalysts for producing conjugated dienes by gas phase catalytic oxidative dehydrogenation of monoolefins having 4 or more carbon atoms, and further improvements are desired. It was rare.
本発明は上記問題点を解決するためになされたものである。すなわち、本発明は炭素数４以上のモノオレフィンを原料として酸素含有ガスとの気相接触酸化脱水素反応により共役ジエンを製造する際に用いる複合酸化物触媒として、原料が触媒と接触する時間が短い条件下でも原料の転化率に優れ、且つ所望とする共役ジエンの選択率を高く維持し、収率の向上が可能となる複合酸化物触媒であり、また、長期間安定的に気相接触酸化脱水素反応を行える強度に優れた複合酸化物触媒と、この複合酸化物触媒を用いた共役ジエンの製造方法を提供することを目的とする。 The present invention has been made to solve the above problems. That is, the present invention provides a composite oxide catalyst used when a conjugated diene is produced by a gas phase catalytic oxidative dehydrogenation reaction with an oxygen-containing gas using a monoolefin having 4 or more carbon atoms as a raw material. It is a complex oxide catalyst that excels in conversion of raw materials even under short conditions, maintains a high selectivity for the desired conjugated diene, and can improve yields. An object of the present invention is to provide a composite oxide catalyst having excellent strength capable of performing oxidative dehydrogenation and a method for producing a conjugated diene using the composite oxide catalyst.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、特定元素の酸化物を含み、比表面積及び細孔容積が特定範囲内であり、細孔径が特定範囲にある細孔により占められる細孔容積が全細孔容積に対し特定範囲の複合酸化物触媒であれば、これを炭素数４以上のモノオレフィンの気相接触酸化脱水素反応に使用した場合、酸化反応時間が短い条件下でも原料の転化率に優れ、生成する共役ジエンの選択率を高く維持することができ、収率の向上が可能で、且つ、高転化率の反応条件下においても高選択率を維持し、高収率で共役ジエンの製造が可能となることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention include an oxide of a specific element, the specific surface area and the pore volume are within a specific range, and the pore diameter is occupied by a pore within the specific range. If the pore volume to be produced is a complex oxide catalyst having a specific range relative to the total pore volume, the oxidation reaction time is short when it is used for the gas phase catalytic oxidative dehydrogenation of monoolefins having 4 or more carbon atoms. The conversion rate of the raw material is excellent even under the above, the selectivity of the conjugated diene to be generated can be maintained high, the yield can be improved, and the high selectivity is maintained even under high conversion rate reaction conditions, The inventors have found that conjugated dienes can be produced with a high yield, and have reached the present invention.
すなわち、本発明の要旨は以下の通りである。 That is, the gist of the present invention is as follows.
［１］ 炭素数４以上のモノオレフィンを酸素含有ガスにより気相接触酸化脱水素反応させて対応する共役ジエンを製造する際に用いる複合酸化物触媒であって、
該複合酸化物触媒がモリブデンの酸化物、ビスマスの酸化物、コバルトの酸化物、ニッケルの酸化物、鉄の酸化物及びシリカを含み、比表面積が５ｍ２／ｇ〜２５ｍ２／ｇであり、細孔容積が０．２０ｍｌ／ｇ〜０．５０ｍｌ／ｇであり、かつ、細孔径分布において細孔径が０．１μｍ〜１．０μｍに存在する細孔により占められる細孔容積は全細孔容積のうちの５０％〜６８％、及び細孔径が０．１μｍ未満に存在する細孔により占められる細孔容積は全細孔容積のうちの２７％〜５０％である複合酸化物触媒。
[1] A composite oxide catalyst used for producing a corresponding conjugated diene by subjecting a monoolefin having 4 or more carbon atoms to gas phase catalytic oxidative dehydrogenation reaction with an oxygen-containing gas,
The composite oxide catalyst is an oxide of molybdenum, an oxide of bismuth, cobalt oxide, nickel oxide, comprises an oxide and silica iron, specific surface area of 5m 2 / g~25m 2 / g, The pore volume occupied by pores having a pore volume of 0.20 ml / g to 0.50 ml / g and a pore diameter of 0.1 μm to 1.0 μm in the pore size distribution is the total pore volume. A composite oxide catalyst in which the pore volume occupied by pores having a pore diameter of less than 0.1 μm is 27% to 50% of the total pore volume.
［２］ 前記複合酸化物触媒が下記組成式（１）で表される［１］に記載の複合酸化物触媒。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＳｉｈＯｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）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）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種の元素である。また、ａ〜ｊはそれぞれの元素の原子比を表し、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜１０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。）
[2] The composite oxide catalyst according to [1], wherein the composite oxide catalyst is represented by the following composition formula (1).
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
Wherein X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B) , Phosphorus (P), arsenic (As), and tungsten (W), and at least one element selected from the group consisting of tungsten (W), and a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5-7, c = 0.1-10, d = 0.1-10, e = 0.05-5, f = 0-2, g = 0-3, h = 1-48. And i is a numerical value that satisfies the oxidation state of other elements.)
［３］ 前記炭素数４以上のモノオレフィンがｎ−ブテンであり、前記共役ジエンがブタジエンである［１］又は［２］に記載の複合酸化物触媒。 [3] The composite oxide catalyst according to [1] or [2], wherein the monoolefin having 4 or more carbon atoms is n-butene, and the conjugated diene is butadiene.
［４］ ［１］〜［３］のいずれかに記載の複合金属酸化物触媒を使用して、炭素数４以上のモノオレフィンと酸素を含む原料混合ガスから接触気相酸化脱水素反応により共役ジエンを製造する共役ジエンの製造方法。 [4] Using the composite metal oxide catalyst according to any one of [1] to [3], conjugation is performed by a catalytic gas phase oxidative dehydrogenation reaction from a raw material mixed gas containing a monoolefin having 4 or more carbon atoms and oxygen. A method for producing a conjugated diene for producing a diene.
［５］ 前記炭素数４以上のモノオレフィンがｎ−ブテンであり、前記共役ジエンがブタジエンである［４］に記載の共役ジエンの製造方法。 [5] The method for producing a conjugated diene according to [4], wherein the monoolefin having 4 or more carbon atoms is n-butene, and the conjugated diene is butadiene.
［６］ 前記ｎ−ブテンの空間速度が１００ｈ−１〜４００ｈ−１の範囲である［５］に記載の共役ジエンの製造方法。 [6] The method for producing a conjugated diene according to the a [5] Range space velocity of 100h -1 ~400h -1 of the n- butenes.
［７］ 前記原料混合ガス中のｎ−ブテンの含有量が６体積％〜１２体積％の範囲である、［５］又は［６］に記載の共役ジエンの製造方法。 [7] The method for producing a conjugated diene according to [5] or [6], wherein the content of n-butene in the raw material mixed gas is in the range of 6% by volume to 12% by volume.
本発明の複合酸化物触媒を用いて、炭素数４以上のモノオレフィンの気相接触酸化脱水素反応を行うと、モノオレフィンの転化率に優れ、高選択率で共役ジエンを製造することができる。更に、本発明の複合酸化物触媒は、機械的強度が大きく、粉化が少ないことより、反応器に該複合酸化物触媒を充填し、気相接触酸化脱水素反応を開始した当初より、長期間にわたり、安定して効率よく共役ジエンを製造することができる。 When the gas phase catalytic oxidative dehydrogenation reaction of a monoolefin having 4 or more carbon atoms is performed using the composite oxide catalyst of the present invention, it is excellent in conversion of monoolefin and can produce conjugated dienes with high selectivity. . Furthermore, since the composite oxide catalyst of the present invention has high mechanical strength and less pulverization, the composite oxide catalyst is filled in the reactor and the gas phase catalytic oxidative dehydrogenation reaction is started from the beginning. A conjugated diene can be produced stably and efficiently over a period of time.
以下に、本発明について詳細に説明する。 The present invention is described in detail below.
［複合酸化物触媒］
本発明の複合酸化物触媒はモリブデンの酸化物、ビスマスの酸化物、コバルトの酸化物、ニッケルの酸化物、鉄の酸化物及びシリカを含む。
[Composite oxide catalyst]
The composite oxide catalyst of the present invention includes molybdenum oxide, bismuth oxide, cobalt oxide, nickel oxide, iron oxide and silica.
本発明の複合酸化物触媒は下記組成式（１）で表されることが好ましい。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＳｉｈＯｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）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）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種の元素である。また、ａ〜ｊはそれぞれの元素の原子比を表し、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜１０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。）
The composite oxide catalyst of the present invention is preferably represented by the following composition formula (1).
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
Wherein X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B) , Phosphorus (P), arsenic (As), and tungsten (W), and at least one element selected from the group consisting of tungsten (W), and a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5-7, c = 0.1-10, d = 0.1-10, e = 0.05-5, f = 0-2, g = 0-3, h = 1-48. And i is a numerical value that satisfies the oxidation state of other elements.)
上記組成式（１）の複合酸化物触媒とすることで、より高収率で共役ジエンを製造することができる。 By using the composite oxide catalyst of the composition formula (1), a conjugated diene can be produced with higher yield.
＜比表面積＞
本発明の複合酸化物触媒の比表面積は５ｍ２／ｇ〜２５ｍ２／ｇである。複合酸化物触媒の比表面積は好ましくは７ｍ２／ｇ〜２０ｍ２／ｇであり、より好ましくは８ｍ２／ｇ〜１８ｍ２／ｇである。上記範囲よりも比表面積が大きすぎると、触媒の活性成分に覆われていない担体部分が多くなり、目的生成物の選択率が低くなり、収率が低下する場合があり、比表面積が小さすぎると触媒の活性成分の分散性が低下し、目的生成物の収率が低下する可能性がある。なお、ここでいう比表面積は複合酸化物触媒単位重量あたりの表面積であり、窒素吸着によるＢＥＴ法により測定される。
<Specific surface area>
The specific surface area of the composite oxide catalyst of the present invention is 5m 2 / g~25m 2 / g. The specific surface area of the composite oxide catalyst is preferably 7m 2 / g~20m 2 / g, more preferably 8m 2 / g~18m 2 / g. If the specific surface area is too larger than the above range, the support part not covered with the active component of the catalyst will increase, the selectivity of the target product will be low, and the yield may be reduced, and the specific surface area will be too small. As a result, the dispersibility of the active component of the catalyst is lowered, and the yield of the target product may be lowered. Here, the specific surface area is a surface area per unit weight of the composite oxide catalyst, and is measured by a BET method by nitrogen adsorption.
