JP7209578B2 - Catalyst and its manufacturing method - Google Patents
Catalyst and its manufacturing method Download PDFInfo
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- JP7209578B2 JP7209578B2 JP2019076738A JP2019076738A JP7209578B2 JP 7209578 B2 JP7209578 B2 JP 7209578B2 JP 2019076738 A JP2019076738 A JP 2019076738A JP 2019076738 A JP2019076738 A JP 2019076738A JP 7209578 B2 JP7209578 B2 JP 7209578B2
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- catalyst
- producing
- metal oxide
- conjugated diolefin
- silica
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 146
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 89
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000377 silicon dioxide Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 29
- -1 diolefin compound Chemical class 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 22
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 59
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 58
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 36
- 239000002994 raw material Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 20
- 239000012752 auxiliary agent Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 150000001993 dienes Chemical class 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 150000005673 monoalkenes Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000002036 drum drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、高活かつ高収率で目的物を得られる新規触媒およびその製造方法に関するものであり、特に不飽和アルデヒド、不飽和カルボン酸、又は共役ジエンを酸化的に製造する際に、高活性、高収率を実現するものである。
特に、炭素原子数４以上のモノオレフィン原料から酸化脱水素反応により共役ジオレフィン、具体的にはｎ－ブテン原料から酸化脱水素反応によりブタジエンを製造する際に効果が大きく、高活性かつ高収率な運転を可能とする触媒およびその製造方法を特徴とする。
TECHNICAL FIELD The present invention relates to a novel catalyst capable of obtaining a target product with high activity and high yield, and a method for producing the same. It realizes activity and high yield.
In particular, it is highly effective in producing conjugated diolefins by oxidative dehydrogenation from monoolefin raw materials having 4 or more carbon atoms, more specifically, butadiene is produced from n-butene raw materials by oxidative dehydrogenation, resulting in high activity and high yield. It features a catalyst that enables efficient operation and a method for producing the same.
従来、合成ゴム等の原料であるブタジエンは、工業的にはナフサ留分の熱分解および抽出により製造されているが、今後、ブタジエンの市場への安定供給の悪化が懸念されることから、新たなブタジエンの製造方法が求められている。そこで、ｎ－ブテンと分子状酸素を含む混合ガスから、触媒の存在下でｎ－ブテンを酸化脱水素する方法が注目されている。 Conventionally, butadiene, a raw material for synthetic rubber, is industrially produced by thermal decomposition and extraction of naphtha fractions. There is a need for a method for producing butadiene with Therefore, a method of oxidative dehydrogenation of n-butene from a mixed gas containing n-butene and molecular oxygen in the presence of a catalyst has attracted attention.
工業プラントでの経済性の観点から、目的生成物であるブタジエンを高い収率および選択率で得られる点のみならず、通常（以下、通常とは一般的なビスマスモリブデート触媒を使用する酸化脱水素反応での反応浴温度を示す。）より低い反応浴温度においても高活性を維持し、運転することが求められる。すなわち、触媒が高活性および高選択率を示すことにより、反応後に残存する原料ｎ－ブテンをリサイクルするプロセスにおいても高い経済優位性を示すことができる。工業プラントにおける熱媒のランニングコストを抑制するため、低い反応浴温度でも高活性である触媒が求められている。 From the viewpoint of economy in industrial plants, not only is it possible to obtain the desired product butadiene with high yield and selectivity, but oxidative dehydration using a normal (hereinafter referred to as normal) bismuth molybdate catalyst It shows the reaction bath temperature in the elementary reaction.) It is required to operate while maintaining high activity even at lower reaction bath temperatures. That is, since the catalyst exhibits high activity and high selectivity, it can exhibit high economic superiority even in the process of recycling raw material n-butene remaining after the reaction. In order to reduce the running costs of heat transfer media in industrial plants, catalysts that are highly active even at low reaction bath temperatures are desired.
上記ｎ－ブテン原料から酸化脱水素反応によるブタジエン製造プロセスにおいて、殊に高活性または高選択率を示す触媒の研究については既に数多くの報告がなされている。特許文献１は、特定の元素比におけるビスマスモリブデート複合金属酸化物触媒に関するものである。 Numerous reports have already been made on research on catalysts exhibiting particularly high activity or high selectivity in the process of producing butadiene by oxidative dehydrogenation reaction from the n-butene starting material. Patent Document 1 relates to a bismuth molybdate mixed metal oxide catalyst with a specific element ratio.
特許文献２は、調合順序や調合液のｐＨ等を規定したビスマスモリブデート複合金属酸化物触媒の製造方法に関するものである。 Patent Document 2 relates to a method for producing a bismuth molybdate mixed metal oxide catalyst in which the order of preparation and the pH of the prepared solution are specified.
特許文献３は、触媒細孔の大きさを制御したビスマスモリブデート複合金属酸化物触媒に関するものである。 Patent Document 3 relates to a bismuth-molybdate mixed metal oxide catalyst with controlled catalyst pore size.
特許文献４は、触媒の酸量かつ比表面積を制御したビスマスモリブデート複合金属酸化物触媒に関するものである。 Patent Document 4 relates to a bismuth molybdate mixed metal oxide catalyst in which the acid amount and specific surface area of the catalyst are controlled.
しかしながら、特許文献１～４の触媒では、プラントでの運転制御の観点で工業用触媒として十分な性能が得られておらず、更なる改良が望まれていた。また、ビスマスモリブデート複合金属酸化物触媒においては、従来よりシリカ及びアルミナが不活性担体として使用されてきたものの、シリカ及びアルミナの両方を含む検討はこれまで実施されておらず、さらにシリカ及びアルミナがどの程度の比率で共存すれば、良好な触媒性能を示すのかは不明確であった。 However, the catalysts of Patent Documents 1 to 4 do not have sufficient performance as industrial catalysts from the viewpoint of plant operation control, and further improvements have been desired. In addition, in bismuth molybdate mixed metal oxide catalysts, silica and alumina have been conventionally used as inert carriers. It was unclear at what ratio the coexistence of N and N would lead to good catalytic performance.
本発明は、高活かつ高収率で目的物を得られる新規触媒およびその製造方法に関するものであり、特に不飽和アルデヒド、不飽和カルボン酸、又は共役ジエンを酸化的に製造する際に、高活性、高収率を実現するものである。
特に、炭素原子数４以上のモノオレフィン原料から酸化脱水素反応により共役ジオレフィン、具体的にはｎ－ブテン原料から酸化脱水素反応によりブタジエンを製造する際に効果が大きく、高活性かつ高収率な運転を可能とする触媒およびその製造方法を提供することを目的とする。
TECHNICAL FIELD The present invention relates to a novel catalyst capable of obtaining a target product with high activity and high yield, and a method for producing the same. It realizes activity and high yield.
In particular, it is highly effective in producing conjugated diolefins by oxidative dehydrogenation from monoolefin raw materials having 4 or more carbon atoms, more specifically, butadiene is produced from n-butene raw materials by oxidative dehydrogenation, resulting in high activity and high yield. An object of the present invention is to provide a catalyst that enables efficient operation and a method for producing the same.
本発明者らは前記課題を解決すべく鋭意研究の結果、炭素原子数４以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するプロセスにおいて、シリカ（ＳｉＯ２）及びアルミナ（Ａｌ２Ｏ３）を含有し、その含有量比が特定の範囲にある触媒を使用することで、より高活性かつ高収率で共役ジオレフィンを製造することができることを見出し、本発明を完成させるに至った。
なお、本発明の触媒は、ビスマスモリブデート複合金属酸化物触媒であるが、本明細書中では単に触媒と表現する場合もある。
また本明細書中「～」は以上以下を意味する。すなわち「～」を挟む前後の数値は含むものとする。
As a result of intensive research to solve the above problems, the present inventors found that silica ( SiO 2 ) and alumina (Al 2 O 3 ), and by using a catalyst whose content ratio is within a specific range, it is possible to produce a conjugated diolefin with higher activity and yield. This led to the completion of the present invention.
Although the catalyst of the present invention is a bismuth-molybdate mixed metal oxide catalyst, it may be simply expressed as a catalyst in this specification.
In addition, "-" in this specification means above and below. That is, numbers before and after sandwiching "~" shall be included.
即ち、本発明は以下１）～９）に関する。
１）
シリカ（ＳｉＯ２）及びアルミナ（Ａｌ２Ｏ３）を不活性成分として含有する触媒であって、シリカの含有量とアルミナの含有量の重量比率が１：０．０１～１：５０．００である、ビスマスモリブデート複合金属酸化物触媒。
２）
シリカ（ＳｉＯ２）及びアルミナ（Ａｌ２Ｏ３）を不活性成分として含有する触媒であって、平均粒子径が２．５０ｍｍ以上４．４９ｍｍ以下である、上記１）に記載のビスマスモリブデート複合金属酸化物触媒。
３）
活性成分としての触媒組成が、下記式（１）で表される上記１）又は２）に記載の共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
Ｍｏ１２ＢｉａＦｅｂＣｏｃＮｉｄＸｅＹｆＺｇ・・・・（１）
（式中、Ｘはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも１種の元素を示し、Ｙはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも１種の元素を示し、Ｚはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、タリウムから選ばれる少なくとも１種の元素を示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、およびｇは各々モリブデン１２に対するビスマス、鉄、コバルト、ニッケル、Ｘ、Ｙ、Ｚの原子比を示し、０．３＜ａ＜３．５、０．６＜ｂ＜３．４、５．０＜ｃ＜８．０、０．０＜ｄ＜３．０、０．０＜ｅ＜０．５、０．０≦ｆ≦４．０、０≦ｇ≦２．０の範囲にあり、式（１）中に記載はないが酸素原子Ｏは他の元素の酸化状態を満足させる適当な原子比となる）。
４）
シリカ及びアルミナが不活性担体として触媒に含有されている上記１）乃至３）のいずれか一項に記載の、炭素原子数４以上のモノオレフィン化合物と分子状酸素を含む混合ガスを原料とした接触酸化脱水素反応による共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
５）
不活性担体の気孔率が、０％以上６０％以下である上記４）に記載の共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
６）
不活性担体の吸水率が、２％以上５０％以下である上記４）又は５）に記載の共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
７）
炭素原子数４以上のモノオレフィン化合物と分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィン化合物を製造するための上記１）乃至６）のいずれか一項に記載の共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
８）
下記工程を含むことを特徴とする上記１）乃至７）のいずれか一項に記載のビスマスモリブデート複合金属酸化物触媒の製造方法、
工程（Ａ１）：複合金属酸化物の各金属を含有する化合物を含む混合溶液またはスラリーを２０℃以上９０℃以下の条件下で調製し、スプレー乾燥して乾燥粉体を得る工程、
工程（Ａ２）：工程（Ａ１）で得られた乾燥粉体を予備焼成し、予備焼成粉体を得る工程、
工程（Ａ３）：工程（Ａ２）で得られた予備焼成粉体を成形し、成形品を得る工程、
工程（Ａ４）：工程（Ａ３）で得られた成形品を本焼成する工程。
９） 予備焼成の温度が２００℃以上６００℃以下であり、本焼成温度が２００℃以上６００℃以下である上記８）に記載のビスマスモリブデート複合金属酸化物触媒の製造方法。
That is, the present invention relates to the following 1) to 9).
