JP7070031B2 - Catalyst group - Google Patents
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- JP7070031B2 JP7070031B2 JP2018083830A JP2018083830A JP7070031B2 JP 7070031 B2 JP7070031 B2 JP 7070031B2 JP 2018083830 A JP2018083830 A JP 2018083830A JP 2018083830 A JP2018083830 A JP 2018083830A JP 7070031 B2 JP7070031 B2 JP 7070031B2
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- 239000003054 catalyst Substances 0.000 title claims description 224
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 56
- 150000001299 aldehydes Chemical class 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 37
- 230000003197 catalytic effect Effects 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 21
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 13
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000012071 phase Substances 0.000 description 20
- 239000012808 vapor phase Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- -1 pressure loss Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、触媒群に関する。詳しくは、オレフィン又はターシャリーブタノールを気相
接触酸化反応させて対応する不飽和アルデヒド及び／又は不飽和カルボン酸を製造する際
に用いる触媒群に関する。
The present invention relates to a group of catalysts. More specifically, the present invention relates to a group of catalysts used in producing the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by subjecting an olefin or tertiary butanol to a gas-phase catalytic oxidation reaction.
従来、オレフィン又はターシャリーブタノールを気相接触酸化反応させて対応する不飽
和アルデヒド及び／又は不飽和カルボン酸を製造するために用いる触媒の形状については
種々提案されている。
Conventionally, various shapes of catalysts used for producing the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by subjecting an olefin or tertiary butanol to a gas-phase catalytic oxidation reaction have been proposed.
例えば、特許文献１には、中空円筒体状に成形され、該中空円筒体状の端面が湾曲して
いる不均一系触媒反応用の成形触媒が記載されている。特許文献２には、プロピレン等か
らアクロレインを製造するための触媒として、Ｍｏ、Ｂｉ及びＦｅを少なくとも含有する
リング状の非担持触媒であり、特定の長さ、外径及び壁厚を有し、端面が湾曲している又
は湾曲していない触媒が記載されている。また、特許文献３には、環状担体の両正面が内
から外へ斜めに面取りされて、円筒外壁の長さが円筒内壁の長さに比して少なくとも２０
％だけ短くなっている、バナジウム及びチタン及び／又はジルコンを含有する無水フタル
酸を製造するための担持触媒が記載されている。
For example, Patent Document 1 describes a molding catalyst for a non-homogeneous catalytic reaction, which is formed into a hollow cylindrical body and whose end face of the hollow cylindrical body is curved.
A carrier catalyst for producing phthalic anhydride containing vanadium and titanium and / or zircon, which is shortened by%, is described.
しかしながら、これら従前知られた触媒では、該触媒が充填された反応器等によりオレ
フィン又はターシャリーブタノールを流通して気相接触酸化反応により対応する不飽和ア
ルデヒド及び／又は不飽和カルボン酸を製造する場合、圧力損失が高く、オレフィン又は
ターシャリーブタノールの転化率が低く、対応する不飽和アルデヒド及び／又は不飽和カ
ルボン酸の選択率が低く、収率が低下するという問題があった。
However, in these previously known catalysts, an olefin or a tertiary butanol is circulated by a reactor or the like filled with the catalyst to produce a corresponding unsaturated aldehyde and / or an unsaturated carboxylic acid by a vapor phase catalytic oxidation reaction. In the case, there are problems that the pressure loss is high, the conversion rate of the olefin or the catalysty butanol is low, the selectivity of the corresponding unsaturated aldehyde and / or the unsaturated carboxylic acid is low, and the yield is lowered.