＜細孔容積＞
本発明の複合酸化物触媒の細孔容積は０．２０ｍｌ／ｇ〜０．５０ｍｌ／ｇである。複合酸化物触媒の細孔容積は好ましくは０．２１ｍｌ／ｇ〜０．４４ｍｌ／ｇであり、更に好ましくは０．２２ｍｌ／ｇ〜０．３９ｍｌ／ｇである。上記範囲よりも細孔容積が大きすぎると触媒の密度が小さくなり触媒を取扱う際に高い粉化率となる場合があり、細孔容積が小さすぎると原料の反応する場が少なくなり転化率が低下し、低収率となる可能性がある。なお、細孔容積は水銀圧入法によるポロシメーターで測定される。
<Pore volume>
The pore volume of the composite oxide catalyst of the present invention is 0.20 ml / g to 0.50 ml / g. The pore volume of the composite oxide catalyst is preferably 0.21 ml / g to 0.44 ml / g, more preferably 0.22 ml / g to 0.39 ml / g. If the pore volume is too larger than the above range, the density of the catalyst may be reduced and a high pulverization rate may be obtained when the catalyst is handled. If the pore volume is too small, the reaction field of the raw material is reduced and the conversion rate is reduced. It may be reduced and yield may be low. The pore volume is measured with a porosimeter by mercury porosimetry.
＜細孔径分布＞
本発明の複合酸化物触媒の細孔径分布において、細孔径（細孔の直径）が０．１μｍ〜１．０μｍに存在する細孔により占められる細孔容積は全細孔容積のうちの５０％〜６８％であり、好ましくは５１％〜６７％であり、より好ましくは５２％〜６６％である。細孔径が０．１μｍ〜１．０μｍに存在する細孔により占められる細孔容積の割合が小さすぎると触媒の活性が低下し、原料の転化率が上昇しない場合があり、触媒の活性を補てんするために気相接触酸化脱水素反応温度を上昇させると、目的生成物の収率が低下する可能性がある。該割合が大きすぎると触媒の強度が低下し、粉化率が上昇する可能性がある。
<Pore size distribution>
In the pore size distribution of the composite oxide catalyst of the present invention, the pore volume occupied by pores having a pore diameter (pore diameter) of 0.1 μm to 1.0 μm is 50% of the total pore volume. It is ˜68%, preferably 51% to 67%, more preferably 52% to 66%. If the ratio of the pore volume occupied by pores with a pore diameter of 0.1 μm to 1.0 μm is too small, the activity of the catalyst may decrease, and the conversion rate of the raw material may not increase, thus supplementing the activity of the catalyst. If the gas-phase catalytic oxidative dehydrogenation reaction temperature is increased, the yield of the target product may be reduced. When the ratio is too large, the strength of the catalyst is lowered, and the powdering rate may be increased.
本発明の複合酸化物触媒の細孔径分布において、細孔径（細孔の直径）が０．１μｍ未満に存在する細孔により占められる細孔容積は全細孔容積のうちの２７％〜５０％であり、好ましくは２８％〜４６％であり、より好ましくは２９％〜４２％である。細孔径が０．１μｍ未満に存在する細孔により占められる細孔容積の割合が小さすぎると触媒の強度が低下し、粉化率が上昇する場合があり、大きすぎると生成した目的生成物が更に反応しやすくなり、選択率が低下し、収率が低下する場合がある。
なお、細孔径分布は水銀圧入法によりポロシメーターで測定される。
以下において、全細孔容積に対する、細孔径が０．１μｍ〜１．０μｍに存在する細孔により占められる細孔容積の割合を「０．１〜１．０μｍ細孔容積割合」と称し、同じく、細孔径が０．１μｍ未満に存在する細孔により占められる細孔容積の割合を「０．１μｍ未満細孔容積割合」と称す場合がある。
In the pore size distribution of the composite oxide catalyst of the present invention, the pore volume occupied by pores having a pore size (pore diameter) of less than 0.1 μm is 27% to 50% of the total pore volume. And preferably 28% to 46%, more preferably 29% to 42%. If the ratio of the pore volume occupied by pores having a pore diameter of less than 0.1 μm is too small, the strength of the catalyst may be reduced, and the powdering rate may be increased. Furthermore, it becomes easy to react, a selectivity may fall and a yield may fall.
The pore size distribution is measured with a porosimeter by the mercury intrusion method.
Hereinafter, the ratio of the pore volume occupied by pores having a pore diameter of 0.1 μm to 1.0 μm with respect to the total pore volume is referred to as “0.1 to 1.0 μm pore volume ratio”. The ratio of the pore volume occupied by pores having a pore diameter of less than 0.1 μm may be referred to as “less than 0.1 μm pore volume ratio”.
＜複合酸化物触媒の製造方法＞
以下に本発明に好適な複合酸化物触媒の製造方法について説明する。
本発明の複合酸化物触媒の製造方法としては、該複合酸化物触媒を構成する各成分元素の供給源化合物を水系内で一体化して加熱する工程を経て製造する方法が好ましい。例えば、モリブデン化合物、シリカ、更に鉄化合物、ニッケル化合物及びコバルト化合物等を含む原料化合物水溶液、又は該原料化合物水溶液を更に乾燥して得た乾燥物を加熱処理して触媒前駆体を製造する前工程と、該触媒前駆体、モリブデン化合物及びビスマス化合物等を水性溶媒とともに一体化し、乾燥、焼成する後工程とを経て製造されたものが好ましい。
<Method for producing composite oxide catalyst>
Hereinafter, a method for producing a composite oxide catalyst suitable for the present invention will be described.
As the method for producing the composite oxide catalyst of the present invention, a method of producing the composite oxide catalyst through a step of integrating and heating the source compounds of the component elements constituting the composite oxide catalyst in an aqueous system is preferable. For example, a pre-process for producing a catalyst precursor by heat-treating a raw material compound aqueous solution containing molybdenum compound, silica, iron compound, nickel compound and cobalt compound, or a dried material obtained by further drying the raw material compound aqueous solution The catalyst precursor, the molybdenum compound, the bismuth compound and the like are integrated with an aqueous solvent, dried and fired, and then manufactured through a post-process.
（各成分元素の供給源化合物）
本発明の複合酸化物触媒の製造にあたり、モリブデン（Ｍｏ）の供給源化合物としては、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、リンモリブデン酸アンモニウム、リンモリブデン酸等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。
ここで、リンモリブデン酸アンモニウム、リンモリブデン酸は、モリブデンの供給源化合物であると共に、組成式（１）におけるＹであるリン（Ｐ）の供給源化合物でもある。即ち、複合酸化物触媒の製造に用いる各元素の供給源化合物とは、各元素のそれぞれについてのそれぞれの化合物のみを意味するのではなく、リンモリブデン酸アンモニウム、リンモリブデン酸のような複数の元素を共に含む化合物を包含するものである。
(Source compounds for each component element)
In the production of the composite oxide catalyst of the present invention, examples of the molybdenum (Mo) source compound include ammonium paramolybdate, molybdenum trioxide, molybdic acid, ammonium phosphomolybdate, and phosphomolybdic acid. These may be used alone or in combination of two or more.
Here, ammonium phosphomolybdate and phosphomolybdic acid are both a source compound for molybdenum and a source compound for phosphorus (P) as Y in the composition formula (1). That is, the source compound for each element used in the production of the composite oxide catalyst does not mean only the respective compound for each element, but a plurality of elements such as ammonium phosphomolybdate and phosphomolybdic acid. Including both compounds.
ビスマス（Ｂｉ）の供給源化合物としては、塩化ビスマス、硝酸ビスマス、酸化ビスマス、次炭酸ビスマス等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。ビスマスの供給源化合物量は、前記組成式（１）において、ａ＝１２のとき、ｂ＝０．５〜７となるように添加することが好ましく、より好ましくはｂ＝０．５〜４．４となるように添加する。ｂが前記範囲内であることにより原料の転化率に優れ、高選択率で目的生成物を製造することができる複合酸化物触媒とすることができる。
また、前記組成式（１）において、ビスマスの供給源化合物量とケイ素（Ｓｉ）の供給源化合物の比（ｂ／ｈ比）は、０．０１〜５とすることが好ましく、０．０２〜３とすることがより好ましく、０．０５〜１とすることが更に好ましい。ｂ／ｈ比が前記範囲内にあることにより、より高収率で目的生成物を製造することができる複合酸化物触媒とすることができる。
Examples of the bismuth (Bi) source compound include bismuth chloride, bismuth nitrate, bismuth oxide, and bismuth subcarbonate. These may be used alone or in combination of two or more. The amount of the bismuth source compound is preferably added so that b = 0.5-7 when a = 12, and more preferably b = 0.5-4. Add to 4. When b is in the above range, a composite oxide catalyst that is excellent in the conversion rate of the raw material and can produce the target product with high selectivity can be obtained.
In the compositional formula (1), the ratio (b / h ratio) between the amount of the bismuth source compound and the silicon (Si) source compound is preferably 0.01 to 5, preferably 0.02 to 0.02. 3 is more preferable, and 0.05 to 1 is still more preferable. When the b / h ratio is within the above range, a composite oxide catalyst capable of producing the target product with higher yield can be obtained.
コバルト（Ｃｏ）の供給源化合物としては、硝酸コバルト、硫酸コバルト、塩化コバルト、炭酸コバルト、酢酸コバルト等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。コバルトの供給源化合物は、前記組成式（１）において、ａ＝１２のとき、ｃ＝０．１〜１０となるように添加することが好ましく、より好ましくはｃ＝０．５〜８、更に好ましくはｃ＝１〜５となるように添加する。 Examples of cobalt (Co) supply source compounds include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt acetate. These may be used alone or in combination of two or more. The cobalt source compound is preferably added so that c = 0.1 to 10 when a = 12 in the composition formula (1), more preferably c = 0.5 to 8, Preferably, it adds so that it may become c = 1-5.