1)
A catalyst containing silica (SiO 2 ) and alumina (Al 2 O 3 ) as inert components, wherein the weight ratio of silica content to alumina content is 1:0.01 to 1:50.00 A bismuth molybdate mixed metal oxide catalyst.
2)
The bismuth molybdate composite according to 1) above, which is a catalyst containing silica (SiO 2 ) and alumina (Al 2 O 3 ) as inert components and having an average particle size of 2.50 mm or more and 4.49 mm or less. Metal oxide catalyst.
3)
A bismuth molybdate mixed metal oxide catalyst for producing a conjugated diolefin compound according to 1) or 2) above, wherein the catalyst composition as an active component is represented by the following formula (1).
Mo12BiaFebCocNidXeYfZg ( 1 ) _ _ _ _
(In the formula, X represents at least one element selected from alkali metals selected from lithium, sodium, potassium, rubidium and cesium, and Y represents at least one element selected from alkaline earth metals selected from magnesium, calcium, strontium and barium. represents an element, Z represents at least one element selected from lanthanum, cerium, praseodymium, neodymium, samarium, eurobium, antimony, tungsten, lead, zinc and thallium, a, b, c, d, e, f, and g represent the atomic ratios of bismuth, iron, cobalt, nickel, X, Y and Z to molybdenum 12, respectively, 0.3<a<3.5, 0.6<b<3.4, 5.0< c < 8.0, 0.0 < d < 3.0, 0.0 < e < 0.5, 0.0 ≤ f ≤ 4.0, 0 ≤ g ≤ 2.0, and the formula ( 1) Although not described therein, the oxygen atom O has an appropriate atomic ratio that satisfies the oxidation state of other elements).
4)
Using as a raw material a mixed gas containing a monoolefin compound having 4 or more carbon atoms and molecular oxygen according to any one of 1) to 3) above, wherein silica and alumina are contained in the catalyst as inert carriers. Bismuth molybdate mixed metal oxide catalyst for the production of conjugated diolefin compounds by catalytic oxidative dehydrogenation.
5)
The bismuth molybdate mixed metal oxide catalyst for producing a conjugated diolefin compound according to 4) above, wherein the inert carrier has a porosity of 0% or more and 60% or less.
6)
The bismuth molybdate mixed metal oxide catalyst for producing a conjugated diolefin compound according to 4) or 5) above, wherein the inert carrier has a water absorption of 2% or more and 50% or less.
7)
The conjugated diolefin according to any one of 1) to 6) above for producing a conjugated diolefin compound by a catalytic oxidative dehydrogenation reaction from a mixed gas containing a monoolefin compound having 4 or more carbon atoms and molecular oxygen. Bismuth molybdate mixed metal oxide catalyst for compound production.
8)
The method for producing the bismuth molybdate mixed metal oxide catalyst according to any one of 1) to 7) above, which comprises the following steps:
Step (A1): A step of preparing a mixed solution or slurry containing a compound containing each metal of the composite metal oxide under conditions of 20° C. or higher and 90° C. or lower, and spray-drying to obtain a dry powder;
Step (A2): a step of pre-baking the dry powder obtained in step (A1) to obtain a pre-baked powder;
Step (A3): a step of molding the pre-fired powder obtained in step (A2) to obtain a molded product;
Step (A4): A step of firing the molded product obtained in step (A3).
9) The method for producing a bismuth molybdate mixed metal oxide catalyst according to 8) above, wherein the pre-calcination temperature is 200°C or higher and 600°C or lower, and the main calcination temperature is 200°C or higher and 600°C or lower.
本発明の触媒は、酸化反応用触媒として非常に有用である。特に酸化脱水素反応に好適に用いられ、オレフィンからジオレフィンを製造する触媒として有用な機能を有する。 従って、本発明の触媒を使用することにより、製造効率及び生産性が高く、高収率にブタジエンを生成することができる。 本発明の触媒の別の利点として、反応の長期安定性が挙げられる。特にオレフィンからジオレフィンを製造する触媒においては、反応中に炭素（コーク状物質）の析出（コーキング）が生じ、特に固定床型反応器においては触媒が破損される、あるいは反応管内の圧力損失が増大し安定に反応が継続できなくなる点が課題として挙げられる。本発明の触媒を使用することで、炭素析出の前駆体物質の触媒内部の滞留およびそれらの堆積によるコーキングを抑制することができ、高収率かつ安定に反応を長期間継続させることができる。 The catalyst of the present invention is very useful as an oxidation reaction catalyst. It is particularly suitable for oxidative dehydrogenation reactions and has a useful function as a catalyst for producing diolefins from olefins. Therefore, by using the catalyst of the present invention, production efficiency and productivity are high, and butadiene can be produced in high yield. Another advantage of the catalysts of the present invention is the long term stability of the reaction. Especially in catalysts for producing diolefins from olefins, precipitation of carbon (coke-like substances) occurs during the reaction (coking), and especially in fixed-bed reactors, the catalyst is damaged, or the pressure loss inside the reaction tube occurs. The problem is that it increases and the reaction cannot continue stably. By using the catalyst of the present invention, retention of precursor substances for carbon deposition inside the catalyst and coking due to their deposition can be suppressed, and the reaction can be stably continued for a long period of time with high yield.
炭素原子数４以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造する反応に使用でき、好ましくはｎ－ブテンと分子状酸素を含む混合ガスから接触酸化脱水素反応によりブタジエンを製造する反応に使用できる触媒およびその製造方法であり、以下その詳細について説明する。 It can be used in a reaction for producing a conjugated diolefin by catalytic oxidation dehydrogenation from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen, preferably catalytic oxidation from a mixed gas containing n-butene and molecular oxygen. A catalyst that can be used in a reaction for producing butadiene by dehydrogenation and a method for producing the same, the details of which will be described below.
本発明における炭素原子数４以上のモノオレフィンとは、炭素－炭素二重結合１個を含む炭素原子数４以上の不飽和炭化水素であり、ブテン、ペンテン、へキセン、ヘプテン、オクテン、ノネンおよびデセン等が挙げられ、ｎ－ブテンとは１－ブテン、トランス－２－ブテン、シス－２－ブテン、イソブチレンのうち、単一成分のガス、もしくは少なくとも一つの成分を含む混合ガスを意味するものとし、共役ジオレフィン化合物とは、１つの単結合を介して結合している２つの炭素－炭素二重結合をもつ炭化水素化合物であり、好ましくはブタジエン、特に好ましくは１，３－ブタジエンを意味するものとする。 The monoolefins having 4 or more carbon atoms in the present invention are unsaturated hydrocarbons having 4 or more carbon atoms and containing one carbon-carbon double bond, and include butene, pentene, hexene, heptene, octene, nonene and decene and the like, and n-butene means a gas of a single component or a mixed gas containing at least one component among 1-butene, trans-2-butene, cis-2-butene and isobutylene. and the conjugated diolefin compound is a hydrocarbon compound having two carbon-carbon double bonds bonded via one single bond, preferably butadiene, particularly preferably 1,3-butadiene. It shall be.
本発明において高活性とは、通常より低い反応浴温度において、後述するｎ－ブテン転化率が一定以上の値を示すこと、および同じ反応浴温度においてより高いｎ－ブテン転化率の値を示すこと、のいずれかまたはその両方を意味し、本発明において活性および転化率とは、特に断りがない限り後述するｎ－ブテン転化率と同義、また収率とは後述するブタジエン収率と同義、さらに選択率とは後述するブタジエン選択率と同義である。後述するようにｎ－ブテン転化率が低い反応浴温度および反応条件で触媒を運転する場合、商業プラントでは一般にリサイクルプロセスを行う。リサイクルプロセスとは、反応器を通過した生成ガスおよび／または生成液の一部または全部より、生成物および副生成物を一定量除去した後のガス成分（リサイクルガス）を、再度反応器に流通反応させるプロセスのことを意味し、リサイクルガスはその他原料ガスと混合されて必要に応じ適宜加温されるプロセスを含む。後述する実施例で示すような、リサイクルプロセスを使用しない（ワンパス）での選択率とは、リサイクルプロセスにおける収率と同義であり、それゆえ本発明における高収率とは、ワンパスにおける選択率が高いことを含む。 In the present invention, high activity means that the n-butene conversion rate, which will be described later, shows a certain value or higher at a reaction bath temperature lower than usual, and that the n-butene conversion rate shows a higher value at the same reaction bath temperature. , In the present invention, activity and conversion are synonymous with n-butene conversion, which will be described later, unless otherwise specified. Yield is synonymous with butadiene yield, which will be described later. The selectivity is synonymous with the butadiene selectivity described later. When the catalyst is operated at reaction bath temperatures and reaction conditions with low n-butene conversions, as described below, commercial plants generally employ a recycling process. The recycling process refers to the gas component (recycle gas) after a certain amount of products and by-products have been removed from part or all of the product gas and/or product liquid that has passed through the reactor, and then circulated to the reactor again. It means a process of reacting, and includes a process in which the recycled gas is mixed with other raw material gases and appropriately heated as necessary. The selectivity without using the recycling process (one pass) as shown in the examples described later is synonymous with the yield in the recycling process, and therefore the high yield in the present invention means that the selectivity in the one pass is Including high.
［シリカの含有量とアルミナの含有量の重量比率］
本発明の共役ジオレフィン化合物製造用触媒は、触媒中にシリカ（ＳｉＯ２）とアルミナ（ＡｌＯ３）を含有し、その重量比率（ＳｉＯ２：Ａｌ２Ｏ３）が１：０．０１～１：５０．００である。シリカとアルミナは一般的には、不活性成分とされ、過度な反応の進行を抑え、適切にコントロールしたり、触媒の物理的硬度を調整したりする成分とされている。従って、シリカやアルミナの触媒中での含有量については従来から鋭意検討されてきた。しかし、本発明者は、シリカとアルミナの反応をコントロールする程度の違い、それぞれの物理的硬度に与える影響の違い等に着目し、鋭意検討した結果、その重量比率が１：０．０１～１：５０．００である場合に、触媒の性能を大幅に向上できることを発見し、本発明に至った。
[Weight ratio of silica content and alumina content]
The catalyst for producing a conjugated diolefin compound of the present invention contains silica (SiO 2 ) and alumina (AlO 3 ) in the catalyst, and the weight ratio (SiO 2 :Al 2 O 3 ) is 1:0.01 to 1. : 50.00. Silica and alumina are generally regarded as inert components, which are components for suppressing the progress of excessive reactions, appropriately controlling them, and adjusting the physical hardness of the catalyst. Therefore, the contents of silica and alumina in catalysts have been extensively studied. However, the present inventor paid attention to the difference in the degree of control of the reaction between silica and alumina, the difference in the effect on physical hardness, etc., and as a result of intensive investigation, the weight ratio was 1: 0.01 to 1. : 50.00, the performance of the catalyst can be significantly improved, leading to the present invention.