例えばリング形状の触媒では、反応器に均一に充填されない場合があり、反応場が反応
器内で不均一となり、転化率、選択率の低下が起こる可能性がある。又、中空円筒体状の
端面が湾曲している触媒では、例えば打錠成形法で製造した場合、湾曲している部分が剥
がれやすく、成形が困難となる（「紛体の圧縮成型技術」日刊工業新聞社発行 １９９８
年 ７９－８０頁）。加えて、成形品においても湾曲している部分が剥がれやすいために
、衝撃に対して弱く、特に不飽和アルデヒド及び／又は不飽和カルボン酸を工業的に製造
する固定床管型反応器のように、充填層の長い反応管に充填した場合、反応管内で触媒の
粉化等が生じ、圧力損失の増大や触媒性能の低下につながる可能性がある。加えて、触媒
体積に対する触媒表面積が小さく、反応活性点が少ないため、触媒数が多くなるにつれ、
反応の効率が低くなり、転化率、選択率が低下する場合がある。
For example, in a ring-shaped catalyst, the reactor may not be uniformly filled, the reaction field may become non-uniform in the reactor, and the conversion rate and selectivity may decrease. Further, in the case of a catalyst having a curved end face in the shape of a hollow cylinder, for example, when manufactured by a tableting molding method, the curved portion is easily peeled off, which makes molding difficult ("Compression molding technology for powder" Nikkan Kogyo. Published by Shimbun 1998
Year 79-80). In addition, even in molded products, the curved portion is easily peeled off, so that it is vulnerable to impact, especially like a fixed bed tube type reactor that industrially produces unsaturated aldehydes and / or unsaturated carboxylic acids. When the reactor is filled with a long packed layer, the catalyst may be pulverized in the reactor, which may lead to an increase in pressure loss and a decrease in catalyst performance. In addition, since the catalyst surface area with respect to the catalyst volume is small and the reaction active sites are small, as the number of catalysts increases,
The efficiency of the reaction may decrease, and the conversion rate and selectivity may decrease.
また、不飽和アルデヒド及び／又は不飽和カルボン酸の製造において、触媒表面に炭化
物が付着するが、該炭化物の触媒表面への付着（コーキング）は多管式反応器の圧力損失
が高い反応管において、ガス量が少なくなることにより発生しやすい。一旦コーキングが
発生すると、更に圧力損失が高くなるので、より炭化物の触媒表面への付着が加速する悪
循環が生じ、最終的には反応を停止せざるを得ない状況に追い込まれる可能性がある。
Further, in the production of unsaturated aldehyde and / or unsaturated carboxylic acid, charcoal adheres to the catalyst surface, but the adhesion (coking) of the charcoal to the catalyst surface occurs in a reaction tube having a high pressure loss in a multi-tube reactor. , It tends to occur due to a small amount of gas. Once caulking occurs, the pressure loss becomes even higher, which may lead to a vicious cycle in which the adhesion of carbides to the catalyst surface is accelerated, and eventually the reaction must be stopped.
本発明は上記問題点を解決するためになされたものである。すなわち、本発明は、オレ
フィン又はターシャリーブタノールを気相接触酸化反応させて対応する不飽和アルデヒド
及び／又は不飽和カルボン酸を製造する際に、圧力損失を低減してガス量を高く保持し、
それによりコーキングを抑制することができ、高収率で対応する不飽和アルデヒド及び／
又は不飽和カルボン酸を製造することができる触媒群を提供することを目的とする。
The present invention has been made to solve the above problems. That is, the present invention reduces the pressure loss and keeps the gas amount high when the olefin or tertiary butanol is subjected to a gas phase catalytic oxidation reaction to produce the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid.
It can suppress caulking and in high yield the corresponding unsaturated aldehyde and /
Alternatively, it is an object of the present invention to provide a group of catalysts capable of producing unsaturated carboxylic acids.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、オレフィン又はターシャリ
ーブタノールを気相接触酸化反応させて対応する不飽和アルデヒド及び／又は不飽和カル
ボン酸を製造する際に用いる、直胴部及び空胴部を有するリング形状の触媒を２００以上
含む触媒群であって、下記（１）及び（２）を満たす触媒群とすることにより、圧力損失
を低く抑えることができ、高収率で対応する不飽和アルデヒド及び／又は不飽和カルボン
酸を製造することが可能となることを見いだし、本発明に至った。
（１）該直胴部の長さが該空胴部の長さより短く、該直胴部が該空胴部の一方の端部を含
む面と他方の端部を含む面との間にあり、且つ、少なくとも一方の端部において該直胴部
の端部から該空胴部の端部までが直線状である及び／又は凹曲している触媒（Ａ）を含む
。
（２）該触媒群の振とう試験による上向き比率が５０％以下である。
As a result of diligent research to solve the above problems, the present inventors use olefins or catalysts for catalytic oxidation reaction to produce corresponding unsaturated aldehydes and / or unsaturated carboxylic acids. A catalyst group containing 200 or more ring-shaped catalysts having a straight body portion and an empty body portion, and by forming a catalyst group satisfying the following (1) and (2), pressure loss can be suppressed low and high. We have found that it is possible to produce the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid in terms of yield, and have reached the present invention.