ニッケル（Ｎｉ）の供給源化合物としては、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、酢酸ニッケル等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。ニッケルの供給源化合物は、前記組成式（１）において、ａ＝１２のとき、ｄ＝０．１〜１０なるように添加することが好ましく、より好ましくはｄ＝０．５〜８、更に好ましくはｄ＝１〜５となるように添加する。 Examples of nickel (Ni) supply source compounds include nickel nitrate, nickel sulfate, nickel chloride, nickel carbonate, and nickel acetate. These may be used alone or in combination of two or more. The nickel source compound is preferably added so that d = 0.1 to 10, more preferably d = 0.5 to 8, even more preferably when a = 12 in the composition formula (1). Is added so that d = 1-5.
鉄（Ｆｅ）の供給源化合物としては、硝酸第二鉄、硫酸第二鉄、塩化第二鉄、酢酸第二鉄等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。鉄の供給源化合物は、前記組成式（１）において、ａ＝１２のとき、ｅ＝０．０５〜５となるように添加することが好ましく、より好ましくはｅ＝０．１〜４、更に好ましくはｅ＝０．３〜２となるように添加する。 Examples of the iron (Fe) source compound include ferric nitrate, ferric sulfate, ferric chloride, and ferric acetate. These may be used alone or in combination of two or more. In the composition formula (1), the iron source compound is preferably added so that e = 0.05 to 5 when a = 12, more preferably e = 0.1 to 4, Preferably, it is added so that e = 0.3-2.
ケイ素（Ｓｉ）の供給源化合物としては、シリカ、粒状シリカ、コロイダルシリカ、ヒュームドシリカ等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。容易に触媒の比表面積、細孔容積、細孔容積の分布を制御できることから、熱分解シリカであるヒュームドシリカが好ましい。 Examples of the silicon (Si) source compound include silica, granular silica, colloidal silica, and fumed silica. These may be used alone or in combination of two or more. Since the specific surface area, pore volume, and pore volume distribution of the catalyst can be easily controlled, fumed silica which is pyrolytic silica is preferred.
得られる複合酸化物触媒の比表面積、細孔容積、細孔径分布を制御するための好ましいケイ素の供給源化合物の物性については後述する。 The physical properties of a preferred silicon source compound for controlling the specific surface area, pore volume, and pore size distribution of the resulting composite oxide catalyst will be described later.
ケイ素の供給源化合物は、前記組成式（１）において、ａ＝１２のとき、ｈ＝１〜４８となるように添加することが好ましく、より好ましくはｈ＝５〜３０、更に好ましくはｈ＝１０〜２５となるように添加する。ｈが小さすぎると複合酸化物触媒の活性成分の分散性が低下する傾向にあり、ｈが大きすぎると複合酸化物触媒の活性成分の割合が少なくなり、十分な触媒性能が得られない可能性がある。 In the composition formula (1), the silicon source compound is preferably added so that h = 1 to 48 when a = 12, more preferably h = 5 to 30, and still more preferably h =. Add to 10-25. If h is too small, the dispersibility of the active component of the composite oxide catalyst tends to decrease, and if h is too large, the ratio of the active component of the composite oxide catalyst decreases, and sufficient catalyst performance may not be obtained. There is.
Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であれば特に限定されないが、ナトリウム（Ｎａ）、カリウム（Ｋ）及びセシウム（Ｃｓ）からなる群から選ばれる少なくとも１種であることがより好ましく、ナトリウム（Ｎａ）及び／又はカリウム（Ｋ）であることが更に好ましい。Ｘを含むことで、目的生成物の選択性が向上する。 X is not particularly limited as long as it is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and thallium (Tl), but sodium (Na), More preferably, it is at least one selected from the group consisting of potassium (K) and cesium (Cs), more preferably sodium (Na) and / or potassium (K). By including X, the selectivity of the target product is improved.
Ｘの供給源化合物は、前記組成式（１）において、ａ＝１２のときに、ｆ＝０〜２となるように添加することが好ましいが、より好ましくはｆ＝０．１〜１．５、更に好ましくはｆ＝０．２〜１．２となるように添加する。ｆが小さすぎると、目的生成物の選択率が低下する傾向にあり、ｆが大きすぎると触媒の活性が低下する可能性がある。 The source compound of X is preferably added so that f = 0 to 2 when a = 12, and more preferably f = 0.1 to 1.5 in the composition formula (1). More preferably, it is added so that f = 0.2 to 1.2. If f is too small, the selectivity of the target product tends to decrease, and if f is too large, the activity of the catalyst may decrease.
Ｙはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）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種の元素であれば特に限定されないが、ホウ素（Ｂ）、リン（Ｐ）及び砒素（Ａｓ）からなる群から選ばれる少なくとも１種であることがより好ましく、ホウ素（Ｂ）であることが更に好ましい。 Y is not particularly limited as long as it is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As), and tungsten (W), but boron (B), phosphorus (P), and More preferred is at least one selected from the group consisting of arsenic (As), and even more preferred is boron (B).
Ｙの供給源化合物は、前記組成式（１）において、ａ＝１２のときに、ｇ＝０〜３となるように添加することが好ましいが、より好ましくはｇ＝０．１〜２．０、更に好ましくはｇ＝０．２〜１．０となるように添加する。 The source compound of Y is preferably added so that g = 0 to 3 when a = 12, and more preferably g = 0.1 to 2.0 in the composition formula (1). More preferably, it is added so that g = 0.2 to 1.0.
上記Ｘ，Ｙの供給源化合物としては、各々の元素の酸化物、硝酸塩、炭酸塩、アンモニウム塩、水酸化物、カルボン酸塩、カルボン酸アンモニウム塩、ハロゲン化アンモニウム塩、水素酸、アセチルアセテート、アルコキシド等が挙げられ、その具体例としては、下記のようなものが挙げられる。 Examples of the X and Y source compounds include oxides, nitrates, carbonates, ammonium salts, hydroxides, carboxylates, ammonium carboxylates, ammonium halides, hydrogen acids, acetyl acetate, Examples include alkoxides, and specific examples thereof include the following.
ナトリウム（Ｎａ）の供給源化合物としては、硝酸ナトリウム、硫酸ナトリウム、塩化ナトリウム、炭酸ナトリウム、酢酸ナトリウム等が挙げられる。
カリウム（Ｋ）の供給源化合物としては、硝酸カリウム、硫酸カリウム、塩化カリウム、炭酸カリウム、酢酸カリウム等が挙げられる。
ルビジウム（Ｒｂ）の供給源化合物としては、硝酸ルビジウム、硫酸ルビジウム、塩化ルビジウム、炭酸ルビジウム、酢酸ルビジウム等が挙げられる。
セシウム（Ｃｓ）の供給源化合物としては、硝酸セシウム、硫酸セシウム、塩化セシウム、炭酸セシウム、酢酸セシウム等が挙げられる。
タリウム（Ｔｌ）の供給源化合物としては、硝酸第一タリウム、塩化第一タリウム、炭酸タリウム、酢酸第一タリウム等が挙げられる。
また、Ｘ成分（Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｔｌの１種又は２種以上）は、これを固溶させた、ビスマス（Ｂｉ）とＸ成分との複合炭酸塩化合物として供給することもできる。
例えば、Ｘ成分としてナトリウム（Ｎａ）を用いる場合、炭酸ナトリウム又は重炭酸ナトリウムの水溶液等に、硝酸ビスマス等の水溶性ビスマス化合物の水溶液を滴下混合し、得られた沈殿を水洗、乾燥することによって製造されたＢｉとＮａとの複合炭酸塩化合物として添加することもできる。
これらはいずれも、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
Examples of the source compound for sodium (Na) include sodium nitrate, sodium sulfate, sodium chloride, sodium carbonate, and sodium acetate.
Examples of the source compound for potassium (K) include potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, and potassium acetate.
Examples of the source compound for rubidium (Rb) include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium carbonate, and rubidium acetate.
Examples of the source compound of cesium (Cs) include cesium nitrate, cesium sulfate, cesium chloride, cesium carbonate, and cesium acetate.
Examples of the thallium (Tl) supply source compound include thallium nitrate, thallium chloride, thallium carbonate, and thallium acetate.
Further, the X component (one or more of Na, K, Rb, Cs, and Tl) can be supplied as a complex carbonate compound of bismuth (Bi) and the X component in which this is dissolved. .
For example, when sodium (Na) is used as the X component, an aqueous solution of a water-soluble bismuth compound such as bismuth nitrate is added dropwise to an aqueous solution of sodium carbonate or sodium bicarbonate, and the resulting precipitate is washed with water and dried. It can also be added as a complex carbonate compound of produced Bi and Na.
Any of these may be used alone or in combination of two or more.
ホウ素（Ｂ）の供給源化合物としては、ホウ砂、ホウ酸アンモニウム、ホウ酸等が挙げられる。
リン（Ｐ）の供給源化合物としては、リンモリブデン酸アンモニウム、リン酸アンモニウム、リン酸、五酸化リン等が挙げられる。
砒素（Ａｓ）の供給源化合物としては、ジアルセノ十八モリブデン酸アンモニウム、ジアルセノ十八タングステン酸アンモニウム等が挙げられる。
タングステン（Ｗ）の供給源化合物としては、パラタングステン酸アンモニウム、メタタングステン酸アンモニウム、三酸化タングステン、タングステン酸、リンタングステン酸等が挙げられる。
これらはいずれも、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
Examples of the source compound for boron (B) include borax, ammonium borate, and boric acid.
Examples of the phosphorus (P) source compound include ammonium phosphomolybdate, ammonium phosphate, phosphoric acid, and phosphorus pentoxide.
Examples of the arsenic (As) source compound include dialsenooctammonium ammonium molybdate, dialsenooctammonium ammonium tungstate, and the like.
Examples of the source compound for tungsten (W) include ammonium paratungstate, ammonium metatungstate, tungsten trioxide, tungstic acid, and phosphotungstic acid.
Any of these may be used alone or in combination of two or more.