本発明において、シリカとアルミナの重量比率とは、触媒中に含有するシリカの重量を１としたアルミナとの重量比率を意味し、不活性成分としてのシリカおよび不活性成分としてのアルミナの化学状態は触媒反応において当業者にとって触媒反応に対して不活性と見なされるならば、結晶相や表面粗さ等物性含めその詳細を問わないが、たとえばシリカに関しては結晶性シリカ、シリカゲルや非結晶性シリカが挙げられ、特に結晶性シリカが好ましく、アルミナに関してはアランダムやα－アルミナが挙げられ、特にα－アルミナが好ましい。また本発明においてシリカ及びアルミナが前記の化学状態を満たすための製法も当業者であれば明らかなように、１０００℃以上の温度で焼成されたものを指す。すなわちたとえば、シリカゾルを出発原料の一部として６００℃以下の温度で焼成された触媒のシリカは、不活性成分としてのシリカではなく活性成分としてのシリカとなる。そして、シリカとアルミナの比率は１：０．０１～１：５０．００であれば良いが、好ましくは１：０．１０～１：２５．００であり、更に好ましくは１：０．２０～１：１０．００であり、特に好ましくは１：０．３０～１：６．００、最も好ましくは１：２．００～１：３．５０である。また本発明において不活性成分とは、当業者にとって触媒反応に対して不活性と見なされるならばその詳細を定義しないが、たとえば後述する反応条件において転化率が０．１％以下のものを指す。
本発明においてシリカとアルミナの重量比率は、その他の不活性成分も含め内部標準を加えた、あるいは絶対検量線にて当業者にとって自明な方法で校正された各種元素分析装置にて測定される実測値により算出されるものとする。その詳細な測定方法は、上記の範囲内であれば問わないが、例えば蛍光Ｘ線測定による以下方法となる。測定装置として、リガク社製Ｐｒｉ ｍｉｎｉを用い、測定温度は３５℃、測定圧力は１Ｐａ、測定時間４５分、光源としてＰｄ管球を用い、Ｘ線強度は４０ｋｅＶ（１．２５ｍＡ）、分光結晶としてＬｉＦｌを使用し、検出器としてＳＣおよびＦ－ＰＣの両方を使用する。
本発明においてシリカ、アルミナは触媒活性成分と共存しても、後記するように、不活性担体として触媒活性成分を担持させた形で存在しても良い。なお、共存するとは活性成分と合せて、例えば混練された場合等を意味する。
In the present invention, the weight ratio of silica and alumina means the weight ratio of alumina to the weight of silica contained in the catalyst as 1, and the chemical state of silica as an inert component and alumina as an inert component is considered to be inert to the catalytic reaction by those skilled in the art, the details including physical properties such as crystalline phase and surface roughness do not matter, but for silica, crystalline silica, silica gel and amorphous silica Crystalline silica is particularly preferred, and alumina includes alundum and α-alumina, and α-alumina is particularly preferred. In addition, in the present invention, the production method for silica and alumina to satisfy the above-mentioned chemical conditions also refers to calcination at a temperature of 1000° C. or higher, as is clear to those skilled in the art. That is, for example, the silica of the catalyst calcined at a temperature of 600° C. or less using silica sol as a part of the starting material becomes silica as an active component, not silica as an inactive component. The ratio of silica and alumina may be 1:0.01 to 1:50.00, preferably 1:0.10 to 1:25.00, more preferably 1:0.20 to 1:10.00, particularly preferably 1:0.30 to 1:6.00, most preferably 1:2.00 to 1:3.50. Further, in the present invention, the inert component is not defined in detail if it is regarded as inert to the catalytic reaction by those skilled in the art, but for example, it refers to a component with a conversion rate of 0.1% or less under the reaction conditions described later. .
In the present invention, the weight ratio of silica and alumina, including other inert components, is measured by various elemental analyzers calibrated by a method obvious to those skilled in the art by adding an internal standard or using an absolute calibration curve. It shall be calculated by the value. The detailed measurement method is not limited as long as it is within the above range, but for example, the following method by fluorescent X-ray measurement is used. Rigaku's Pri mini was used as the measurement device, the measurement temperature was 35°C, the measurement pressure was 1 Pa, the measurement time was 45 minutes, the light source was a Pd tube, the X-ray intensity was 40 keV (1.25 mA), and the analyzing crystal was LiFl is used and both SC and F-PC are used as detectors.
In the present invention, silica and alumina may coexist with the catalytically active component, or may exist in the form of supporting the catalytically active component as an inert carrier, as will be described later. In addition, the coexistence means, for example, the case where they are kneaded together with the active ingredient.
［平均粒子径］
本発明の触媒の形状は、特に制限されるものではく、球状、円柱状、リング状等を挙げることができるが、好ましくは球状である。球状とは、実質的に球状であることを意味し、真球である必要はない。
そしてその平均粒子径は、無作為にサンプリングした一部の触媒について測定したものであればその詳細を問わないが、例えば３００個以上の触媒を測定すれば良い。
なお、測定方法としては、各触媒球の長さ（Ｌ）、幅（Ｂ）、厚さ（Ｔ）の平均から求めた三軸平均径による。
本発明の触媒は、上記方法で求めた平均粒子径が２．５０ｍｍ以上４．４９ｍｍ以下である場合が好ましい。そして、より好ましい上限は４．４７ｍｍであり、更に好ましくは４．４５ｍｍであり、特に好ましくは４．４３ｍｍである。またより好ましい下限は３．００ｍｍであり、更に好ましくは３．３０ｍｍであり、特に好ましくは３．６０ｍｍである。従って、最も好ましい平均粒子径は３．６０ｍｍ以上４．４３ｍｍ以下である。
この平均粒子径は、大きくなると酸化的脱水素反応自体が発熱反応であるがために触媒内部の蓄熱効果が高くなり、目的生成物のブタジエン選択率が低下する傾向があり、平均粒子径が小さくなると反応器内のガスの流れ方が複雑かつ不均一になり、望ましくない副反応が生じるために目的生成物のブタジエン選択率が低下する傾向がある。このため前述の通り、酸化的脱水素反応における球状触媒の平均粒子径には、望ましい数値範囲が生じることになることが本発明者らによって明らかにされた。
[Average particle size]
The shape of the catalyst of the present invention is not particularly limited, and may be spherical, cylindrical, ring-shaped, etc., preferably spherical. "Spherical" means substantially spherical, and does not have to be perfectly spherical.
The average particle size is not particularly limited as long as it is measured for some randomly sampled catalysts. For example, 300 or more catalysts may be measured.
The measurement method is based on the triaxial average diameter calculated from the average length (L), width (B) and thickness (T) of each catalyst sphere.
The catalyst of the present invention preferably has an average particle size of 2.50 mm or more and 4.49 mm or less as determined by the above method. A more preferable upper limit is 4.47 mm, more preferably 4.45 mm, and particularly preferably 4.43 mm. A more preferable lower limit is 3.00 mm, more preferably 3.30 mm, and particularly preferably 3.60 mm. Therefore, the most preferable average particle size is 3.60 mm or more and 4.43 mm or less.
As the average particle size increases, the oxidative dehydrogenation reaction itself is an exothermic reaction, so the heat storage effect inside the catalyst tends to increase, and the butadiene selectivity of the target product tends to decrease. Then, the flow of gas in the reactor becomes complicated and non-uniform, and undesirable side reactions tend to occur, which tends to reduce the selectivity of butadiene to the desired product. Therefore, as described above, the present inventors have clarified that the average particle size of the spherical catalyst in the oxidative dehydrogenation reaction has a desirable numerical range.
［気孔率］
本発明において使用される不活性担体の気孔率は、０％以上６０％以下であることが好ましく、より好ましい上限は５５％、さらに好ましい上限は５０％、最も好ましい上限は４７％であり、より好ましい下限は１０％、さらに好ましい下限は２０％、最も好ましい下限は３０％である。本気孔率の測定は、当業者であれば容易に知りえる一般的な方法であればその詳細を問わないが、好ましくはＪＩＳ Ｒ２２０５に規定される方法となる。
[Porosity]
The porosity of the inert carrier used in the present invention is preferably 0% or more and 60% or less, a more preferable upper limit is 55%, a further preferable upper limit is 50%, and the most preferable upper limit is 47%. A preferred lower limit is 10%, a more preferred lower limit is 20%, and the most preferred lower limit is 30%. The measurement of the air porosity is not limited in detail as long as it is a general method easily known by those skilled in the art, but the method defined in JIS R2205 is preferable.
［吸水率］
本発明において使用される不活性担体の吸水率は、２％以上５０％以下であることが好ましく、より好ましい上限は３０％、さらに好ましい上限は２８％、最も好ましい上限は２５％であり、より好ましい下限は８％、さらに好ましい下限は１５％、最も好ましい下限は１８％である。本吸水率の測定は、当業者であれば容易に知りえる一般的な方法であればその詳細を問わないが、好ましくはＪＩＳ Ｒ２２０５に規定される方法となる。
[Water absorption]
The water absorption rate of the inert carrier used in the present invention is preferably 2% or more and 50% or less, a more preferable upper limit is 30%, a further preferable upper limit is 28%, and the most preferable upper limit is 25%. A preferred lower limit is 8%, a more preferred lower limit is 15%, and the most preferred lower limit is 18%. The water absorption rate can be measured by any general method easily known to those skilled in the art, but the method specified in JIS R2205 is preferable.
［触媒組成］
本発明の共役ジオレフィン化合物製造用触媒は、その反応に寄与する活性成分として下記式（１）で表される組成である場合が好ましい（本発明の触媒活性成分）。
Ｍｏ１２ＢｉａＦｅｂＣｏｃＮｉｄＸｅＹｆＺｇ・・・（１）
上記式（１）中、Ｘはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも１種の元素を示す。このうち好ましくはカリウム、ルビジウム、セシウムあり、さらに好ましくはセシウムである。
Ｙはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも１種の元素を示す。このうち好ましくはマグネシウム、カルシウム、ストロンチウムであり、さらに好ましくはマグネシウム、カルシウムである。
Ｚはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、タリウムから選ばれる少なくとも１種の元素を示す。このうち好ましくはランタン、セリウム、プラセオジム、サマリウム、アンチモン、タングステン、鉛、亜鉛、タリウムであり、さらに好ましくはラセリウム、プラセオジム、タングステン、鉛、タリウムである。
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、およびｇは各々モリブデン１２に対するビスマス、鉄、コバルト、ニッケル、Ｘ、Ｙ、Ｚの原子比を示す。それぞれの範囲として、０．３＜ａ＜３．５、０．６＜ｂ＜３．４、５．０＜ｃ＜８．０、０．０＜ｄ＜３．０、０．０＜ｅ＜０．５、０．０≦ｆ≦４．０、０．０≦ｇ≦２．０が好ましいが、さらに好ましくは０．５＜ａ＜１．７、１．２＜ｂ＜３．０、５．５＜ｃ＜７．２、０．８＜ｄ＜２．５、０．０１＜ｅ＜０．２、０．０≦ｆ≦１．５、０．０≦ｇ≦１．５であり、式（１）中に記載はないが酸素原子Ｏは他の元素の酸化状態を満足させる適当な原子比となる。ただし、上記活性成分とは別に不活性成分として含まれるシリカとアルミナの含有比は、上述の通りである。
[Catalyst composition]
The catalyst for producing a conjugated diolefin compound of the present invention preferably has a composition represented by the following formula (1) as an active component that contributes to the reaction (catalytically active component of the present invention).