(1) The length of the straight body portion is shorter than the length of the empty body portion, and the straight body portion is located between the surface including one end of the empty body portion and the surface including the other end portion. And includes the catalyst (A), which is linear and / or concave from the end of the straight body to the end of the empty body at at least one end.
(2) The upward ratio of the catalyst group in the shaking test is 50 % or less.
すなわち、本発明は以下である。
［１］ オレフィン又はターシャリーブタノールを気相接触酸化反応させて対応する不飽
和アルデヒド及び／又は不飽和カルボン酸を製造する際に用いる、直胴部及び空胴部を有
するリング形状の触媒を２００以上含む触媒群であって、下記（１）及び（２）を満たす
触媒群。
（１）該直胴部の長さが該空胴部の長さより短く、該直胴部が該空胴部の一方の端部を含
む面と他方の端部を含む面との間にあり、且つ、少なくとも一方の端部において該直胴部
の端部から該空胴部の端部までが直線状である及び／又は凹曲している触媒（Ａ）を含む
。
（２）該触媒群の振とう試験による上向き比率が５０％以下である。
（触媒群の振とう試験による上向き比率の測定法）
触媒群中、無作為に抽出したリング形状の触媒１００個をステンレス角バット（幅２９
６ｍｍ、奥行２３１ｍｍ、高さ４９ｍｍ）に入れ、該ステンレス角バットをデジタルシェ
ーカーFLK-L330-D（アズワン株式会社製）に装着し、往復振とう幅１０ｍｍで、振とう速
度３５０往復／分により１分間振とうさせた後、該リング形状の触媒１００個に対して、
空胴部が上を向いている触媒の個数を上向き比率とする。
That is, the present invention is as follows.
[1] A ring-shaped catalyst having a straight body portion and an empty body portion, which is used when olefin or tertiary butanol is subjected to a gas-phase catalytic oxidation reaction to produce a corresponding unsaturated aldehyde and / or an unsaturated carboxylic acid, is used. A catalyst group including the above, which satisfies the following (1) and (2).
(1) The length of the straight body portion is shorter than the length of the empty body portion, and the straight body portion is located between the surface including one end of the empty body portion and the surface including the other end portion. And includes the catalyst (A), which is linear and / or concave from the end of the straight body to the end of the empty body at at least one end.
(2) The upward ratio of the catalyst group in the shaking test is 50 % or less.
(Measurement method of upward ratio by shaking test of catalyst group)
100 ring-shaped catalysts randomly selected from the catalyst group are placed in a stainless square bat (width 29).
6 mm, depth 231 mm, height 49 mm), the stainless square bat is attached to the digital shaker FLK-L330-D (manufactured by AS ONE Corporation), the reciprocating shaking width is 10 mm, and the shaking speed is 350 reciprocations / minute. After shaking for a minute, for 100 of the ring-shaped catalysts,
The number of catalysts with the empty body facing upward is defined as the upward ratio.
［２］ 前記触媒（Ａ）の、前記直胴部の端部と前記空胴部の端部との間の距離（ｍｍ）
に対する、前記直胴部の端部と前記空胴部の端部を結ぶ面と前記直線状部又は凹曲した面
との最大距離（ｍｍ）との比が０以上０．２以下である［１］に記載の触媒群。
［３］ 前記触媒（Ａ）の両方の端部において、前記直胴部の端部から前記空胴部の端部
までが直線状である及び／又は凹曲している［１］又は［２］に記載の触媒群。
［４］ ［１］乃至［３］のいずれかに記載の触媒群の存在下、プロピレンを気相接触酸
化するアクロレイン及び／又はアクリル酸の製造方法。
[2] The distance (mm) of the catalyst (A) between the end of the straight body and the end of the empty body.
The ratio of the maximum distance (mm) between the surface connecting the end of the straight body portion and the end of the empty body portion and the linear portion or the concave surface is 0 or more and 0.2 or less []. 1] The catalyst group.
[3] At both ends of the catalyst (A), from the end of the straight body portion to the end of the empty body portion is linear and / or concave [1] or [2]. ] The catalyst group described in.