（一体化及び加熱工程）
本発明の複合酸化物触媒は、各成分元素の供給源化合物の水性系での一体化及び加熱を含む工程を経て製造されることが好ましい。各成分元素の供給源化合物の水性系での一体化とは、各成分元素の供給源化合物の水溶液あるいは水分散液を一括に、あるいは段階的に混合又は熟成処理、混合及び熟成処理を行うことをいう。即ち、（イ）上記の各供給源化合物を一括して混合する方法、（ロ）上記の各供給源化合物を一括して混合し、そして熟成処理する方法、（ハ）上記の各供給源化合物を段階的に混合する方法、（ニ）上記の各供給源化合物を段階的に混合・熟成処理を繰り返す方法、及び（イ）〜（ニ）を組み合わせる方法のいずれもが、各成分元素の供給源化合物の水性系での一体化という概念に含まれる。ここで、熟成とは、工業原料もしくは半製品を、一定時間、一定温度等の特定条件のもとに処理して、必要とする物理性、化学性の取得、上昇あるいは所定反応の進行等を図る操作をいい、本発明における一定時間とは、通常３０分〜１２時間の範囲であり、一定温度とは通常室温〜水溶液又は水分散液の沸点範囲をいう。
(Integration and heating process)
The composite oxide catalyst of the present invention is preferably produced through a process including integration and heating of each component element source compound in an aqueous system. The integration of each component element source compound in an aqueous system means that an aqueous solution or an aqueous dispersion of each component element source compound is mixed or aged in stages or mixed and aged. Say. (B) a method of mixing the above-mentioned source compounds in a lump, (b) a method of mixing the above-mentioned source compounds in a lump and aging, and (c) a method of mixing each of the above-mentioned source compounds. Supply of each component element is a method of stepwise mixing, (d) a method of repeatedly mixing and aging the above-mentioned source compounds stepwise, and a method of combining (b) to (d). It is included in the concept of integration of the source compound in an aqueous system. Here, aging refers to the processing of industrial raw materials or semi-finished products under specific conditions such as constant temperature for a certain period of time to obtain the required physical and chemical properties, increase or advance the prescribed reaction, etc. The constant time in the present invention is usually in the range of 30 minutes to 12 hours, and the constant temperature is usually in the range of room temperature to the boiling point of the aqueous solution or aqueous dispersion.
また、上記加熱とは、上記各成分元素の供給源化合物それぞれの酸化物及び／又は複合酸化物の形成、並びに／あるいは一体化により生じた複合化合物の酸化物及び／又は複合酸化物の形成、並びに／あるいは生成最終複合酸化物の形成のための熱処理をいう。そして、加熱は必ずしも１回とは限られない。即ち、この加熱は上記（イ）〜（ニ）で示される一体化の各段階で任意で行うことができ、また一体化後に必要に応じて追加して行ってもよい。この加熱温度は、通常２００℃〜６００℃の範囲である。 The heating is the formation of oxides and / or composite oxides of the source compounds of the component elements, and / or the formation of oxides and / or composite oxides of the composite compounds produced by integration, And / or heat treatment for forming the final composite oxide. And heating is not necessarily performed once. That is, this heating can be optionally performed at each stage of integration shown in the above (a) to (d), and may be additionally performed as necessary after integration. This heating temperature is usually in the range of 200 ° C to 600 ° C.
さらに、上記の一体化及び加熱においては、これら以外に、例えば、乾燥、粉砕等をその前後や途中に実施してもよい。 Furthermore, in the above integration and heating, for example, drying, pulverization, etc. may be performed before, after, or during the process.
また、上記のようにして複合酸化物触媒を製造する場合、ケイ素の供給源化合物として、熱分解シリカを用いることが好ましい。この好適なケイ素の供給源化合物については後述する。
また、ビスマスの供給源化合物として、（１）酸化ビスマスまたは次炭酸ビスマスのいずれか一方、（２）所要のＮａの少なくとも一部を固溶した次炭酸ビスマス、（３）成分の少なくとも一部を含むＢｉとＸとの複合炭酸塩化合物、あるいは（４）所要のＮａおよびＸ成分のそれぞれ少なくとも一部を含むＢｉとＮａとＸとの複合炭酸塩化合物を組み合わせて用いることにより、容易に触媒比表面積、細孔容積、細孔径分布を制御した工業的に優れた触媒を製造できる。上記複合酸化物触媒を、各成分元素の供給源化合物の水性系での一体化及び加熱を含む工程を経て製造する場合、その一部としてモリブデン、鉄、ニッケル又はコバルトの少なくとも一つ、及びシリカを一部として含む原料塩水溶液を乾燥して得た乾燥物を加熱処理して触媒前駆体粉末を製造する前工程を経た後、触媒前駆体粉末とビスマス化合物とを水性溶媒とともに一体化し、乾燥、焼成する後工程を経て調製することが好ましい。
Moreover, when producing a composite oxide catalyst as described above, it is preferable to use pyrogenic silica as the silicon source compound. This preferred silicon source compound is described below.
Further, as a source compound of bismuth, (1) either bismuth oxide or bismuth subcarbonate, (2) bismuth subcarbonate in which at least a part of required Na is dissolved, (3) at least a part of component By using a combined carbonate compound of Bi and X containing Bi, or (4) a combined carbonate compound of Bi, Na and X containing at least a part of each of the required Na and X components, a catalyst ratio can be easily obtained. An industrially excellent catalyst with controlled surface area, pore volume and pore size distribution can be produced. When the composite oxide catalyst is manufactured through a process including integration and heating of the source compounds of the component elements in an aqueous system, at least one of molybdenum, iron, nickel, or cobalt and silica as a part thereof The dried product obtained by drying the raw material salt aqueous solution containing the catalyst as a part is subjected to a pre-process for producing a catalyst precursor powder by heat treatment, and then the catalyst precursor powder and the bismuth compound are integrated with an aqueous solvent and dried. It is preferable to prepare it after the post-baking process.
上記の原料塩水溶液又はこれを乾燥して得た顆粒あるいはケーキ状のものは空気中で２００℃〜４００℃、好ましくは２５０℃〜３５０℃の温度域で短時間の熱処理を行う。その際の炉の形式及びその方法については特に限定はなく、例えば、通常の箱型加熱炉、トンネル型加熱炉等を用いて乾燥物を固定した状態で加熱してもよいし、また、ロータリーキルン等を用いて乾燥物を流動させながら加熱してもよい。 The raw material salt aqueous solution or a granule or cake obtained by drying the raw salt solution is heat-treated in the air in a temperature range of 200 ° C to 400 ° C, preferably 250 ° C to 350 ° C. There are no particular limitations on the type and method of the furnace at that time, and for example, it may be heated with a dry matter fixed using a normal box-type furnace, tunnel-type furnace, etc., or a rotary kiln. It is possible to heat the dried product while flowing it.
得られたスラリーは充分に撹拌した後、乾燥する。このようにして得られた乾燥品を、押出成型、打錠成型、造粒成型あるいは担持成型等の方法により所望の形状に賦形する。
次に、得られた成型体を、好ましくは４５０℃〜６５０℃の温度条件にて３０分〜１０時間程度の最終熱処理に付すことで、本発明の複合酸化物触媒を得ることができる。
The obtained slurry is sufficiently stirred and then dried. The dried product thus obtained is shaped into a desired shape by a method such as extrusion molding, tableting molding, granulation molding or support molding.
Next, the composite oxide catalyst of the present invention can be obtained by subjecting the obtained molded body to a final heat treatment of preferably about 30 minutes to 10 hours under a temperature condition of 450 ° C. to 650 ° C.
（成型条件）
上記の各成型方法による成型時の条件等は、得られる複合酸化物触媒の比表面積、細孔容積、細孔径分布に影響を与えるため、目的とする比表面積、細孔容積、細孔径分布の複合酸化物触媒が得られるように適宜調整する。
(Molding conditions)
The molding conditions by the above molding methods affect the specific surface area, pore volume, and pore size distribution of the resulting composite oxide catalyst. It adjusts suitably so that a complex oxide catalyst may be obtained.
この観点から、成型方法が押出成型の場合、押出圧力は１０ｋｇｆ／ｃｍ２〜２５ｋｇｆ／ｃｍ２が好ましく、１５ｋｇｆ／ｃｍ２〜２０ｋｇｆ／ｃｍ２がより好ましい。該押出圧力範囲内で押出成型を行うことにより、適度な比表面積を有する複合酸化物触媒とすることが可能となり、更に、良好な細孔容積及び細孔径分布を有する複合酸化物触媒とすることができる。 In this respect, if the molding method of extrusion, the extrusion pressure is preferably from 10kgf / cm 2 ~25kgf / cm 2 , 15kgf / cm 2 ~20kgf / cm 2 is more preferable. By performing extrusion molding within the extrusion pressure range, a composite oxide catalyst having an appropriate specific surface area can be obtained, and further, a composite oxide catalyst having a good pore volume and pore size distribution can be obtained. Can do.
また、成型方法が打錠成型の場合、打錠成型の圧力は１５ｋｇｆ／ｃｍ２〜３５ｋｇｆ／ｃｍ２が好ましく、２０ｋｇｆ／ｃｍ２〜２５ｋｇｆ／ｃｍ２がより好ましい。該圧力範囲内で打錠成型を行うことにより、適度な比表面積を有する複合酸化物触媒とすることが可能となり、更に、良好な細孔容積及び細孔径分布を有する複合酸化物触媒とすることができる。 Further, the molding method is the case of the tablet compression, the pressure of tablet compression is preferably 15kgf / cm 2 ~35kgf / cm 2 , 20kgf / cm 2 ~25kgf / cm 2 is more preferable. By performing tableting molding within the pressure range, it becomes possible to obtain a composite oxide catalyst having an appropriate specific surface area, and further to provide a composite oxide catalyst having a good pore volume and pore size distribution. Can do.
前記成型の際、製造される複合酸化物触媒の強度を上昇させ、触媒の粉化率を低減する効果があるものとして一般に知られているガラス繊維などの無機繊維、各種ウィスカーなどを成型前の粉体等に添加してもよい。また、触媒物性を再現よく制御するために、硝酸アンモニウム、セルロース、デンプン、ポリビニルアルコール、ステアリン酸など一般に粉体結合剤として知られている添加物を使用することもできる。 During the molding, inorganic fibers such as glass fibers and various whiskers, which are generally known to have an effect of increasing the strength of the produced composite oxide catalyst and reducing the powdering rate of the catalyst, are formed before molding. You may add to powder etc. In order to control the physical properties of the catalyst with good reproducibility, additives generally known as powder binders such as ammonium nitrate, cellulose, starch, polyvinyl alcohol and stearic acid can also be used.