Mo12BiaFebCocNidXeYfZg ( 1 ) _ _ _ _
In the above formula (1), X represents at least one alkali metal element selected from lithium, sodium, potassium, rubidium and cesium. Among them, potassium, rubidium and cesium are preferred, and cesium is more preferred.
Y represents at least one alkaline earth metal element selected from magnesium, calcium, strontium and barium. Among these, magnesium, calcium and strontium are preferred, and magnesium and calcium are more preferred.
Z represents at least one element selected from lanthanum, cerium, praseodymium, neodymium, samarium, eurobium, antimony, tungsten, lead, zinc and thallium. Among these, lanthanum, cerium, praseodymium, samarium, antimony, tungsten, lead, zinc and thallium are preferred, and racerium, praseodymium, tungsten, lead and thallium are more preferred.
a, b, c, d, e, f, and g indicate the atomic ratios of bismuth, iron, cobalt, nickel, X, Y, Z to molybdenum 12, respectively. As each range, 0.3 < a < 3.5, 0.6 < b < 3.4, 5.0 < c < 8.0, 0.0 < d < 3.0, 0.0 < e <0.5, 0.0≤f≤4.0, 0.0≤g≤2.0, more preferably 0.5<a<1.7, 1.2<b<3.0 , 5.5<c<7.2, 0.8<d<2.5, 0.01<e<0.2, 0.0≦f≦1.5, 0.0≦g≦1.5 Although not described in formula (1), the oxygen atom O has an appropriate atomic ratio that satisfies the oxidation state of other elements. However, the content ratio of silica and alumina, which are contained as inactive ingredients separately from the active ingredients, is as described above.
［不活性担体］
本発明の共役ジオレフィン化合物製造用触媒は、不活性担体に担持された触媒であっても良い。不活性担体としてはシリカ、アルミナ、チタニア、ジルコニア、ニオビア、シリカアルミナ、炭化ケイ素、炭化物、およびこれらの混合物など公知の物質が挙げられる。そして、不活性担体としてシリカ及び／又はアルミナを使用する場合、活性成分と共存するシリカ、アルミナと合せて、上記シリカの含有量とアルミナの含有量の重量比率を算出する。なお、シリカ及びアルミナが不活性担体として触媒に含有されている場合が好ましい。上記含有比率の範囲内であれば、シリカ及びアルミナの一方のみが不活性担体として用いられていても、双方が不活性担体として用いられていても良く、またシリカの一部やアルミナの一部が不活性担体として使用されていても良いが、シリカ及びアルミナの双方が全量不活性担体として使用されている場合が最も好ましい。その好ましい組成比については上述の通りである。
不活性担体への担持の方法は特に制限はないが、バインダーを用いた転動造粒法によりコーティングさせる方法が好ましい。
またその際の担持率は、以下式によって算出される。
担持率（質量％）＝（成形に使用した予備焼成粉体の質量）／｛（成形に使用した予備焼成粉体の質量）＋（成形に使用した担体の質量）｝×１００
上記担持率としての好ましい上限は、７０％であり、さらに好ましくは６０％である。担持率が高くなると、触媒中の活性成分の厚みは増す傾向にあり、その内部で蓄熱または発熱反応が生じ、好ましくない副反応により選択率は低下し、さらに副反応により原料ガス中の分子状酸素を消費するために触媒層の下層側で反応に必要な分子状酸素が不足し、入口ガス組成にもよるが結果として転化率が下がることがある。これは、不活性担体として本発明の範囲外の担体を使用した場合にも触媒内部で蓄熱または発熱が生じるため同様の結果を招く。
また好ましい下限は、２５％であり、さらに好ましくは３５％である。担持率が低くなると充填体積当たりの活性成分が減るために低活性となり、商業プラントとして必要な転化率で反応をするには反応浴温度を上げる必要があり、結果的にランニングコストの増加及び反応浴温度上昇による選択率低下が生じることとなる。なお不活性担体としては、シリカ及びアルミナを含有し、その比率が上記の範囲内であれば他の不活性成分を含有しても良い。他の不活性成分とは例えばチタニア、ジルコニア、ニオビア、炭化ケイ素、炭化物、およびこれらの混合物などである。
なお本発明の実施例においては、最終形態の触媒の粒径を揃えるよう調製しているが、不活性担体の嵩比重が異なるために、上記式の定義の通り担持率が若干変わりうる。
[Inert carrier]
The catalyst for producing a conjugated diolefin compound of the present invention may be a catalyst supported on an inert carrier. Inert supports include known materials such as silica, alumina, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof. When silica and/or alumina are used as the inert carrier, the weight ratio of the silica content to the alumina content is calculated by combining the silica and alumina coexisting with the active ingredient. It is preferable that the catalyst contains silica and alumina as inert carriers. As long as the content ratio is within the above range, only one of silica and alumina may be used as the inert carrier, or both may be used as the inert carrier, and part of silica and part of alumina may be used as the inert carrier, but it is most preferred if both silica and alumina are used entirely as the inert carrier. The preferred composition ratio is as described above.
The method of loading on the inert carrier is not particularly limited, but a method of coating by tumbling granulation using a binder is preferred.
Further, the carrying rate at that time is calculated by the following formula.
Support rate (% by mass) = (mass of pre-fired powder used for molding)/{(mass of pre-fired powder used for molding) + (mass of carrier used for molding)} x 100
A preferable upper limit of the loading rate is 70%, more preferably 60%. As the loading ratio increases, the thickness of the active component in the catalyst tends to increase, heat storage or exothermic reaction occurs inside it, the selectivity decreases due to unfavorable side reactions, and the molecular Due to the consumption of oxygen, the lower layer side of the catalyst layer lacks the molecular oxygen necessary for the reaction, and depending on the inlet gas composition, the conversion rate may decrease as a result. This results in the same result when a carrier outside the scope of the present invention is used as the inert carrier because heat accumulation or heat generation occurs inside the catalyst.
A preferred lower limit is 25%, more preferably 35%. When the loading rate is low, the active ingredient per filling volume is reduced, resulting in low activity, and it is necessary to raise the reaction bath temperature in order to react at the conversion rate required for a commercial plant, resulting in an increase in running cost and reaction. A decrease in selectivity occurs due to an increase in bath temperature. The inert carrier contains silica and alumina, and may contain other inert components as long as the ratio is within the above range. Other inert ingredients include, for example, titania, zirconia, niobia, silicon carbide, carbides, and mixtures thereof.
In the examples of the present invention, the catalysts in the final form are prepared so as to have the same particle size. However, since the bulk specific gravity of the inert carrier differs, the loading rate may vary slightly as defined by the above formula.
本発明の触媒を得るための各金属元素の原料としては特に制限はないが、各金属元素を少なくとも一種含む硝酸塩、亜硝酸塩、硫酸塩、アンモニウム塩、有機酸塩、酢酸塩、炭酸塩、次炭酸塩、塩化物、無機酸、無機酸の塩、ヘテロポリ酸、ヘテロポリ酸の塩、水酸化物、酸化物、金属、合金等、またはこれらの混合物を用いることができる。このうち好ましいのは硝酸塩原料である。硝酸塩原料を用いることにより、本発明のように調合液にアルカリ溶液を添加した場合でも、調合液は共沈または沈殿を生じず、適度な粘度のスラリーとなり、スプレー乾燥による乾燥が可能となり、高い生産性で触媒の製造が可能となり、製造コストを低く抑えることが可能となる。すなわち、本発明では原料において硝酸塩原料またはそれに準ずる酸成分を適度に含んだ原料を使用することにより、上記の通り製造コストを低く抑えることが可能となる。各金属元素の酸成分の含有率としては、各金属元素単独での原料の飽和水溶液のｐＨで規定でき、－２．０以上１０．０以下が好ましく、－１．０以上７．０以下がさらに好ましく、０．０以上５．０以下が最も好ましい。 Raw materials of each metal element for obtaining the catalyst of the present invention are not particularly limited. Carbonates, chlorides, inorganic acids, salts of inorganic acids, heteropolyacids, salts of heteropolyacids, hydroxides, oxides, metals, alloys, etc., or mixtures thereof can be used. Of these, nitrate raw materials are preferred. By using a nitrate raw material, even when an alkaline solution is added to the prepared liquid as in the present invention, the prepared liquid does not cause coprecipitation or precipitation, becomes a slurry with an appropriate viscosity, can be dried by spray drying, and has a high The catalyst can be manufactured with high productivity, and the manufacturing cost can be kept low. That is, in the present invention, the production cost can be kept low as described above by using a nitrate raw material or a raw material containing an appropriate amount of an acid component corresponding to the nitrate raw material. The content of the acid component of each metal element can be defined by the pH of the saturated aqueous solution of the raw material of each metal element alone, and is preferably -2.0 or more and 10.0 or less, and -1.0 or more and 7.0 or less. More preferably, it is most preferably 0.0 or more and 5.0 or less.
本発明の触媒の調製法としては特に制限はないが、好ましいのは触媒活性成分を粉末として得た後、有機助剤を添加または使用することなく成形する方法であり、以下に詳細を記載する。なお、以下では各工程の順を好ましい例として記載しているが、最終的な触媒製品を得るための各工程の順番、工程数、各工程の組み合わせについて制限はないものとする。 The method for preparing the catalyst of the present invention is not particularly limited, but a preferred method is to obtain the catalytically active component as a powder and then mold it without adding or using an organic auxiliary agent, which will be described in detail below. . Although the order of each step is described below as a preferred example, the order of steps, the number of steps, and the combination of steps for obtaining the final catalyst product are not limited.
本発明の製造方法に使用する調合液とは、後述する触媒の製造工程（Ａ１）または（Ｂ１）において調製される、触媒活性成分である複合金属酸化物の原料のうち少なくとも一成分を含む混合溶液またはスラリーを意味するものとする。 The preparation liquid used in the production method of the present invention is a mixture containing at least one component among the raw materials of the composite metal oxide, which is the catalytically active component, prepared in the catalyst production step (A1) or (B1) described later. shall mean a solution or slurry.
本発明の触媒の製造方法としては、その詳細は後述するが、下記工程を含むことを特徴とする：
工程（Ａ１）：複合金属酸化物の各金属を含有する化合物を含む混合溶液またはスラリーを２０℃以上９０℃以下の条件下で調製し、該混合溶液またはスラリーのｐＨを前日の範囲内に適宜制御するようアルカリ溶液を添加し、スプレー乾燥して乾燥粉体を得る工程。
上記工程（Ａ１）において調合液のｐＨが高すぎると後述する乾燥噴霧（スプレー乾燥）法においては、触媒活性成分原料が共沈または一部沈殿が生じるために流路での目詰まり等が発生し均一な乾燥粉体が得られない、またはスプレー乾燥設備（スプレードライヤー）が安定して実施できない点が課題として生じうる。調合液のｐＨが高すぎることによる触媒活性成分原料の共沈または一部沈殿を避ける目的で、公知である分散剤を必要に応じて必要量投入する方法も本発明に包括される。
The method for producing the catalyst of the present invention, which will be described in detail later, is characterized by including the following steps:
Step (A1): A mixed solution or slurry containing a compound containing each metal of the composite metal oxide is prepared under conditions of 20° C. or higher and 90° C. or lower, and the pH of the mixed solution or slurry is appropriately adjusted within the range of the previous day. adding an alkaline solution in a controlled manner and spray drying to obtain a dry powder;
In the above step (A1), if the pH of the prepared solution is too high, in the dry spraying (spray drying) method described later, coprecipitation or partial precipitation of the raw material of the catalytically active component occurs, causing clogging in the flow path. However, problems may arise in that a uniform dry powder cannot be obtained, or that the spray drying equipment (spray dryer) cannot be stably operated. For the purpose of avoiding coprecipitation or partial precipitation of the raw material for the catalytically active component due to too high a pH of the prepared solution, the method of adding a required amount of a known dispersant as needed is also included in the present invention.