[4] A method for producing acrolein and / or acrylic acid that undergoes gas-phase catalytic oxidation of propylene in the presence of the catalyst group according to any one of [1] to [3].
本発明の触媒群によれば、該触媒群が充填された反応器を用いてプロピレン等のオレフ
ィン又はターシャリーブタノールと酸素含有ガスとの気相接触酸化によりアクロレイン等
の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造する際の圧力損失
が低減されて、ガス量を高く保持することができる。それによりコーキングを抑えること
ができ、プロピレン等のオレフィン又はターシャリーブタノールより高収率でアクロレイ
ン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造することがで
きる。
According to the catalyst group of the present invention, an unsaturated aldehyde such as acrolein and / or acrylic by vapor phase catalytic oxidation of an olefin such as propylene or tertiary butanol and an oxygen-containing gas using a reactor filled with the catalyst group. The pressure loss in producing an unsaturated carboxylic acid such as an acid is reduced, and the amount of gas can be kept high. As a result, coking can be suppressed, and unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid can be produced in higher yields than olefins such as propylene or tertiary butanol.
また、コーキングされた状態であったとしても、従来の形状の触媒と比較して、圧力損
失低減の効果は保持されるので、デコーキングの頻度を低減できる。
Further, even in the caulked state, the effect of reducing the pressure loss is maintained as compared with the catalyst having a conventional shape, so that the frequency of decoking can be reduced.
以下、本発明を実施するための形態について詳細に説明する。尚、本発明は以下に説明
する実施形態の限定されるものではない。
尚、本明細書においてモリブデン（Ｍｏ）、ビスマス（Ｂｉ）、ケイ素（Ｓｉ）、コバ
ルト（Ｃｏ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、
ルビジウム（Ｒｂ）、セシウム（Ｃｓ）、タリウム（Ｔｌ）、ホウ素（Ｂ）、リン（Ｐ）
、ヒ素（Ａｓ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、亜鉛（Ｚｎ）、セリウム
（Ｃｅ）、サマリウム（Ｓｍ）の各元素は、それぞれカッコ内の元素記号を用いて表記す
る場合がある。
本明細書において、リング形状の触媒の「端部」とは、リング形状の触媒の開口方向（
軸方向）における末端周辺の領域を指す。リング形状の触媒は２つの端部（上端及び下端
）を有する。
本明細書において、リング形状の触媒の「直胴部」とは、リング形状の触媒において、
外形が一定である部分をいう。「直胴部の長さ」とは、直胴部の、軸方向の長さをいう。
「直胴部の端部」とは、直胴部の軸方向の末端における、リング形状の触媒の外縁部をい
う。リング形状の触媒は、２つの直胴部の端部（上端及び下端）を有する。
本明細書において、リング形状の触媒の「空胴部」とは、リング形状の触媒の中空部分
における、内径が一定の部分を指す。「空胴部の長さ」とは、空胴部の、軸方向の長さを
いうが、図３に示すようにリング形状の触媒が底面部を有する場合は、空胴部の軸方向の
末端における、リング形状の触媒の外縁部をいう。リング形状の触媒は２つの空胴部の末
端（上端及び下端）を有する。
Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below.
In the present specification, molybdenum (Mo), bismuth (Bi), silicon (Si), cobalt (Co), nickel (Ni), iron (Fe), sodium (Na), potassium (K), and the like.
Rubidium (Rb), cesium (Cs), thallium (Tl), boron (B), phosphorus (P)
, Arsenic (As), Magnesium (Mg), Calcium (Ca), Zinc (Zn), Cerium (Ce), and Samalium (Sm) may be expressed using the element symbols in parentheses.
In the present specification, the "end" of the ring-shaped catalyst is the opening direction of the ring-shaped catalyst (
Refers to the area around the end in the axial direction). The ring-shaped catalyst has two ends (top and bottom).
In the present specification, the "straight body portion" of the ring-shaped catalyst means the ring-shaped catalyst.
A part with a constant outer shape. The "length of the straight body portion" means the length of the straight body portion in the axial direction.
The "end of the straight body" refers to the outer edge of the ring-shaped catalyst at the axial end of the straight body. The ring-shaped catalyst has two straight body ends (upper and lower ends).