（粉化率）
複合酸化物触媒の強度が低いと触媒を取り扱う際、特に反応器に充填する際に触媒に粉化や割れが生じ、差圧（反応管入口と出口の圧力差）が大きくなる場合がある。差圧が大きくなると、ｎ−ブテン等の原料と酸素含有ガスを含む原料混合ガスを複合酸化物触媒が充填された反応器に送風するコンプレッサー等に多大な負荷がかかる。
(Powdering rate)
When the composite oxide catalyst is low in strength, when the catalyst is handled, particularly when the reactor is charged, the catalyst may be pulverized or cracked, and the differential pressure (pressure difference between the reaction tube inlet and the outlet) may increase. When the differential pressure increases, a great load is imposed on a compressor or the like that blows a raw material mixed gas containing a raw material such as n-butene and an oxygen-containing gas to a reactor filled with a composite oxide catalyst.
また、気相接触酸化脱水素反応が進むにつれ、複合酸化物触媒の粉化が生じる場合には、時間と共に差圧が上昇することになり、コンプレッサーのフィード能力の限界を超え、原料混合ガスを反応管に送り込めなくなる場合がある。更には、粉化と共に、複合酸化物触媒の活性成分が剥離してしまう場合があり、必要とされる触媒性能が発現しなくなることもある。 In addition, as the gas phase catalytic oxidative dehydrogenation proceeds, if the composite oxide catalyst is pulverized, the differential pressure will increase with time, exceeding the limit of the feed capacity of the compressor, It may become impossible to send to the reaction tube. Furthermore, with powdering, the active component of the composite oxide catalyst may be peeled off, and the required catalyst performance may not be exhibited.
これらの理由で本発明の複合酸化物触媒の粉化率は２．０％以下であることが好ましく、１．５％以下がより好ましく、１．０％以下が更に好ましい。 For these reasons, the pulverization rate of the composite oxide catalyst of the present invention is preferably 2.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less.
触媒の粉化を抑制するためには、複合酸化物触媒の製造時にガラス繊維を添加したり、成型時の圧力を上げたりすることで対応可能であるが、このようにすることで、細孔容積に影響を与えて触媒性能が低下する可能性もあるので注意が必要である。なお粉化率とは、複合酸化物触媒を１ｍの高さより落下させたときの微粒が生じた割合を表し、具体的には後述の実施例の項に記載される方法で測定される。 In order to suppress the powdering of the catalyst, it is possible to add glass fibers during the production of the composite oxide catalyst or increase the pressure during molding. Care must be taken because the catalyst performance may be reduced by affecting the volume. The pulverization rate represents the rate at which fine particles were generated when the composite oxide catalyst was dropped from a height of 1 m, and is specifically measured by the method described in the section of Examples below.
（ケイ素の供給源化合物）
本発明の複合酸化物触媒の製造に当たり、前述の上記のケイ素の供給源化合物は、水等の媒体に添加して分散処理を施した分散液として用いることが好ましい。該分散液とすることにより、複合酸化物触媒の比表面積、細孔容積、細孔径分布を良好に制御することが可能となる。
(Silicon source compound)
In the production of the composite oxide catalyst of the present invention, the above-mentioned silicon source compound is preferably used as a dispersion which is added to a medium such as water and subjected to a dispersion treatment. By using the dispersion, the specific surface area, pore volume, and pore size distribution of the composite oxide catalyst can be well controlled.
ケイ素の供給源化合物の分散液の調製方法は、例えば、ケイ素の供給源化合物を水等の媒体に添加・混合し、懸濁状態とした後に、媒体の流動、衝突、圧力差、超音波等の分散原理を利用し、ケイ素の供給源化合物を媒体中に微分散させて分散液とする方法が挙げられる。ケイ素の供給源化合物を媒体中に微分散させて分散液とする分散装置としては、例えばホモジナイザー、ホモミキサー、高剪断ブレンダー、ビーズミル、超音波分散装置が挙げられ、中でも、微分散させたケイ素の供給源化合物の粒径分布がシャープとなることより、ホモジナイザー、ホモミキサーが好ましく、ホモジナイザーがより好ましい。 The method for preparing the dispersion of the silicon source compound is, for example, adding and mixing the silicon source compound to a medium such as water to make it into a suspended state, and then the flow of the medium, collision, pressure difference, ultrasonic wave, etc. And a dispersion method by finely dispersing a silicon source compound in a medium. Examples of the dispersion apparatus in which a silicon source compound is finely dispersed in a medium to form a dispersion liquid include a homogenizer, a homomixer, a high shear blender, a bead mill, and an ultrasonic dispersion apparatus. A homogenizer and a homomixer are preferable, and a homogenizer is more preferable because the particle size distribution of the source compound becomes sharp.
ケイ素の供給源化合物を使用するに当たり、適度な比表面積を有する供給源化合物を選択することが重要である。該供給源化合物の比表面積は通常６０ｍ２／ｇ〜３００ｍ２／ｇであることが好ましく、６０ｍ２／ｇ〜２５０ｍ２／ｇであることがより好ましく、６０ｍ２／ｇ〜２００ｍ２／ｇであることが更に好ましく、６０ｍ２／ｇ〜１９０ｍ２／ｇであることが特に好ましい。適度な比表面積の供給源化合物を選択することにより、得られる複合酸化物触媒の比表面積、細孔容積、細孔径分布を良好に制御することが可能となる。
ここで、ケイ素の供給源化合物の比表面積は窒素吸着によるＢＥＴ１点法により触媒単位重量あたりの表面積を測定して求めた。具体的には、ケイ素の供給源化合物を２５０℃で１５分間、窒素ガス送風状態で処理したサンプルを、測定装置：マックソーブＨＭ Ｍｏｄｅｌ−１２０１（株式会社マウンテック製）を用いて、ＢＥＴ１点法（吸着ガス：窒素）にて比表面積を測定した値である。
In using a silicon source compound, it is important to select a source compound having an appropriate specific surface area. It is preferred that the specific surface area of wherein the source compounds are typically 60m 2 / g~300m 2 / g, more preferably 60m 2 / g~250m 2 / g, at 60m 2 / g~200m 2 / g more preferably in, particularly preferably 60m 2 / g~190m 2 / g. By selecting a source compound having an appropriate specific surface area, it is possible to satisfactorily control the specific surface area, pore volume, and pore size distribution of the obtained composite oxide catalyst.
Here, the specific surface area of the silicon source compound was determined by measuring the surface area per unit weight of the catalyst by the BET one-point method using nitrogen adsorption. Specifically, a sample obtained by treating a silicon source compound at 250 ° C. for 15 minutes in a nitrogen gas blowing state is measured using a measuring device: Macsorb HM Model-1201 (manufactured by Mountec Co., Ltd.) with a BET one-point method (adsorption) It is a value obtained by measuring the specific surface area with gas (nitrogen).
また、ケイ素の供給源化合物の体積平均粒径は０．０５μｍ〜３μｍが好ましく、０．０５μｍ〜１μｍがより好ましく、０．０５μｍ〜０．５μｍがさらに好ましく、０．０５μ〜０．３μｍがその中でも好ましく、０．０５μｍ〜０．２５μｍが特に好ましい。該体積平均粒径が上記範囲内であることにより、得られる複合酸化物触媒の比表面積、細孔容積、細孔径分布のなかでもとりわけ、細孔径分布を良好に制御することが可能となる。 The volume average particle size of the silicon source compound is preferably 0.05 μm to 3 μm, more preferably 0.05 μm to 1 μm, further preferably 0.05 μm to 0.5 μm, and 0.05 μm to 0.3 μm. Among these, 0.05 μm to 0.25 μm is particularly preferable. When the volume average particle size is in the above range, the pore size distribution can be well controlled among the specific surface area, pore volume and pore size distribution of the obtained composite oxide catalyst.
また、ケイ素の供給源化合物における１μｍ以上の粒径の粒子全体に対する割合（以下、この割合を「１μｍ以上の粒子割合」と称す場合がある。）は、５重量％以下が好ましく、３重量％以下がより好ましく、１重量％以下がさらに好ましく、０．８重量％以下が特に好ましい。１μｍ以上の粒子割合が上記上限以下であることにより、得られる複合酸化物触媒の比表面積、細孔容積、細孔径分布のなかでもとりわけ、細孔径分布を良好に制御することが可能となる。 Further, the ratio of the particle size of 1 μm or more in the silicon source compound to the whole particles (hereinafter, this ratio may be referred to as “particle ratio of 1 μm or more”) is preferably 5% by weight or less, preferably 3% by weight. The following is more preferable, 1% by weight or less is further preferable, and 0.8% by weight or less is particularly preferable. When the particle ratio of 1 μm or more is not more than the above upper limit, the pore size distribution can be favorably controlled among the specific surface area, pore volume, and pore size distribution of the obtained composite oxide catalyst.
なお、上記ケイ素の供給源化合物の体積平均粒径はレーザー回折散乱式粒度分布測定法により測定することができ、体積基準５０％径を体積平均粒径とする。ケイ素の供給源化合物を分散液で使用する場合は該分散液を測定サンプルとして、体積平均粒径を測定し、ケイ素の供給源化合物を固体で使用する場合はケイ素の供給源化合物を水に投入後、均一なケイ素の供給源化合物の濃度とした液をサンプルとして体積平均粒径を測定する。 The volume average particle diameter of the silicon source compound can be measured by a laser diffraction / scattering particle size distribution measurement method, and the volume-based 50% diameter is defined as the volume average particle diameter. When the silicon source compound is used as a dispersion, the volume average particle diameter is measured using the dispersion as a measurement sample. When the silicon source compound is used as a solid, the silicon source compound is added to water. Thereafter, the volume average particle diameter is measured using a liquid having a uniform concentration of the silicon source compound as a sample.
前記ケイ素の供給源化合物の分散液中のケイ素の供給源化合物濃度は１重量％〜５０重量％が好ましく、１０重量％〜３０重量％がより好ましい。この濃度が１重量％より小さいと、水等の媒体量が多大となり、乾燥工程において経済的に不利となる場合がある。一方、５０重量％より大きいと、分散液の流動性は極めて悪くなり他の触媒成分との混合操作が困難となる場合がある。 The concentration of the silicon source compound in the silicon source compound dispersion is preferably 1 wt% to 50 wt%, more preferably 10 wt% to 30 wt%. If this concentration is less than 1% by weight, the amount of medium such as water becomes large, which may be economically disadvantageous in the drying process. On the other hand, if it is larger than 50% by weight, the fluidity of the dispersion becomes extremely poor, and mixing with other catalyst components may be difficult.