さらに下記工程を含むことを特徴とする：
工程（Ａ２）：工程（Ａ１）で得られた乾燥粉体を予備焼成し、予備焼成粉体を得る工程、
工程（Ａ３）：工程（Ａ２）で得られた予備焼成粉体を成形し、成形品を得る工程、
工程（Ａ４）：工程（Ａ３）で得られた成形品を本焼成する工程。
Further characterized by including the following steps:
Step (A2): a step of pre-baking the dry powder obtained in step (A1) to obtain a pre-baked powder;
Step (A3): a step of molding the pre-fired powder obtained in step (A2) to obtain a molded product;
Step (A4): A step of firing the molded product obtained in step (A3).
工程（Ａ１）調合と乾燥
触媒活性成分原料の混合溶液またはスラリーを調製し、沈殿法、ゲル化法、共沈法、水熱合成法等の工程を経た後、乾燥噴霧（スプレー乾燥、スプレードライ）法、蒸発乾固法、ドラム乾燥法、凍結乾燥法等の公知の乾燥方法を用いて、本発明の乾燥粉体を得る。この混合溶液またはスラリーは、溶媒として水、有機溶剤、またはこれらの混合溶液のいずれでも良く、また適宜混合溶液またはスラリーにｐＨ調整をする目的でアルカリ溶液を添加することが可能であり、触媒活性成分の原料濃度も制限はなく、さらに、この混合溶液またはスラリーの液温、雰囲気等の調合条件および乾燥条件について特に制限はないが、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、２０℃から９０℃の条件下で触媒活性成分の原料の混合溶液またはスラリーを形成させ、適宜アルカリ溶液によりｐＨを調整し、これを噴霧乾燥器に導入して乾燥器出口温度が７０℃から１５０℃、得られる乾燥粉体の平均粒径が１０μｍから７００μｍとなるよう熱風入口温度、噴霧乾燥器内部の圧力、およびスラリーの流量を調節する方法である。また、本工程の混合溶液またはスラリーの調製から前記乾燥までにおいて、後述する無機助剤または／および有機助剤を任意の量で添加することも本発明の触媒の製造方法に属するものとする。さらに、上記アルカリ溶液の種類に関しても公知なアルカリ溶液であればその濃度や成分および溶媒に制限はないが、アンモニア水や炭酸アンモニウム水溶液が好ましい。
Step (A1) Preparation and Drying A mixed solution or slurry of raw materials for catalytic active components is prepared, and after undergoing steps such as precipitation method, gelation method, coprecipitation method, hydrothermal synthesis method, etc., it is dried and sprayed (spray drying, spray drying ) method, evaporation to dryness method, drum drying method, freeze-drying method and other known drying methods are used to obtain the dry powder of the present invention. This mixed solution or slurry may be any of water, an organic solvent, or a mixed solution thereof as a solvent, and an alkaline solution may be added to the mixed solution or slurry for the purpose of adjusting the pH. There are no restrictions on the raw material concentrations of the components, and there are no particular restrictions on the mixing conditions such as the liquid temperature and atmosphere of this mixed solution or slurry, and the drying conditions. An appropriate range should be selected in consideration of efficiency and the like. Among these, the most preferred method in the present invention is to form a mixed solution or slurry of raw materials for catalytically active components under conditions of 20° C. to 90° C., adjust the pH with an alkaline solution as appropriate, and introduce this into a spray dryer. In this method, the hot air inlet temperature, the pressure inside the spray dryer, and the flow rate of the slurry are adjusted so that the dryer outlet temperature is 70° C. to 150° C. and the average particle size of the resulting dry powder is 10 μm to 700 μm. Further, addition of an arbitrary amount of an inorganic auxiliary agent and/or an organic auxiliary agent, which will be described later, from the preparation of the mixed solution or slurry in this step to the drying also belongs to the method for producing a catalyst of the present invention. Furthermore, regarding the type of the alkaline solution, there are no restrictions on its concentration, components and solvent as long as it is a known alkaline solution, but ammonia water and an aqueous ammonium carbonate solution are preferred.
工程（Ａ２）予備焼成
こうして得られた乾燥粉体を２００℃以上６００℃以下で予備焼成し、平均粒径が１０μｍから１００μｍである予備焼成粉体を得ることができる。この予備焼成の条件に関しても、焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、トンネル焼成炉において３００℃以上６００℃以下の範囲で１時間以上１２時間以下、空気雰囲気下による方法である。また、本工程の予備焼成前または予備焼成後において、後述する無機助剤または／および有機助剤を任意の量で添加することも本発明の触媒の製造方法に属するものとする。
Step (A2) Pre-Baking The dry powder thus obtained is pre-baked at 200° C. or higher and 600° C. or lower to obtain a pre-baked powder having an average particle size of 10 μm to 100 μm. As for the conditions of this preliminary calcination, there are no particular restrictions on the calcination time or the atmosphere during calcination. An appropriate range should be selected in consideration of physical strength, formability, production efficiency, etc. Among these methods, the most preferred method in the present invention is a method in which the temperature ranges from 300° C. to 600° C. for 1 hour to 12 hours in an air atmosphere in a tunnel firing furnace. In addition, before or after the preliminary calcination in this step, addition of an arbitrary amount of an inorganic auxiliary agent and/or an organic auxiliary agent, which will be described later, also belongs to the method for producing a catalyst of the present invention.
工程（Ａ３）成形
こうして得られた予備焼成粉体をそのまま触媒として使用することもできるが、成形して使用することもできる。成形品の形状は球状、円柱状、リング状など特に制限されないが、一連の調製で最終的に得られる触媒における機械的強度、反応器、調製の生産効率等を考慮して選択するべきである。成形方法についても特に制限はないが、以下に示す担体や有機助剤、無機助剤、バインダー等を予備焼成粉体に添加して円柱状、リング状に成形する際には打錠成形機や押出成形機などを用い、球状に成形する際には造粒機などを用いて成形品を得る。予備焼成粉体を不活性球状担体に担持した球状の被覆成形品を得る方法が好ましい。
Step (A3) Molding The pre-baked powder thus obtained can be used as it is as a catalyst, but it can also be used after being molded. The shape of the molded product is not particularly limited, and may be spherical, cylindrical, ring-shaped, etc., but should be selected in consideration of the mechanical strength of the catalyst finally obtained in a series of preparations, the reactor, the production efficiency of preparation, etc. . The molding method is not particularly limited, either. An extruder or the like is used, and when molding into a spherical shape, a granulator or the like is used to obtain a molded product. A method of obtaining a spherical coated molded article in which the pre-fired powder is supported on an inert spherical carrier is preferred.
無機助剤の添加量は、予備焼成粉体の質量に対して０．１質量％から２５質量％であり、０．３質量％から１０質量％が好ましく、０．５質量％から５質量％が最も好ましい。また無機助剤の材質および成分組成にも特に制限はないが、たとえばＥガラスのような無アルカリガラスや、シラン処理等各種化学的な不活性化処理を行ったガラスが、触媒反応に対する副生成物の生成などの悪影響を与えない点でより好ましい。また、無機助剤は、成形の前に粉砕工程を実施しても良く、粉砕の方法としては特に制限はないが、例えばボールミル、ロッドミル、ＳＡＧミル、ジェットミル、自主粉砕ミル、ハンマーミル、ペレットミル、ディスクミル、ローラーミル、高圧粉砕ロール、ＶＳＩミルなどを単独または組み合わせて実施され、この粉砕の対象は無機助剤単独でもよいが、予備焼成粉体その他成形工程に添加される触媒原料を混合したものでもよい。 The amount of the inorganic auxiliary added is 0.1% by mass to 25% by mass, preferably 0.3% by mass to 10% by mass, and 0.5% by mass to 5% by mass, based on the mass of the pre-fired powder. is most preferred. Although there are no particular restrictions on the material and component composition of the inorganic auxiliary agent, alkali-free glass such as E-glass, and glass that has been subjected to various chemical deactivation treatments such as silane treatment, can be used as a by-product of the catalytic reaction. It is more preferable in that it does not give adverse effects such as production of products. In addition, the inorganic auxiliary agent may be subjected to a pulverization process before molding, and the method of pulverization is not particularly limited, but for example, ball mill, rod mill, SAG mill, jet mill, self-pulverization mill, hammer mill, pellet Mills, disk mills, roller mills, high-pressure pulverizing rolls, VSI mills, etc. are used alone or in combination. The target of this pulverization may be the inorganic auxiliary agent alone, but the pre-baked powder and other catalyst raw materials added to the molding process may be used. A mixture may also be used.
本発明の触媒に使用する無機助剤とは、主に６００℃の熱処理においても焼失しない任意の無機物による任意の形状の助剤であり、後述する本焼成工程によりそのすべてが焼失しないものとする。無機助剤は、後述する本焼成工程においても残留するため、予備焼成粉体同士を結びつける役割があり、破損にかかる負荷が触媒に生じた際にも破損を抑制する効果が生じる。本発明において無機助剤の材質としてモース硬度は特に限定されないが、たとえば任意の硫化鉱物、酸化鉱物、ハロゲン化鉱物、無機酸塩鉱物、有機鉱物等を単独または組み合わせたものをガラス転移温度以上で熱処理したもののうちモース硬度が２以上のものが好ましく、これら材質の原料としては無機酸塩鉱物がさらに好ましい。また無機助剤に対して、酸処理、アルカリ処理、およびシラン処理等を各々単独または組み合わせて実施することで、触媒反応に不活性となる点で好適となる。 The inorganic auxiliary agent used in the catalyst of the present invention is an auxiliary agent of an arbitrary shape made of an arbitrary inorganic substance that is not burned off even in a heat treatment at 600 ° C., and is not completely burned off in the main calcination step described later. . Since the inorganic auxiliary agent remains even in the main sintering step, which will be described later, it has the role of binding the pre-sintered powders together, and has the effect of suppressing breakage even when a load that causes breakage is applied to the catalyst. In the present invention, the material of the inorganic auxiliary agent is not particularly limited in terms of Mohs hardness. Among heat-treated materials, those having a Mohs hardness of 2 or more are preferable, and inorganic acid salt minerals are more preferable as raw materials for these materials. Further, it is preferable to subject the inorganic auxiliary agent to acid treatment, alkali treatment, silane treatment, or the like, either singly or in combination, in order to render the inorganic auxiliary agent inert to the catalytic reaction.