In the present specification, the "empty body portion" of the ring-shaped catalyst refers to a portion of the hollow portion of the ring-shaped catalyst having a constant inner diameter. The "length of the air carrier" means the length of the air body in the axial direction. As shown in FIG. 3, when the ring-shaped catalyst has a bottom surface, the length of the air body is axial. The outer edge of the ring-shaped catalyst at the end. The ring-shaped catalyst has two cavity ends (upper and lower ends).
本発明の触媒群は、オレフィン又はターシャリーブタノールを気相接触酸化反応させて
対応する不飽和アルデヒド及び／又は不飽和カルボン酸を製造する際に用いる、直胴部及
び空胴部を有するリング形状の触媒を２００以上含む触媒群であって、下記（１）及び（
２）を満たす触媒群である。
（１）直胴部の長さが空胴部の長さより短く、直胴部が空胴部の一方の端部を含む面と他
方の端部を含む面との間にあり、且つ、少なくとも一方の端部において直胴部の端部から
空胴部の端部までが直線状である及び／又は凹曲している触媒を含む。
（２）触媒群の振とう試験による上向き比率が５０％以下である。
（触媒群の振とう試験による上向き比率の測定法）
触媒群中、無作為に抽出したリング形状の触媒１００個をステンレス角バット（幅２９
６ｍｍ、奥行２３１ｍｍ、高さ４９ｍｍ）に入れ、該ステンレス角バットをデジタルシェ
ーカーFLK-L330-D（アズワン株式会社製）に装着し、往復振とう幅１０ｍｍで、振とう速
度３５０往復／分により１分間振とうさせた後、リング形状の触媒１００個に対して、空
胴部が上を向いている触媒の個数を上向き比率とする。
なお、「空胴部が上を向いている」とは、リング形状の触媒の開口方向（軸方向）がス
テンレス角バットの底面に対して垂直であることをいう。
なお、以下において直胴部の長さが空胴部の長さより短く、直胴部が空胴部の一方の端
部を含む面と他方の端部を含む面との間にあり、且つ、少なくとも一方の端部において直
胴部の端部から空胴部の端部までが直線状である及び／又は凹曲している触媒を「触媒（
Ａ）」ともいう。
本発明の触媒群は直胴部及び空胴部を有するリング形状の触媒を２００以上含む触媒群
である。該触媒群に含まれるリング形状の触媒の数は２５０以上が好ましく、３００以上
がより好ましく、１０００以上がさらに好ましく、２０００以上がとりわけ好ましく、３
０００以上が特に好ましい。前記範囲であることにより、該触媒群を反応管等に充填し、
プロピレンと酸素含有ガスとの気相接触酸化によりアクロレイン及び／又はアクリル酸を
製造する際の圧力損失が低減され、プロピレンの転化率を高め、高選択率でアクロレイン
及び／又はアクリル酸を製造することができる。尚、上限は反応管への充填量の観点より
、２００００が好ましく、１５０００がより好ましく、１２０００がさらに好ましい。
The catalyst group of the present invention has a ring shape having a straight body portion and an empty body portion, which is used when olefin or tertiary butanol is subjected to a gas-phase catalytic oxidation reaction to produce a corresponding unsaturated aldehyde and / or an unsaturated carboxylic acid. A group of catalysts containing 200 or more catalysts of (1) and (1) below.
A group of catalysts that satisfy 2).
(1) The length of the straight body portion is shorter than the length of the empty body portion, the straight body portion is between the surface including one end of the empty body portion and the surface including the other end portion, and at least. Includes a catalyst that is linear and / or concave at one end from the end of the straight body to the end of the empty body.
(2) The upward ratio of the catalyst group in the shaking test is 50 % or less.
(Measurement method of upward ratio by shaking test of catalyst group)
100 ring-shaped catalysts randomly selected from the catalyst group are placed in a stainless square bat (width 29).
6 mm, depth 231 mm, height 49 mm), the stainless square bat is attached to the digital shaker FLK-L330-D (manufactured by AS ONE Corporation), the reciprocating shaking width is 10 mm, and the shaking speed is 350 reciprocations / minute. After shaking for a minute, the number of catalysts whose body faces upward is defined as the upward ratio with respect to 100 ring-shaped catalysts.