触媒調製の際に、ケイ素源化合物の比表面積もしくはその使用量によって活性成分の高分散そして単位シリカ当たりの活性成分の含有量を増やすことによって高活性の触媒が得られる。さらに、上記比表面積をもつケイ素の供給源化合物を使用することにより、０．１〜１．０μｍ容積割合が増加し、目的とする生成物の選択性の低下を抑制することができ、高い転化率条件でも収率の向上を図ることができる。 In the preparation of the catalyst, a highly active catalyst can be obtained by increasing the content of the active component per unit silica and increasing the dispersion of the active component depending on the specific surface area of the silicon source compound or the amount of the silicon source compound used. Furthermore, by using the silicon source compound having the above specific surface area, the volume ratio of 0.1 to 1.0 μm is increased, and the decrease in selectivity of the target product can be suppressed, and high conversion is achieved. The yield can be improved even under rate conditions.
以上のようにして、高い転化率条件で、目的とする生成物を高い収率で与える本発明の複合酸化物触媒を製造することができる。 As described above, it is possible to produce the composite oxide catalyst of the present invention that gives the target product in high yield under high conversion conditions.
［共役ジエンの製造方法］
上記のようにして製造された本発明の複合酸化物触媒は、炭素数４以上のモノオレフィンの気相接触酸化脱水素反応で共役ジエンを製造する反応、好ましくは、ｎ−ブテンの気相接触酸化脱水素反応でブタジエンを製造する反応に使用される。
[Method for producing conjugated diene]
The composite oxide catalyst of the present invention produced as described above is a reaction for producing a conjugated diene by a gas phase catalytic oxidative dehydrogenation reaction of a monoolefin having 4 or more carbon atoms, preferably a gas phase contact of n-butene. Used in reactions for producing butadiene by oxidative dehydrogenation.
ｎ−ブテンからブタジエンを製造する気相接触酸化脱水素反応は、原料混合ガス組成として好ましくは６〜１２体積％のｎ−ブテン、５〜１８体積％の分子状酸素、０〜４０体積％の水蒸気及び２０〜８０体積％の不活性ガス（例えば窒素、炭酸ガス等）からなる原料混合ガスを前記のようにして製造した複合酸化物触媒に３００℃〜４５０℃の温度範囲及び常圧〜１５０ｋＰａＧ（ゲージ圧）の圧力下で接触させることにより行うことができる。
具体的には、上記の原料混合ガスを本発明の複合酸化物触媒を充填した反応管に所定の反応条件で流通させて反応を行う。
The gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from n-butene is preferably 6 to 12% by volume of n-butene, 5 to 18% by volume of molecular oxygen, and 0 to 40% by volume of the raw material mixed gas composition. A composite oxide catalyst prepared as described above using a raw material mixed gas composed of water vapor and 20 to 80% by volume of an inert gas (for example, nitrogen, carbon dioxide, etc.) is heated to a temperature range of 300 ° C. to 450 ° C. and normal pressure to 150 kPaG. It can carry out by making it contact under the pressure of (gauge pressure).
Specifically, the reaction is carried out by flowing the raw material mixed gas through a reaction tube filled with the composite oxide catalyst of the present invention under predetermined reaction conditions.
上記原料混合ガス中のｎ−ブテンのより好ましい含有量は６体積％〜１０体積％の範囲であり、かつ、ｎ−ブテンの空間速度は５０ｈ−１〜５００ｈ−１の範囲が好ましく、１００ｈ−１〜４００ｈ−１の範囲であることがより好ましい。空間速度が低い条件、すなわち、ｎ−ブテンの負荷が低い条件では副生成物が多くなり、生成目的物の収率が低下する原因になる。また、空間速度が高い条件、すなわち、ｎ−ブテンの負荷が高い条件では転化率が低くなり、原料であるｎ−ブテンの未反応量が多くなって生産量及びコスト面から好ましくない。原料混合ガス中のｎ−ブテンの含有量は、高いほど時間当たりの生産量が増加し工業的に有利となるが、ｎ−ブテンの含有量が高すぎると触媒への炭素分（コーク）が蓄積しやすくなる傾向にあり、長期の安定運転や触媒寿命に影響を与えることがある。本発明の複合酸化物触媒は、原料混合ガス中のｎ−ブテンの含有量が前記範囲であっても、触媒への炭素分の蓄積を防ぎ長期にわたり安定的に酸化脱水素反応させることができる。 More preferable content of n- butenes of the raw material mixed gas is in the range of 6 to 10 vol%, and, n- space velocity butene is preferably in the range of 50h -1 ~500h -1, 100h - More preferably, it is in the range of 1 to 400 h −1 . Under conditions where the space velocity is low, that is, under a condition where the load of n-butene is low, the amount of by-products increases, causing the yield of the product to be reduced. Further, under conditions where the space velocity is high, that is, when the load of n-butene is high, the conversion rate is low, and the amount of unreacted n-butene as a raw material increases, which is not preferable from the viewpoint of production and cost. The higher the content of n-butene in the raw material mixed gas, the more the production per hour increases, which is industrially advantageous. However, if the content of n-butene is too high, the carbon content (coke) in the catalyst is reduced. It tends to accumulate, and may affect long-term stable operation and catalyst life. The composite oxide catalyst of the present invention can prevent oxidative dehydrogenation stably over a long period of time by preventing carbon from accumulating in the catalyst even when the content of n-butene in the raw material mixed gas is within the above range. .
なお、空間速度とは次式で示される値である。
空間速度ＳＶ（ｈ−１）＝反応器に供給するｎ−ブテンの体積流量（０℃、１気圧条件）／反応器に充填された複合金属酸化物触媒の体積（反応性の無い固形物は含まない）
The space velocity is a value represented by the following equation.
Space velocity SV (h −1 ) = volume flow rate of n-butene supplied to the reactor (0 ° C., 1 atm condition) / volume of the composite metal oxide catalyst charged in the reactor (non-reactive solids are Not included)
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に何ら限定されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
（１）比表面積の測定
複合酸化物触媒の比表面積は、窒素吸着によるＢＥＴ１点法により触媒単位重量あたりの表面積を測定して求めた。具体的には、複合酸化物触媒を２５０℃で１５分間、窒素ガス送風状態で処理したサンプルを、測定装置：マックソーブＨＭ Ｍｏｄｅｌ−１２０１（株式会社マウンテック製）を用いて、ＢＥＴ１点法（吸着ガス：窒素）にて比表面積を測定した。
(1) Measurement of specific surface area The specific surface area of the composite oxide catalyst was determined by measuring the surface area per unit weight of the catalyst by the BET one-point method by nitrogen adsorption. Specifically, a sample obtained by treating the composite oxide catalyst at 250 ° C. for 15 minutes in a nitrogen gas blowing state is measured using a measuring apparatus: Macsorb HM Model-1201 (manufactured by Mountec Co., Ltd.), and a BET one-point method (adsorbed gas). : Nitrogen) and the specific surface area was measured.
（２）細孔容積の測定及び細孔容積の割合の算出
複合酸化物触媒の細孔容積は、ポロシメーター（水銀圧入法）により複合酸化物触媒単位重量あたりの細孔直径と細孔容積及びその分布を測定して求めた。具体的には複合酸化物触媒をオートポアＩＶ ９５２０型（マイクロメトリックス社製）を用いて、減圧下（５０μｍＨｇ以下）で１０分間処理した後、水銀圧入退出曲線を測定し、細孔分布を求めた。
(2) Measurement of pore volume and calculation of ratio of pore volume The pore volume of the composite oxide catalyst is determined by a porosimeter (mercury intrusion method) with respect to the pore diameter and pore volume per unit weight of the composite oxide catalyst. It was determined by measuring the distribution. Specifically, the composite oxide catalyst was treated for 10 minutes under reduced pressure (50 μmHg or less) using Autopore IV 9520 (manufactured by Micrometrics), and then the mercury intrusion / retraction curve was measured to obtain the pore distribution. .
（３）複合酸化物触媒の粉化率の測定
複合酸化物触媒を目開き２．３６ｍｍの篩により篩別し、篩上のものを粉化率測定サンプルとした。アクリル製の高さ１ｍの円筒（φ６６ｍｍ）の上部に漏斗（円錐上部口径１５０ｍｍ、円錐下部口径２５ｍｍ）を挿入し、円筒下部に受け皿を設置した。該粉化率測定サンプル約２０ｇを精秤し、漏斗の円錐上部より投入し、該円筒を介して該受け皿に落下させた。落下した該粉化率測定サンプルを該受け皿より回収し、目開き２．３６ｍｍの篩により篩別した微粒の重量（粉化重量）を測定し、以下の式から触媒粉化率を算出した。
触媒粉化率（％）＝（粉化重量／粉化率測定サンプル重量）×１００
(3) Measurement of pulverization rate of composite oxide catalyst The composite oxide catalyst was sieved with a sieve having a mesh size of 2.36 mm, and the sample on the sieve was used as a pulverization rate measurement sample. A funnel (conical upper caliber 150 mm, conical lower caliber 25 mm) was inserted into the top of an acrylic cylinder (φ66 mm) with a height of 1 m, and a saucer was installed at the bottom of the cylinder. About 20 g of the powder rate measurement sample was precisely weighed, poured from the top of the funnel cone, and dropped onto the tray through the cylinder. The fallen powder rate measurement sample was collected from the saucer, and the weight (pulverization weight) of the fine particles sieved with a sieve having an aperture of 2.36 mm was measured, and the catalyst powder rate was calculated from the following equation.