本発明の触媒に使用する有機助剤とは、主に２００℃以上６００℃以下の熱処理により焼失する有機物よりなる任意の粉状、顆粒状、繊維状、鱗片状の助剤とし、後述する本焼成工程によりその一部またはすべてが焼失するものとし、たとえばポリエチレングリコールや各種エステルなどの重合物またはポリマービーズ、高吸水性樹脂の乾燥体または任意の吸水率による吸水物、各種界面活性剤、小麦粉または精製デンプン等の各種デンプン類、および結晶性またはアモルファス状のセルロースおよびその誘導体、が挙げられる。 The organic auxiliary agent used in the catalyst of the present invention is an arbitrary powdery, granular, fibrous, or scale-like auxiliary agent mainly composed of an organic substance that is burned off by heat treatment at 200 ° C. or higher and 600 ° C. or lower. Some or all of them are burnt off in the baking process, for example, polymers such as polyethylene glycol and various esters or polymer beads, dried superabsorbent resins or water-absorbing substances with arbitrary water absorption, various surfactants, wheat flour Alternatively, various starches such as refined starch, and crystalline or amorphous cellulose and its derivatives are included.
ここで、本発明の触媒に使用するバインダーとは、その分子直径が予備焼成粉体の平均粒径に対して０．００１以下の範囲である化合物群からなる単独または組み合わせにより構成される液体とし、例えば次のようなものが挙げられる。すなわち、液状の有機溶剤、有機物の分散体、水溶性有機溶剤、およびそれらと水の任意の割合での混合物であり、特に制限はないが、グリセリン等の多価アルコールの水溶液またはイオン交換水が好ましく、さらにイオン交換水が成形性の観点から最も好ましい。バインダーは水または有機物を含むため、後述する本焼成工程にてその一部またはすべてが焼失するが、一般にバインダーに使用される有機物の分子直径は予備焼成粉体の平均粒径と比較すると十分に小さい。また、このバインダーに前記触媒原料の溶液を使用することで、工程（Ａ１）とは異なる態様で触媒の最表面に元素を導入することも可能である。 Here, the binder used in the catalyst of the present invention is a liquid consisting of a group of compounds whose molecular diameter is in the range of 0.001 or less with respect to the average particle diameter of the pre-calcined powder, alone or in combination. , for example: That is, liquid organic solvents, organic substance dispersions, water-soluble organic solvents, and mixtures thereof with water at arbitrary ratios are not particularly limited, but aqueous solutions of polyhydric alcohols such as glycerin or ion exchanged water are Preferred is ion-exchanged water, and most preferred from the viewpoint of moldability. Since the binder contains water or organic matter, some or all of it is burned off in the main firing process described later. small. Also, by using the solution of the catalyst raw material for this binder, it is possible to introduce an element to the outermost surface of the catalyst in a manner different from that of the step (A1).
コーティングによる担持成形の方法としてバインダーの使用量は、予備焼成粉体１００質量部に対して２質量部から６０質量部であり、１０質量部から５０質量部がより好ましい。本発明の反応は酸化的脱水素であり発熱反応であるため、触媒内部の放熱のため、さらには生成した共役ジオレフィンの効率的な拡散による、コーク状物質の生成および／または滞留の抑制のため、担持成形が最も好ましい成形方法である。 The amount of the binder used in the method of carrying and molding by coating is 2 to 60 parts by mass, more preferably 10 to 50 parts by mass, with respect to 100 parts by mass of the pre-baked powder. Since the reaction of the present invention is an oxidative dehydrogenation and an exothermic reaction, it is possible to suppress the formation and/or retention of coke-like substances due to the heat release inside the catalyst and the efficient diffusion of the produced conjugated diolefin. Support molding is therefore the most preferred molding method.
工程（Ａ４）本焼成
このようにして得られた予備焼成粉体または成形品は、比表面積パラメータＳを特定の範囲内にするために反応に使用する前に２００℃以上６００℃以下、好ましくは４００℃以上６００℃以下、さらに好ましくは５００℃以上６００℃以下で再度焼成（本焼成）することが好ましい。本焼成に関しても、焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、トンネル焼成炉において４８０℃以上６００℃以下、好ましくは５００℃以上５８０℃以下、さらに好ましくは５１０℃以上５５０℃以下、最も好ましくは５１５℃以上５３５℃以下の温度範囲で１時間から１２時間、好ましくは１時間から８時間、さらに好ましくは２時間から６時間、好ましくは空気雰囲気下による方法である。
Step (A4) Main Firing The pre-baked powder or molded article thus obtained is heated to 200° C. or more and 600° C. or less, preferably 200° C. or more and 600° C. or less, before being used in the reaction in order to make the specific surface area parameter S within a specific range. It is preferable to perform calcination (main calcination) again at 400° C. or higher and 600° C. or lower, more preferably 500° C. or higher and 600° C. or lower. Regarding main firing, there are no particular restrictions on the firing time or the atmosphere during firing, and there are no particular restrictions on the firing method, such as fluidized bed, rotary kiln, muffle furnace, or tunnel firing furnace. An appropriate range should be selected in consideration of production efficiency and the like. Among these, the most preferable in the present invention is a tunnel firing furnace at 480 ° C. or higher and 600 ° C. or lower, preferably 500 ° C. or higher and 580 ° C. or lower, more preferably 510 ° C. or higher and 550 ° C. or lower, most preferably 515 ° C. or higher and 535 ° C. or lower. It is a method in a temperature range of 1 hour to 12 hours, preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours, preferably in an air atmosphere.
次に、以下では（Ｂ）法による触媒調製方法を記載する。以下では各工程を順に記載しているが、最終的な触媒を得るための各工程の順番、工程数、各工程の組み合わせについて制限はないものとする。 Next, the catalyst preparation method by the (B) method is described below. Although each step is described in order below, there are no restrictions on the order of steps, the number of steps, and the combination of steps for obtaining the final catalyst.
工程（Ｂ１）含浸
触媒活性成分が導入された溶液またはスラリーを調製し、ここに成形担体または（Ａ）法で得た触媒を含浸させ、成形品を得る。ここで、含浸による触媒活性成分の担持手法はディップ法、インシピエントウェットネス法、イオン交換法、ｐＨスイング法など特に制限はなく、前記溶液または前記スラリーの溶媒として水、有機溶剤、またはこれらの混合溶液のいずれでも良く、触媒活性成分の原料濃度も制限はなく、さらに、前記混合溶液または前記スラリーの液温、液にかかる圧力、液の周囲の雰囲気についても特に制限はないが、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。また、前記成形担体および前記（Ａ）法で得た触媒のいずれも形状は球状、円柱状、リング状、粉末状など特に制限はなく、さらに材質、粒径、吸水率、機械的強度も特に制限はない。
Step (B1) Impregnation A solution or slurry into which a catalytically active component has been introduced is prepared and impregnated with a shaped carrier or the catalyst obtained in method (A) to obtain a shaped article. Here, the method for supporting the catalytically active component by impregnation is not particularly limited, such as a dipping method, an incipient wetness method, an ion exchange method, or a pH swing method. Any of the mixed solutions may be used, and the raw material concentration of the catalytically active component is not limited, and the liquid temperature of the mixed solution or slurry, the pressure applied to the liquid, and the atmosphere surrounding the liquid are not particularly limited, but the final An appropriate range should be selected in consideration of the specific catalyst performance, mechanical strength, moldability, production efficiency, and the like. In addition, the shape of both the molded support and the catalyst obtained by the method (A) is not particularly limited, such as spherical, cylindrical, ring, or powder. There are no restrictions.
工程（Ｂ２）乾燥
こうして得られた前記成形品を、蒸発乾固法、ドラム乾燥法、凍結乾燥法等の公知の乾燥方法を用いて２０℃以上２００℃以下の範囲において熱処理を行い、本発明の触媒成形乾燥体を得る。焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。
Step (B2) Drying The molded article thus obtained is heat-treated at a temperature of 20°C or higher and 200°C or lower using a known drying method such as an evaporation drying method, a drum drying method, or a freeze-drying method. is obtained. There are no particular restrictions on the firing time or atmosphere during firing, and there are no particular restrictions on the firing method, such as fluidized bed, rotary kiln, muffle furnace, or tunnel firing furnace, and the final catalyst performance, mechanical strength, moldability, and production efficiency. An appropriate range should be selected in consideration of the above.
工程（Ｂ３）本焼成
こうして得られた前記触媒成形乾燥体を、蒸発乾固法、ドラム乾燥法、凍結乾燥法等の公知の乾燥方法を用いて２００℃以上６００℃以下、好ましくは４００℃以上６００℃以下、さらに好ましくは５００℃以上６００℃以下で熱処理を行い、本発明の触媒を得る。ここで、焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、トンネル焼成炉において４８０℃以上６００℃以下、好ましくは５００℃以上５８０℃以下、さらに好ましくは５１０℃以上５５０℃以下、最も好ましくは５１５℃以上５３５℃以下の温度範囲で１時間から１２時間、好ましくは１時間から８時間、さらに好ましくは２時間から６時間、好ましくは空気雰囲気下による方法である。
Step (B3) Main Firing The catalyst molded dried body thus obtained is dried at 200° C. or higher and 600° C. or lower, preferably 400° C. or higher using a known drying method such as evaporation to dryness, drum drying, or freeze drying. A heat treatment is performed at 600° C. or lower, more preferably 500° C. or higher and 600° C. or lower to obtain the catalyst of the present invention. Here, there are no particular restrictions on the firing time or the atmosphere during firing, and there are no particular restrictions on the firing method such as a fluidized bed, rotary kiln, muffle furnace, or tunnel firing furnace. An appropriate range should be selected in consideration of the production efficiency and the like. Among these, the most preferable in the present invention is a tunnel firing furnace at 480 ° C. or higher and 600 ° C. or lower, preferably 500 ° C. or higher and 580 ° C. or lower, more preferably 510 ° C. or higher and 550 ° C. or lower, most preferably 515 ° C. or higher and 535 ° C. or lower. It is a method in a temperature range of 1 hour to 12 hours, preferably 1 hour to 8 hours, more preferably 2 hours to 6 hours, preferably in an air atmosphere.
本発明において全製造工程とは、触媒原料から本発明の触媒を得るまでの、工程（Ａ１）から工程（Ａ４）および工程（Ｂ１）から工程（Ｂ３）の単独または組み合わせによる全ての工程である。本発明において成形工程とは、工程（Ａ３）のうちその一部またはその全部である。 In the present invention, the term "all production steps" refers to all the steps from step (A1) to step (A4) and from step (B1) to step (B3) alone or in combination until the catalyst of the present invention is obtained from the catalyst starting material. . In the present invention, the molding step is part or all of the step (A3).