In addition, "the empty body portion faces upward" means that the opening direction (axial direction) of the ring-shaped catalyst is perpendicular to the bottom surface of the stainless steel square bat.
In the following, the length of the straight body portion is shorter than the length of the empty body portion, the straight body portion is between the surface including one end of the empty body portion and the surface including the other end portion, and A catalyst that is linear and / or concave from the end of the straight body to the end of the empty body at at least one end is a "catalyst (catalyst (
Also called "A)".
The catalyst group of the present invention is a catalyst group containing 200 or more ring-shaped catalysts having a straight body portion and an empty body portion. The number of ring-shaped catalysts contained in the catalyst group is preferably 250 or more, more preferably 300 or more, further preferably 1000 or more, and particularly preferably 2000 or more.
000 or more is particularly preferable. Within the above range, the catalyst group is filled in a reaction tube or the like, and the catalyst group is filled.
The pressure loss in producing acrolein and / or acrylic acid by vapor phase catalytic oxidation of propylene and oxygen-containing gas is reduced, the conversion rate of propylene is increased, and acrolein and / or acrylic acid is produced with high selectivity. Can be done. The upper limit is preferably 20000, more preferably 15000, and even more preferably 12000 from the viewpoint of the filling amount in the reaction tube.
本発明の触媒群におけるリング形状の触媒の総数に対する触媒（Ａ）の数の比率は１０
％以上が好ましく、５０％以上がより好ましく、８０％以上が更に好ましく、９５％以上
が特に好ましい。前記範囲であることにより該触媒群を反応器に充填し、プロピレン等の
オレフィン又はターシャリーブタノールと酸素含有ガスとの気相接触酸化によりアクロレ
イン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造する際の圧
力損失が低減され、高収率でアクロレイン等の不飽和アルデヒド及び／又はアクリル酸等
の不飽和カルボン酸を製造することができる。
The ratio of the number of catalysts (A) to the total number of ring-shaped catalysts in the catalyst group of the present invention is 10.
% Or more is preferable, 50% or more is more preferable, 80% or more is further preferable, and 95% or more is particularly preferable. Within the above range, the catalyst group is filled in the reactor, and unsaturated aldehyde such as acrolein and / or unsaturated acid such as acrylic acid is saturated by vapor phase catalytic oxidation of olefin such as propylene or tertiary butanol and oxygen-containing gas. The pressure loss in producing the carboxylic acid is reduced, and an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid can be produced in high yield.
本発明の触媒群の振とう試験による上向き比率は７０％以下であり、好ましくは５０％
以下であり、より好ましくは４０％以下であり、さらに好ましくは３０％以下であり、と
りわけ好ましくは２５％以下である。該上向き比率の下限は好ましくは１％であり、より
好ましくは３％であり、さらに好ましくは５％である。前記範囲内であることにより、該
触媒群を反応管等の反応器に充填し、プロピレン等のオレフィン又はターシャリーブタノ
ールと酸素含有ガスとの気相接触酸化によりアクロレイン等の不飽和アルデヒド及び／又
はアクリル酸等の不飽和カルボン酸を製造する際の、圧力損失が低減され、高収率でアク
ロレイン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造するこ
とができる。
The upward ratio of the catalyst group of the present invention in the shaking test is 70% or less, preferably 50%.
It is less than or equal to, more preferably 40% or less, still more preferably 30% or less, and particularly preferably 25% or less. The lower limit of the upward ratio is preferably 1%, more preferably 3%, and even more preferably 5%. When it is within the above range, the catalyst group is filled in a reactor such as a reaction tube, and unsaturated aldehyde such as acrolein and / or by vapor-phase catalytic oxidation of olefin such as propylene or tertiary butanol and oxygen-containing gas. The pressure loss in producing an unsaturated carboxylic acid such as acrylic acid is reduced, and an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid can be produced in high yield.
図１（ａ）及び図３（ａ）が直胴部の端部から空胴部の端部までが直線状である触媒（
Ａ）の例であり、図１（ｂ）及び図３（ｂ）が直胴部の端部から空胴部の端部までが凹曲
している触媒（Ａ）の例である。
1 (a) and 3 (a) show a catalyst having a linear shape from the end of the straight body to the end of the empty body.
A) is an example, and FIGS. 1 (b) and 3 (b) are examples of a catalyst (A) in which the end of the straight body portion to the end of the empty body portion is concave.