Catalyst dusting rate (%) = (powdering weight / powdering rate measurement sample weight) × 100
（４）シリカの体積平均粒径、粒径分布、比表面積の測定
レーザー回折散乱式粒度分布測定器であるＷｅｔ ｕｎｉｔ ＬＭＳ−２０００ｓ（株式会社セイシン企業製）により、シリカの体積基準粒径分布を測定し、５０％径をシリカの体積平均粒径とした。なお、測定は湿式法により行った。
また、比表面積は、窒素吸着によるＢＥＴ１点法により触媒単位重量あたりの表面積を測定して求めた。具体的には、ケイ素の供給源化合物を２５０℃で１５分間、窒素ガス送風状態で処理したサンプルを、測定装置：マックソーブＨＭ Ｍｏｄｅｌ−１２０１（株式会社マウンテック製）を用いて、ＢＥＴ１点法（吸着ガス：窒素）にて比表面積を測定した。
(4) Measurement of silica volume average particle size, particle size distribution, and specific surface area The volume-based particle size distribution of silica was measured by Wet unit LMS-2000s (manufactured by Seishin Enterprise Co., Ltd.) which is a laser diffraction scattering type particle size distribution measuring instrument. The 50% diameter was measured as the volume average particle diameter of silica. The measurement was performed by a wet method.
The specific surface area was determined by measuring the surface area per unit weight of the catalyst by the BET one-point method using nitrogen adsorption. Specifically, a sample obtained by treating a silicon source compound at 250 ° C. for 15 minutes in a nitrogen gas blowing state is measured using a measuring device: Macsorb HM Model-1201 (manufactured by Mountec Co., Ltd.) with a BET one-point method (adsorption) The specific surface area was measured with gas (nitrogen).
［実施例１（１−１〜１−３）］
＜複合酸化物触媒の調製＞
容器に温水７００ｍｌを入れ、更にパラモリブデン酸アンモニウム１１０．２ｇを加えて溶解させ、溶液とした。次いで、該溶液にヒュームドシリカの水分散液４４８．９ｇを加えて、撹拌し、懸濁液とした（以下、「懸濁液Ａ」と称する）。該ヒュームドシリカ水分散液は、ヒュームドシリカ５ｋｇ（比表面積９２．６ｍ２／ｇ）をイオン交換水２２．５Ｌに加えてヒュームドシリカ懸濁液とした後に、該ヒュームドシリカ懸濁液を、ホモジナイザーであるＵＬＴＲＡ−ＴＵＲＲＡＸ Ｔ１１５ＫＴ（ＩＫＡ社製）により、３０分間分散処理を行い、均一なヒュームドシリカ水分散液としたものである。なお、ヒュームドシリカ水分散液中のシリカの体積平均粒径は０．２４７μｍであり、１μｍ以上の粒子割合は０．７５重量％であった。
[Example 1 (1-1 to 1-3)]
<Preparation of composite oxide catalyst>
700 ml of warm water was put in a container, and 110.2 g of ammonium paramolybdate was further added and dissolved to obtain a solution. Next, 448.9 g of an aqueous dispersion of fumed silica was added to the solution and stirred to obtain a suspension (hereinafter referred to as “suspension A”). The fumed silica aqueous dispersion was prepared by adding 5 kg of fumed silica (specific surface area 92.6 m 2 / g) to 22.5 L of ion-exchanged water to form a fumed silica suspension. Is subjected to a dispersion treatment for 30 minutes by ULTRA-TURRAX T115KT (manufactured by IKA) as a homogenizer to obtain a uniform aqueous fumed silica dispersion. In addition, the volume average particle diameter of the silica in the fumed silica aqueous dispersion was 0.247 μm, and the ratio of particles of 1 μm or more was 0.75% by weight.
別の容器に純水１２０ｍｌを入れ、更に硝酸第二鉄１５．１ｇ、硝酸コバルト６５．７ｇ及び硝酸ニッケル５２．５ｇを加えて、加温して溶解させた（以下、「溶液Ｂ」と称する）。溶液Ｂを懸濁液Ａに添加し、均一になるように攪拌し、加熱乾燥し、固形物を得た。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した（以下、「固形分Ｍ」と称する）。 In another container, 120 ml of pure water was added, and then 15.1 g of ferric nitrate, 65.7 g of cobalt nitrate and 52.5 g of nickel nitrate were added and heated to dissolve (hereinafter referred to as “solution B”). ). Solution B was added to suspension A, stirred uniformly and dried by heating to obtain a solid. Next, the solid was heat-treated at 300 ° C. for 1 hour in an air atmosphere (hereinafter referred to as “solid content M”).
更に、別の容器に純水１２０ｍｌ、アンモニア水１０ｍｌを入れ、パラモリブデン酸アンモニウム１６．１ｇを加えて溶解し、「溶液Ｃ」とした。次いで、溶液Ｃにホウ砂１．４ｇ及び硝酸カリウム０．３９ｇを加えて溶解し、「溶液Ｄ」とした。前記熱処理した固形物Ｍの１２６ｇを溶液Ｄに添加し、均一になるように混合した。次いでＮａを０．５３重量％固溶した次炭酸ビスマス１４．６ｇを加えて３０分間混合した後、水分を除去するため加熱乾燥し、乾燥品を得た。該乾燥品を粉砕し、得られた粉体を、高さ方向の圧縮強度が２０ｋｇｆ〜２５ｋｇｆとなるように円柱状に打錠成型し、成型体（外径：５ｍｍ、高さ３ｍｍ）とした。なお、該圧縮強度は木屋式強度測定機により測定したものである。
該成型体を空気雰囲気下、５１５℃で２時間焼成して複合酸化物触媒を得た。
上記のように調製した複合酸化物触媒の比表面積、細孔容積、細孔容積割合、組成比は表１に示す通りである。また、この複合酸化物触媒の粉化率は表２に示す通りであった。
Furthermore, 120 ml of pure water and 10 ml of aqueous ammonia were put in another container, and 16.1 g of ammonium paramolybdate was added and dissolved to obtain “Solution C”. Next, 1.4 g of borax and 0.39 g of potassium nitrate were added to the solution C and dissolved to obtain “solution D”. 126 g of the heat-treated solid M was added to the solution D and mixed to be uniform. Next, 14.6 g of bismuth carbonate in which 0.53% by weight of Na was dissolved was added and mixed for 30 minutes, followed by heating and drying to remove moisture to obtain a dried product. The dried product was pulverized, and the obtained powder was tableted into a cylindrical shape so that the compressive strength in the height direction was 20 kgf to 25 kgf, and a molded body (outer diameter: 5 mm, height 3 mm) was obtained. . In addition, this compressive strength is measured with the Kiya type | mold strength measuring machine.
The molded body was calcined at 515 ° C. for 2 hours in an air atmosphere to obtain a composite oxide catalyst.
The specific surface area, pore volume, pore volume ratio, and composition ratio of the composite oxide catalyst prepared as described above are as shown in Table 1. Moreover, the powdering rate of this composite oxide catalyst was as shown in Table 2.
＜ｎ−ブテンの気相接触酸化脱水素反応＞
得られた複合酸化物触媒を粉砕し、目開き１ｍｍの篩により粗粒を除き、目開き０．５ｍｍの篩により微粒を除いたものをｎ−ブテンの気相接触酸化脱水素反応用の触媒として使用した。該触媒０．４１ｇを内径６ｍｍのパイレックス製反応管に入れ、電気ヒーターで反応器の温調を行い、表２に示す所定の反応温度に加温した。ｎ−ブテン７体積％、スチーム１０体積％、酸素１０体積％、窒素７３体積％の原料混合ガスを圧力５０ｋＰａＧで反応管内に導入し、ｎ−ブテンの気相接触酸化脱水素反応を実施した。この時、ｎ−ブテンの空間速度は３４０ｈ−１であった。反応結果は表２にまとめた。
<Gas-phase catalytic oxidative dehydrogenation of n-butene>
The obtained composite oxide catalyst is pulverized, coarse particles are removed with a sieve having an opening of 1 mm, and fine particles are removed with a sieve having an opening of 0.5 mm, and a catalyst for vapor-phase catalytic oxidative dehydrogenation reaction of n-butene Used as. 0.41 g of the catalyst was placed in a Pyrex reaction tube having an inner diameter of 6 mm, the temperature of the reactor was adjusted with an electric heater, and the temperature was increased to a predetermined reaction temperature shown in Table 2. A raw material mixed gas of 7% by volume of n-butene, 10% by volume of steam, 10% by volume of oxygen, and 73% by volume of nitrogen was introduced into the reaction tube at a pressure of 50 kPaG to carry out gas phase catalytic oxidative dehydrogenation of n-butene. At this time, the space velocity of n-butene was 340 h −1 . The reaction results are summarized in Table 2.
なお、ｎ−ブテンの原料ガスとしては、重油留分を流動接触分解する際に得られる炭素数が４の炭化水素を多く含むガスとして、表３に示される成分組成のガス（ＦＣＣ−Ｃ４）を使用し、反応においては原料ガスに含まれる１−ブテン、シス−２−ブテン、トランス−２−ブテンの合計をｎ−ブテンとして表している。 In addition, as a raw material gas of n-butene, the gas (FCC-C4) of the component composition shown by Table 3 as a gas containing many hydrocarbons with 4 carbon atoms obtained when carrying out fluid catalytic cracking of a heavy oil fraction In the reaction, the total of 1-butene, cis-2-butene and trans-2-butene contained in the raw material gas is expressed as n-butene.
ここで、ｎ−ブテン転化率、ブタジエン選択率、ブタジエン収率の定義は、下記の通りであり、反応管出口ガスのガスクロマトグラフィー分析より求めた。
・ｎ−ブテン転化率（モル％）＝（反応した１−ブテン＋シス−２−ブテン＋トランス−２−ブテンのモル数／供給した１−ブテン＋シス−２−ブテン＋トランス−２−ブテンのモル数）×１００
・ブタジエン選択率（モル％）＝（生成したブタジエンのモル数／反応した１−ブテン＋シス−２−ブテン＋トランス−２−ブテンのモル数）×１００
・ブタジエン収率（モル％）＝（生成したブタジエンのモル数／供給した１−ブテン＋シス−２−ブテン＋トランス−２−ブテンのモル数）×１００
Here, the definitions of n-butene conversion, butadiene selectivity, and butadiene yield are as follows, and were determined by gas chromatography analysis of the reaction tube outlet gas.