［調合液のｐＨの測定］
ｐＨの測定方法に関しては、公知である方法を適用すればその制限はないが、例えば次の方法が挙げられる。ＨＡＮＮＡ製ｐＨｅｐ５を、ｐＨ４．０１および７．０１のｐＨ標準液により２点校正し、測定対象に１０秒以上浸漬させ浸漬中にそのｐＨを確認する。この作業を１セットとし、測定箇所を変えて２セット以上確認したｐＨを平均化し、その触媒の調合液のｐＨとする。校正は、必要に応じてｐＨ１０．０１のｐＨ標準液を加えて３点校正とし、また校正から測定作業までの時間間隔が３時間以上経過した場合には再校正することとする。
[Measurement of pH of preparation]
As for the method for measuring pH, there is no limitation as long as a known method is applied, but the following method can be mentioned, for example. pHep5 manufactured by HANNA is calibrated at two points with pH standard solutions of pH 4.01 and 7.01, and is immersed in the object to be measured for 10 seconds or longer to confirm the pH during the immersion. This operation is regarded as one set, and the pH obtained by checking two or more sets by changing the measurement points is averaged and taken as the pH of the prepared solution of the catalyst. If necessary, a pH standard solution of pH 10.01 is added to calibrate at three points, and if the time interval from calibration to measurement is three hours or longer, recalibration is performed.
本発明の触媒を使用すれば、炭素原子数４以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するプロセス、特にｎ－ブテン原料から酸化脱水素反応によりブタジエンを製造するプロセスにおいて、高活性かつ高収率でブタジエンを得ることが可能である。また、本発明の触媒を使用すれば、上記の通り、炭素析出の前駆体物質の触媒内部の滞留およびそれらの堆積によるコーキングを抑制することができ、高収率かつ安定に反応を長期間継続させることができる。 If the catalyst of the present invention is used, a process for producing conjugated diolefins by catalytic oxidative dehydrogenation reaction from a mixed gas containing monoolefins having 4 or more carbon atoms and molecular oxygen, especially oxidative dehydrogenation reaction from n-butene raw material. In the process of producing butadiene by, it is possible to obtain butadiene with high activity and high yield. In addition, by using the catalyst of the present invention, as described above, retention of precursor substances for carbon deposition inside the catalyst and coking due to their deposition can be suppressed, and the reaction can be stably continued for a long period of time with high yield. can be made
本発明の触媒を使用して炭素原子数４以上のモノオレフィンから共役ジオレフィンを製造する反応の条件は、原料ガス組成として１容量％から２０容量％のモノオレフィン、５容量％から２０容量％の分子状酸素、０容量％から６０容量％の水蒸気及び０容量％から９４容量％の不活性ガス、例えば窒素、炭酸ガスを含む混合ガスを用い、反応浴温度としては２００℃から５００℃の範囲であり、反応圧力としては常圧から１０気圧の圧力下、本発明の触媒成形体に対する原料ガスの空間速度（ＧＨＳＶ）は３５０ｈｒ－１から７０００ｈｒ－１の範囲、より好ましくは５００ｈｒ－１から４０００ｈｒ－１の範囲となる。反応の形態として固定床、移動床、および流動床の中で制約はないが、固定床が好ましい。さらにｎ－ブテンに含まれる１－ブテンのモル組成比は０以上９０未満、好ましくは１以上６０未満、より好ましくは１以上４０未満であり、シス－２－ブテンのモル組成比は０以上９０未満、好ましくは１以上６０未満、より好ましくは１以上４０未満であり、トランス－２－ブテンのモル組成比は０以上９０未満、好ましくは１以上６０未満、より好ましくは１以上４０未満である。また、ブテン原料には調達元によりｎ－ブタンが含まれることがあるが、ｎ－ブタンは前記反応浴温度領域にて本発明の触媒のようなビスマスモリブデート複合金属酸化物触媒においては反応性がなく、前記不活性ガスと同様に扱うこととし、そのモノオレフィンにおけるモル組成比は０以上９０未満、好ましくは０以上５０未満、さらに好ましくは０以上１０未満である。 The reaction conditions for producing a conjugated diolefin from a monoolefin having 4 or more carbon atoms using the catalyst of the present invention are as follows: 1% to 20% by volume of the monoolefin, 5% to 20% by volume of the raw material gas composition; of molecular oxygen, 0% to 60% by volume of water vapor and 0% to 94% by volume of an inert gas such as nitrogen or carbon dioxide, and the reaction bath temperature is 200°C to 500°C. The reaction pressure is from normal pressure to 10 atm, and the space velocity (GHSV) of the raw material gas to the catalyst molded body of the present invention is in the range of 350 hr -1 to 7000 hr -1 , more preferably 500 hr -1 to It is in the range of 4000hr -1 . The form of reaction is not restricted among fixed bed, moving bed and fluidized bed, but fixed bed is preferred. Furthermore, the molar composition ratio of 1-butene contained in n-butene is 0 or more and less than 90, preferably 1 or more and less than 60, more preferably 1 or more and less than 40, and the molar composition ratio of cis-2-butene is 0 or more and 90. less than, preferably 1 or more and less than 60, more preferably 1 or more and less than 40, and the molar composition ratio of trans-2-butene is 0 or more and less than 90, preferably 1 or more and less than 60, more preferably 1 or more and less than 40 . In addition, although the butene raw material may contain n-butane depending on the supplier, n-butane is reactive in the bismuth molybdate mixed metal oxide catalyst such as the catalyst of the present invention in the reaction bath temperature range. The molar composition ratio in the monoolefin is 0 or more and less than 90, preferably 0 or more and less than 50, more preferably 0 or more and less than 10.
本発明の触媒を炭素原子数４以上のモノオレフィンから共役ジオレフィンを製造する反応、特にｎ－ブテンからブタジエンを製造する反応において使用することで、高活性かつ高収率で共役ジオレフィンを製造することができ、これらの結果として公知のブタジエン製造プロセスと比較して、本プロセスによるブタジエンの価格競争力の向上が期待できる。 By using the catalyst of the present invention in a reaction for producing a conjugated diolefin from a monoolefin having 4 or more carbon atoms, particularly in a reaction for producing butadiene from n-butene, a conjugated diolefin is produced with high activity and high yield. As a result, compared with the known butadiene production process, improvement in price competitiveness of butadiene by this process can be expected.
以下、実施例により本発明をさらに詳細に説明するが、本発明はその趣旨を超えない限り、以下の実施例に限定されるものではない。なお、以下において、％は特に断りがない限りモル％を意味する。また、以下においてｎ－ブテン転化率、ブタジエン収率、ＴＯＳの定義とは、以下の通りである。当業者にとって明らかなように、以下の触媒性能の計算にあたっては、校正された純標準ガス等によって、十分な精度で校正を行った各種ガスクロマトグラフィーを用いることとする。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In addition, below, % means mol% unless there is particular notice. Further, the definitions of n-butene conversion rate, butadiene yield, and TOS are as follows. As will be apparent to those skilled in the art, various gas chromatographs that have been calibrated with sufficient accuracy using a calibrated pure standard gas or the like are used in the following calculations of catalytic performance.
ｎ－ブテン転化率（モル％）＝（反応したｎ－ブテンのモル数／供給したｎ－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ｎ－ブテンのモル数）×１００
ＴＯＳ＝混合ガス流通時間（時間）
n-butene conversion rate (mol%) = (number of moles of reacted n-butene/number of moles of supplied n-butene) x 100
Butadiene yield (mol%) = (number of moles of butadiene produced/number of moles of supplied n-butene) x 100
TOS = mixed gas flow time (hours)
［実施例１（触媒１の調製）］
ヘプタモリブデン酸アンモニウム８００質量部を８０℃に加温した純水３０００質量部に完全溶解させた（母液１）。次に、硝酸セシウム２．９質量部を純水３３ｍｌに溶解させて、母液１に加えた。次に、硝酸第二鉄３２０質量部、硝酸コバルト７１４質量部及び硝酸ニッケル２５２質量部を６０℃に加温した純水６８２ｍｌに溶解させ、母液１に加えた。続いて硝酸ビスマス１６５質量部を６０℃に加温した純水１７４ｍｌに硝酸（６０質量％）４２質量部を加えて調製した硝酸水溶液に溶解させ母液１に加えた。前述の母液１をスプレードライ法にて乾燥し、得られた乾燥粉体を４４０℃、５時間の条件で予備焼成した。こうして得られた予備焼成粉体（仕込み原料から計算される原子比はＭｏ：Ｂｉ：Ｆｅ：Ｃｏ：Ｎｉ：Ｃｓ＝１２：０．９：２．１：６．５：２．３：０．０４に対して５質量％分の結晶性セルロースを添加し、十分混合した後、転動造粒法にてバインダーとして３３質量％グリセリン溶液を用い、平均粒径４．０ｍｍの不活性の担体１（シリカ：アルミナ＝１：２．６０の重量比、気孔率＝４５％、吸水率＝２３％）に、担持率が４０質量％となるように球状に担持成形し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒１）
[Example 1 (preparation of catalyst 1)]
800 parts by mass of ammonium heptamolybdate was completely dissolved in 3000 parts by mass of pure water heated to 80° C. (mother liquor 1). Next, 2.9 parts by mass of cesium nitrate was dissolved in 33 ml of pure water and added to mother liquor 1 . Next, 320 parts by mass of ferric nitrate, 714 parts by mass of cobalt nitrate and 252 parts by mass of nickel nitrate were dissolved in 682 ml of pure water heated to 60° C. and added to mother liquor 1 . Subsequently, 165 parts by mass of bismuth nitrate was dissolved in an aqueous nitric acid solution prepared by adding 42 parts by mass of nitric acid (60% by mass) to 174 ml of pure water heated to 60° C. and added to mother liquor 1 . The aforementioned mother liquor 1 was dried by a spray drying method, and the obtained dried powder was preliminarily calcined at 440° C. for 5 hours. The pre-fired powder thus obtained (the atomic ratio calculated from the charged raw materials is Mo:Bi:Fe:Co:Ni:Cs=12:0.9:2.1:6.5:2.3:0. After adding 5% by mass of crystalline cellulose to 04 and sufficiently mixing, using a 33% by mass glycerin solution as a binder by a tumbling granulation method, an inert carrier 1 having an average particle size of 4.0 mm was obtained. (Silica: Alumina = 1:2.60 weight ratio, porosity = 45%, water absorption = 23%) was supported and molded into a spherical shape so that the support rate was 40% by mass, and the average particle size was 4.4 mm. (Catalyst 1 of the present invention)
［実施例２（触媒２の調製）］
不活性な担体として平均粒径３．２ｍｍの不活性の担体２（シリカ：アルミナ＝１：２．６０の重量比、気孔率＝４５％、吸水率＝２３％）に、担持率が５０質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒２）
[Example 2 (preparation of catalyst 2)]
As an inert carrier, an inert carrier 2 (silica: alumina = 1: 2.60 weight ratio, porosity = 45%, water absorption = 23%) with an average particle diameter of 3.2 mm, and a loading rate of 50 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 2 of the present invention)
［実施例３（触媒３の調製）］
不活性な担体として平均粒径３．８ｍｍの不活性の担体３（シリカ：アルミナ＝１：２．６０の重量比、気孔率＝４５％、吸水率＝２３％）に、担持率が５０質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒３）
[Example 3 (preparation of catalyst 3)]