尚、図３に示す例は直胴部からの直線状部又は凹曲した面が空胴部まで達しておらず、
リング形状における底面部に留まっている例であるが、先述の通りリング形状の触媒が底
面部を有する場合は、底面部の軸方向の末端におけるリング形状の触媒の外縁部が空胴部
の端部であり、このような例も触媒（Ａ）に相当する。
本発明における触媒群に含まれる触媒（Ａ）としては、体積に対する表面積が大きいこ
とより、図１のように底面部がない触媒（Ａ）が好ましい。
In the example shown in FIG. 3, the linear portion or the concave surface from the straight body portion does not reach the empty body portion.
This is an example of staying on the bottom surface of the ring shape, but when the ring-shaped catalyst has a bottom surface as described above, the outer edge of the ring-shaped catalyst at the axial end of the bottom surface is the end of the empty body. It is a part, and such an example also corresponds to the catalyst (A).
As the catalyst (A) included in the catalyst group in the present invention, the catalyst (A) having no bottom surface as shown in FIG. 1 is preferable because the surface area is large with respect to the volume.
触媒（Ａ）の端部の総数に対する直胴部の端部から空胴部の端部までが凹曲している端
部の数の割合（以下「凹曲割合」と称する場合がある。）が特定範囲であると、本発明の
触媒群を使用してプロピレン等のオレフィン又はターシャリーブタノールの気相接触酸化
によりアクロレイン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を
製造する際の圧力損失が低減され、高収率でアクロレイン等の不飽和アルデヒド及び／又
はアクリル酸等の不飽和カルボン酸を製造することができる。なお、触媒（Ａ）1つに対
して端部は２つ存在するため、触媒（Ａ）の端部の総数は、触媒（Ａ）の数の２倍である
。
本発明の触媒群において、凹曲割合は４０％以上であることが好ましく、５０％以上が
より好ましく、６０％以上がさらに好ましく、７０％以上がとりわけ好ましく、８０％以
上が目立って好ましく、９０％以上が特に好ましく、９５％以上が特段好ましく、１００
％が最も好ましい。
The ratio of the number of ends in which the end of the straight body to the end of the empty body is concave with respect to the total number of ends of the catalyst (A) (hereinafter, may be referred to as "concave ratio"). Is within a specific range, the catalyst group of the present invention is used to produce unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid by vapor phase catalytic oxidation of olefins such as propylene or tertiary butanol. The pressure loss is reduced, and unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid can be produced in high yield. Since there are two ends for one catalyst (A), the total number of ends of the catalyst (A) is twice the number of the catalyst (A).
In the catalyst group of the present invention, the concave bending ratio is preferably 40% or more, more preferably 50% or more, further preferably 60% or more, particularly preferably 70% or more, remarkably preferable to 80% or more, and 90%. % Or more is particularly preferable, 95% or more is particularly preferable, and 100
% Is most preferable.
尚、例えば、触媒（Ａ）が、一方の端部において、直胴部の端部から空胴部の端部まで
が直線状であり、他方の端部において、直胴部の端部から空胴部の端部までが凹曲してい
る場合には、凹曲割合は５０％である。また、触媒（Ａ）中の半数が、両方の端部におい
て、直胴部の端部から空胴部の端部までが直線状であり、他の半数が、両方の端部におい
て、直胴部の端部から空胴部の端部までが凹曲している場合にも凹曲割合は上記と同じく
５０％となる。すなわち、上記事例のように、凹曲割合とは、触媒（Ａ）中の端部総数に
対する直胴部の端部から空胴部の端部までが凹曲している数の割合のことである。
It should be noted that, for example, the catalyst (A) has a linear shape from the end of the straight body to the end of the empty body at one end, and is empty from the end of the straight body at the other end. When the end of the body is concave, the concave ratio is 50%. Further, half of the catalyst (A) is linear from the end of the straight body to the end of the empty body at both ends, and the other half is straight at both ends. Even when the portion from the end of the portion to the end of the empty body portion is concave, the concave bending ratio is 50% as described above. That is, as in the above example, the concave bending ratio is the ratio of the number of concave portions from the end portion of the straight body portion to the end portion of the empty body portion with respect to the total number of ends in the catalyst (A). be.