N-butene conversion (mol%) = (reacted 1-butene + cis-2-butene + trans-2-butene mol / feed 1-butene + cis-2-butene + trans-2-butene) Number of moles) × 100
Butadiene selectivity (mol%) = (number of moles of butadiene produced / number of moles of reacted 1-butene + cis-2-butene + trans-2-butene) × 100
-Butadiene yield (mol%) = (number of moles of butadiene produced / number of moles of supplied 1-butene + cis-2-butene + trans-2-butene) x 100
［比較例１（１−１〜１−３）］
ケイ素の供給源化合物として、比表面積が５６ｍ２／ｇであるヒュームドシリカを使用した以外は、実施例１と同様にして、複合酸化物触媒を得た。なお、ヒュームドシリカ水分散液中のシリカの体積平均粒径は０．２４４μｍであり、１μｍ以上の粒子割合は０％であった。得られた複合酸化物触媒の比表面積、細孔容積、細孔容積の割合、組成比を表１に示し、粉化率を表２に示した。
また、該複合酸化物触媒を用いて実施例１と同様の条件でｎ−ブテンの気相触媒酸化脱水素反応を行った結果を表２に示した。
[Comparative Example 1 (1-1 to 1-3)]
A composite oxide catalyst was obtained in the same manner as in Example 1 except that fumed silica having a specific surface area of 56 m 2 / g was used as the silicon source compound. In addition, the volume average particle diameter of the silica in the fumed silica aqueous dispersion was 0.244 μm, and the ratio of particles of 1 μm or more was 0%. Table 1 shows the specific surface area, pore volume, pore volume ratio, and composition ratio of the obtained composite oxide catalyst, and Table 2 shows the powdering rate.
In addition, Table 2 shows the results of the gas-phase catalytic oxidative dehydrogenation reaction of n-butene using the composite oxide catalyst under the same conditions as in Example 1.
［実施例２（２−１〜２−３）］
ヒュームドシリカ水分散液の使用量を変えてモリブテン１２に対するシリカの原子比を１６．８とした以外は、実施例１と同様にして複合酸化物触媒を得た。得られた複合酸化物触媒の比表面積、細孔容積、細孔容積割合、組成比を表１に、粉化率を表２に示した。なお、用いたヒュームドシリカ水分散液中のシリカの体積平均粒径は０．２４７μｍであり、１μｍ以上の粒子割合は０．７５重量％であった。
また、該複合酸化物触媒を用いて実施例１と同様の条件でｎ−ブテンの気相触媒酸化脱水素反応を行った結果を表２に示した。
[Example 2 (2-1 to 2-3)]
A composite oxide catalyst was obtained in the same manner as in Example 1 except that the amount of fumed silica aqueous dispersion used was changed so that the atomic ratio of silica to molybdenum 12 was 16.8. Table 1 shows the specific surface area, pore volume, pore volume ratio, and composition ratio of the obtained composite oxide catalyst, and Table 2 shows the powdering rate. In addition, the volume average particle diameter of the silica in the used fumed silica aqueous dispersion was 0.247 μm, and the ratio of particles of 1 μm or more was 0.75 wt%.
In addition, Table 2 shows the results of the gas-phase catalytic oxidative dehydrogenation reaction of n-butene using the composite oxide catalyst under the same conditions as in Example 1.
［比較例２（２−１〜２−３）］
容器に温水７１０ｍｌを入れ、更にパラモリブデン酸アンモニウム５４．９ｇを加えて溶解させ、更に硝酸第二鉄８．２ｇ、硝酸コバルト２６．７ｇ及び硝酸ニッケル４０．０ｇを加えて、加温して溶解させ溶液とした（以下、「溶液ａ」と称する）。次いで、該溶液ａを攪拌しながらヒュームドシリカ（比表面積９２．６ｍ２／ｇ）７３．６ｇを加えて、懸濁液とした（以下、「懸濁液ｂ」と称する）。懸濁液ｂを均一になるように攪拌し、加熱乾燥し、固形物を得た（以下、「固形物ｍ」と称する）。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した。なお、ヒュームドシリカ粉末のシリカの体積平均粒径は３３．９３９μｍであり、１μｍ以上の粒子割合は９６．９４重量％であった。
[Comparative Example 2 (2-1 to 2-3)]
Add 710 ml of warm water to the container, add 54.9 g of ammonium paramolybdate to dissolve, and then add 8.2 g of ferric nitrate, 26.7 g of cobalt nitrate and 40.0 g of nickel nitrate, and warm to dissolve. Solution (hereinafter referred to as “solution a”). Next, 73.6 g of fumed silica (specific surface area 92.6 m 2 / g) was added while stirring the solution a to form a suspension (hereinafter referred to as “suspension b”). The suspension b was stirred uniformly and dried by heating to obtain a solid (hereinafter referred to as “solid m”). The solid was then heat treated in an air atmosphere at 300 ° C. for 1 hour. In addition, the volume average particle diameter of the silica of the fumed silica powder was 33.939 μm, and the ratio of particles of 1 μm or more was 96.94 wt%.
別の容器に純水１２０ｍｌ、アンモニア水１０ｍｌを入れ、パラモリブデン酸アンモニウム３８．１ｇを加えて溶解し、次いで、ホウ砂１．２８ｇ及び硝酸カリウム０．３３ｇを加えて溶解し、溶液とした（以下「溶液ｃ」と称する）。前記熱処理した固形物ｍの８４ｇを溶液ｃに添加し、均一になるように混合した。次いでＮａを０．５３重量％固溶した次炭酸ビスマス４０．０ｇを加えて３０分間混合した後、水分を除去するため加熱乾燥し、乾燥品を得た。該乾燥品を粉砕し、得られた粉体を、高さ方向の圧縮強度が２０ｋｇｆ〜２５ｋｇｆとなるように円柱状に打錠成型し、成形品（外径：５ｍｍ、内径：２ｍｍ、高さ３ｍｍ）とした。なお、該圧縮強度は木屋式強度測定機により測定したものである。
該成形品を空気雰囲気下、５１５℃で２時間焼成して複合酸化物触媒を得た。
上記のように調製した複合酸化物触媒の比表面積、細孔容積、細孔容積割合、組成比を表１に、粉化率を表２に示した。
また、該複合酸化物触媒を用いて実施例１と同様の条件でｎ−ブテンの気相触媒酸化脱水素反応を行った結果を表２に示した。
In a separate container, 120 ml of pure water and 10 ml of ammonia water were added, 38.1 g of ammonium paramolybdate was added and dissolved, and then 1.28 g of borax and 0.33 g of potassium nitrate were added and dissolved to obtain a solution (hereinafter referred to as “the solution”). Referred to as “solution c”). 84 g of the heat-treated solid matter m was added to the solution c and mixed so as to be uniform. Next, 40.0 g of bismuth subcarbonate in which 0.53% by weight of Na was dissolved was added and mixed for 30 minutes, and then dried by heating to remove moisture to obtain a dried product. The dried product was pulverized, and the obtained powder was tableted into a cylindrical shape so that the compressive strength in the height direction was 20 kgf to 25 kgf, and the molded product (outer diameter: 5 mm, inner diameter: 2 mm, height) 3 mm). In addition, this compressive strength is measured with the Kiya type | mold strength measuring machine.
The molded article was calcined at 515 ° C. for 2 hours in an air atmosphere to obtain a composite oxide catalyst.
Table 1 shows the specific surface area, pore volume, pore volume ratio, and composition ratio of the composite oxide catalyst prepared as described above, and Table 2 shows the powdering rate.
In addition, Table 2 shows the results of the gas-phase catalytic oxidative dehydrogenation reaction of n-butene using the composite oxide catalyst under the same conditions as in Example 1.
本発明の複合酸化物触媒は、実施例において示されているように、ｎ−ブテンの気相接触酸化脱水素反応に用いた場合、ｎ−ブテンの転化率に優れ、且つ所望とするブタジエンの選択率が高く維持され、収率の向上が可能となっている。加えて、粉化率が小さいことより、長期間、気相接触酸化脱水素反応を行っても、差圧の上昇等の不具合が起こらず安定的な運転が可能となることが分かる。 As shown in the Examples, the composite oxide catalyst of the present invention is excellent in n-butene conversion when used in the gas phase catalytic oxidative dehydrogenation reaction of n-butene and has a desired butadiene concentration. The selectivity is kept high and the yield can be improved. In addition, since the pulverization rate is small, it can be seen that even if the gas phase catalytic oxidative dehydrogenation reaction is performed for a long period of time, a stable operation is possible without causing problems such as an increase in the differential pressure.
Claims (6)
該複合酸化物触媒がモリブデンの酸化物、ビスマスの酸化物、コバルトの酸化物、ニッケルの酸化物、鉄の酸化物及びシリカを含む、下記組成式（１）で表される複合酸化物触媒であり、
比表面積が５ｍ２／ｇ〜２５ｍ２／ｇであり、細孔容積が０．２０ｍｌ／ｇ〜０．５０ｍｌ／ｇであり、かつ、細孔径分布において細孔径が０．１μｍ〜１．０μｍに存在する細孔により占められる細孔容積は全細孔容積のうちの５０％〜６８％、及び細孔径が０．１μｍ未満に存在する細孔により占められる細孔容積は全細孔容積のうちの２７％〜５０％である複合酸化物触媒。
Ｍｏ ａ Ｂｉ ｂ Ｃｏ ｃ Ｎｉ ｄ Ｆｅ ｅ Ｘ ｆ Ｙ ｇ Ｓｉ ｈ Ｏ ｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）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）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種の元素である。また、ａ〜ｊはそれぞれの元素の原子比を表し、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜１０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。） A composite oxide catalyst used when a monoolefin having 4 or more carbon atoms is subjected to gas phase catalytic oxidative dehydrogenation reaction with an oxygen-containing gas to produce a corresponding conjugated diene,
The composite oxide catalyst is an oxide of molybdenum, an oxide of bismuth, cobalt oxide, nickel oxide, the composite oxide catalyst represented oxide and silica iron including, by the following composition formula (1) And
A specific surface area of 5m 2 / g~25m 2 / g, a pore volume of 0.20ml / g~0.50ml / g, and pore diameter in a pore diameter distribution in 0.1μm~1.0μm The pore volume occupied by the existing pores is 50% to 68% of the total pore volume, and the pore volume occupied by the pores whose pore diameter is less than 0.1 μm is the total pore volume. The composite oxide catalyst which is 27% to 50% of the above.
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
Wherein X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B) , Phosphorus (P), arsenic (As), and tungsten (W), and at least one element selected from the group consisting of tungsten (W), and a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5-7, c = 0.1-10, d = 0.1-10, e = 0.05-5, f = 0-2, g = 0-3, h = 1-48. And i is a numerical value that satisfies the oxidation state of other elements.)
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