As an inert carrier, an inert carrier 3 (silica: alumina = 1: 2.60 weight ratio, porosity = 45%, water absorption = 23%) with an average particle diameter of 3.8 mm, and a loading rate of 50 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 3 of the present invention)
［実施例４（触媒４の調製）］
不活性な担体として平均粒径４．５ｍｍの不活性の担体４（シリカ：アルミナ＝１：２．６０の重量比、気孔率＝４５％、吸水率＝２３％）に、担持率が５０質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径５．３ｍｍの触媒を得た。（本発明の触媒４）
[Example 4 (preparation of catalyst 4)]
As an inert carrier, an inert carrier 4 (silica: alumina = 1: 2.60 weight ratio, porosity = 45%, water absorption = 23%) with an average particle diameter of 4.5 mm, and a loading rate of 50 mass A catalyst having an average particle diameter of 5.3 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a 5.3 mm average particle diameter. (Catalyst 4 of the present invention)
［実施例５（触媒７の調製）］
不活性な担体として平均粒径３．８ｍｍの不活性の担体７（シリカ：アルミナ＝１：０．３９の重量比、気孔率＝４５％、吸水率＝２０％）に、担持率が５０質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒７）
[Example 5 (preparation of catalyst 7)]
As an inert carrier, an inert carrier 7 with an average particle diameter of 3.8 mm (silica: alumina = 1: 0.39 weight ratio, porosity = 45%, water absorption = 20%) with a loading rate of 50 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 7 of the present invention)
［実施例６（触媒８の調製）］
不活性な担体として平均粒径３．８ｍｍの不活性の担体８（シリカ：アルミナ＝１：５．７７の重量比、気孔率＝３６％、吸水率＝１４％）に、担持率が４５質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒８）
[Example 6 (preparation of catalyst 8)]
As an inert carrier, an inert carrier 8 with an average particle diameter of 3.8 mm (silica: alumina = 1: 5.77 weight ratio, porosity = 36%, water absorption = 14%) with a loading rate of 45 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 8 of the present invention)
［比較例１（触媒９の調製）］
不活性な担体として平均粒径３．８ｍｍの不活性の担体９（シリカ：アルミナ＝１：０．００の重量比、気孔率＝５７％、吸水率＝２９％）に、担持率が４９質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒９）
[Comparative Example 1 (Preparation of Catalyst 9)]
As an inert carrier, an inert carrier 9 (silica: alumina = 1:0.00 weight ratio, porosity = 57%, water absorption = 29%) with an average particle diameter of 3.8 mm, and a loading rate of 49 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 9 of the present invention)
［比較例２（触媒１０の調製）］
不活性な担体として平均粒径３．８ｍｍの不活性の担体１０（シリカ：アルミナ＝１：９９２．９０の重量比、気孔率＝５２％、吸水率＝２８％）に、担持率が４８質量％となるように球状に担持成形した以外は実施例１と同様に触媒を調製し、平均粒径４．４ｍｍの触媒を得た。（本発明の触媒１０）
[Comparative Example 2 (preparation of catalyst 10)]
As an inert carrier, an inert carrier 10 with an average particle diameter of 3.8 mm (silica: alumina = 1: 992.90 weight ratio, porosity = 52%, water absorption = 28%) with a loading rate of 48 mass A catalyst having an average particle size of 4.4 mm was obtained in the same manner as in Example 1, except that the catalyst was supported and formed into a spherical shape so as to obtain a spheroidal particle size of 4.4 mm. (Catalyst 10 of the present invention)
上記実施例および比較例で得られた触媒を、以下の方法により反応評価した。各触媒５３ｍｌをステンレス鋼反応管に充填し、ガス体積比率がｎ－ブテン：酸素：窒素：水蒸気＝１：０．８：７：１の混合ガスを用い、常圧下、ＧＨＳＶ１２００ｈｒ－１の条件で、反応浴温度３４０℃にてＴＯＳ２０時間以上のエージング反応後、反応管出口で、コンデンサーにより液成分とガス成分を分離し、ガス成分中の各成分を各々水素炎イオン化検出器と熱伝導検出器が装着されたガスクロマトグラフで定量分析した。ガスクロマトグラフにより得られた各データはファクター補正し、ｎ－ブテン転化率、ブタジエン収率を算出した。なお、本反応で使用したｎ－ブテンのモル組成比は、１－ブテン：シス－２－ブテン：トランス－２－ブテン＝３３．４：３３．３：３３．３であった。 The reaction evaluation of the catalysts obtained in the above Examples and Comparative Examples was performed by the following methods. 53 ml of each catalyst is filled in a stainless steel reaction tube, and a mixed gas with a gas volume ratio of n-butene:oxygen:nitrogen:steam=1:0.8:7:1 is used under normal pressure and under the conditions of GHSV 1200 hr −1 . , After the aging reaction for TOS 20 hours or more at a reaction bath temperature of 340 ° C., the liquid component and the gas component are separated at the reaction tube outlet by a condenser, and each component in the gas component is detected by a hydrogen flame ionization detector and a heat conduction detector. was quantitatively analyzed with a gas chromatograph equipped with Each data obtained by gas chromatography was factor-corrected to calculate n-butene conversion rate and butadiene yield. The molar composition ratio of n-butene used in this reaction was 1-butene:cis-2-butene:trans-2-butene=33.4:33.3:33.3.
表１に実施例１～４について、各々の担体のシリカ：アルミナ重量比率、さらに対応する試験例と比較試験例による反応浴温度３４０℃におけるｎ－ブテン転化率、ブタジエン収率の結果を示す。表１より明らかなように、本発明により高いＧＨＳＶかつｎ－ブテン濃度の条件にもかかわらず、ｎ－ブテン転化率およびブタジエン収率が共に高い触媒を得ることができ、触媒の平均粒径及び担持率と明らかな相関があることが分かった。 Table 1 shows the silica:alumina weight ratio of each carrier, and the results of n-butene conversion rate and butadiene yield at a reaction bath temperature of 340° C. in corresponding test examples and comparative test examples for Examples 1 to 4. As is clear from Table 1, according to the present invention, a catalyst having both high n-butene conversion and high butadiene yield can be obtained despite the conditions of high GHSV and n-butene concentration. It was found that there is a clear correlation with the loading rate.
表２に実施例３、５、６、および比較例１、２について、表１と同様の試験結果を示す。ガスクロマトグラフ測定時のファクターの測定方法が出口ガス組成を模した混合ガスによりファクター補正し、ｎ－ブテン転化率、ブタジエン収率を算出したため、表１と異なる転化率、ブタジエン収率を示している。表２より明らかなように、ブタジエン収率はシリカとアルミナ重量比率より最適範囲があることが分かる。 Table 2 shows test results similar to Table 1 for Examples 3, 5 and 6 and Comparative Examples 1 and 2. The conversion rate and butadiene yield are different from Table 1 because the conversion rate and butadiene yield of n-butene were calculated by performing factor correction using a mixed gas that simulates the composition of the outlet gas. . As is clear from Table 2, the butadiene yield has an optimum range depending on the weight ratio of silica and alumina.
表１、２の結果より、本願発明の構成を充足する実施例１～６はＢＴ３４０℃におけるｎ－ブテン転化率、ブタジエン収率共に高いことが確認された。 From the results in Tables 1 and 2, it was confirmed that Examples 1 to 6 satisfying the constitution of the present invention had high n-butene conversion rate and high butadiene yield at BT 340°C.
本発明によれば、炭素原子数４以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを高活性かつ高収率で製造することが可能である。
According to the present invention, it is possible to produce a conjugated diolefin with high activity and high yield from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen by a catalytic oxidative dehydrogenation reaction.
Claims (6)
平均粒子径が２．５０ｍｍ以上４．４９ｍｍ以下であり、
活性成分としての触媒組成が、下記式（１）で表される共役ジオレフィン化合物製造用ビスマスモリブデート複合金属酸化物触媒。
Ｍｏ １２ Ｂｉ ａ Ｆｅ ｂ Ｃｏ ｃ Ｎｉ ｄ Ｘ ｅ Ｙ ｆ Ｚ ｇ ・・・・（１）
（式中、Ｘはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも１種の元素を示し、Ｙはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも１種の元素を示し、Ｚはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、タリウムから選ばれる少なくとも１種の元素を示し、
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、およびｇは各々モリブデン１２に対するビスマス、鉄、コバルト、ニッケル、Ｘ、Ｙ、Ｚの原子比を示し、０．３＜ａ＜３．５、０．６＜ｂ＜３．４、５．０＜ｃ＜８．０、０．０＜ｄ＜３．０、０．０＜ｅ＜０．５、０．０≦ｆ≦４．０、０≦ｇ≦２．０の範囲にあり、式（１）中に記載はないが酸素原子Ｏは他の元素の酸化状態を満足させる適当な原子比となる）。 Silica (SiO2) and alumina (Al2O.3) to inertcarrierwherein the weight ratio of the silica content and the alumina content is 1:0.20~1:is 10.00,
The average particle diameter is 2.50 mm or more and 4.49 mm or less,
For producing a conjugated diolefin compound having a catalyst composition as an active component represented by the following formula (1)Bismuth molybdate composite metal oxide catalyst.
Mo 12 Bi a Fe b Co c Ni d X e Y. f Z. g (1)
(In the formula, X represents at least one element selected from alkali metals selected from lithium, sodium, potassium, rubidium and cesium, and Y represents at least one element selected from alkaline earth metals selected from magnesium, calcium, strontium and barium. represents an element, Z represents at least one element selected from lanthanum, cerium, praseodymium, neodymium, samarium, eurobium, antimony, tungsten, lead, zinc, and thallium;
a, b, c, d, e, f, and g denote the atomic ratios of bismuth, iron, cobalt, nickel, X, Y, Z to molybdenum 12, respectively, 0.3<a<3.5, 0.3<a<3.5, 6<b<3.4, 5.0<c<8.0, 0.0<d<3.0, 0.0<e<0.5, 0.0≤f≤4.0, 0≤ It is in the range of g≦2.0, and although not described in formula (1), the oxygen atom O has an appropriate atomic ratio that satisfies the oxidation state of other elements).
工程（Ａ１）：複合金属酸化物の各金属を含有する化合物を含む混合溶液またはスラリーを２０℃以上９０℃以下の条件下で調製し、スプレー乾燥して乾燥粉体を得る工程、
工程（Ａ２）：工程（Ａ１）で得られた乾燥粉体を予備焼成し、予備焼成粉体を得る工程、
工程（Ａ３）：工程（Ａ２）で得られた予備焼成粉体を成形し、成形品を得る工程、
工程（Ａ４）：工程（Ａ３）で得られた成形品を本焼成する工程。 The method for producing a bismuth molybdate mixed metal oxide catalyst for producing a conjugated diolefin compound according to any one of claims 1 to 4 , comprising the following steps:
Step (A1): A step of preparing a mixed solution or slurry containing a compound containing each metal of the composite metal oxide under conditions of 20° C. or higher and 90° C. or lower, and spray-drying to obtain a dry powder;
Step (A2): a step of pre-baking the dry powder obtained in step (A1) to obtain a pre-baked powder;
Step (A3): a step of molding the pre-fired powder obtained in step (A2) to obtain a molded product;
Step (A4): A step of firing the molded product obtained in step (A3).
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