前記触媒（Ａ）において、前記直胴部の端部と前記空胴部の端部との間の距離（ｍｍ）
に対する、前記直胴部の端部と前記空胴部の端部を結ぶ面と該凹曲した面（以下「凹曲面
」と称する場合がある。）との最大距離（ｍｍ）との比（以下「凹曲度合い」と称する場
合がある。）が０．０１以上０．２以下であることが好ましく、より好ましくは０．０２
以上０.１５以下であり、さらに好ましくは０．０５以上０．１以下である。前記範囲内
であることにより、該触媒群を多管式反応器等に充填し、プロピレン等のオレフィン又は
ターシャリーブタノールの気相接触酸化によりアクロレイン等の不飽和アルデヒド及び／
又はアクリル酸等の不飽和カルボン酸を製造する際の、圧力損失が低減され、高収率でア
クロレイン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造する
ことができる。
In the catalyst (A), the distance (mm) between the end portion of the straight body portion and the end portion of the empty body portion.
The ratio of the maximum distance (mm) between the surface connecting the end portion of the straight body portion and the end portion of the empty body portion and the concave surface (hereinafter, may be referred to as "concave curved surface"). Hereinafter, it may be referred to as “degree of concaveness”) is preferably 0.01 or more and 0.2 or less, and more preferably 0.02.
It is 0.15 or more, and more preferably 0.05 or more and 0.1 or less. Within the above range, the catalyst group is filled in a multi-tube reactor or the like, and unsaturated aldehydes such as acrolein and / or unsaturated aldehydes such as acrolein are subjected to vapor phase catalytic oxidation of olefins such as propylene or tertiary butanol.
Alternatively, the pressure loss in producing an unsaturated carboxylic acid such as acrylic acid is reduced, and an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid can be produced in high yield.
尚、前記直胴部の端部と前記空胴部の端部を結ぶ面と凹曲面との最大距離とは図２、図
４により明らかなように、前記直胴部の端部と前記空胴部の端部を結ぶ面と凹曲面が最も
離れている部分の長さのことである。
As is clear from FIGS. 2 and 4, the maximum distance between the surface connecting the end of the straight body and the end of the empty body and the concave curved surface is the end of the straight body and the sky. It is the length of the part where the surface connecting the ends of the body and the concave curved surface are farthest from each other.
前記触媒（Ａ）において、両方の端部において直胴部の端部から空胴部の端部までが凹
曲していることが好ましい。この場合、触媒の流動性が良好となり、ロート等を使用して
多管式反応器等へ触媒群を充填されることにより、ロート内で触媒のブリッジングが抑制
され、反応管内に均一に触媒が充填されることにより、充填時間を短くすることができ、
更に多管式反応器等に充填後、プロピレン等のオレフィン又はターシャリーブタノールの
気相接触酸化によりアクロレイン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和
カルボン酸を製造する際の、圧力損失が低減され、高収率でアクロレイン等の不飽和アル
デヒド及び／又はアクリル酸等の不飽和カルボン酸を製造することが可能となる。
In the catalyst (A), it is preferable that both ends are concave from the end of the straight body portion to the end of the empty body portion. In this case, the fluidity of the catalyst becomes good, and by filling the multi-tube reactor or the like with the catalyst group using a funnel or the like, bridging of the catalyst is suppressed in the funnel and the catalyst is uniformly contained in the reaction tube. By filling, the filling time can be shortened,
Further, after filling in a multi-tube reactor or the like, pressure loss in producing unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid by vapor phase catalytic oxidation of olefins such as propylene or tertiary butanol. It becomes possible to produce an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid in a high yield.
前記直胴部と、前記直胴部の端部と前記空胴部の端部とを結ぶ線とのなす角度は４５°
以上８５°以下が好ましく、５５°以上８０°以下がより好ましく、６５°以上７５°以
下が更に好ましい。該角度を前記範囲とすることにより、触媒群を反応器に充填し、プロ
ピレン等のオレフィン又はターシャリーブタノールの気相接触酸化によりアクロレイン等
の不飽和アルデヒド及び／又はアクリル酸等の不飽和カルボン酸を製造する際の、圧力損
失が効率よく低減され、高収率でアクロレイン等の不飽和アルデヒド及び／又はアクリル
酸等の不飽和カルボン酸を製造することが可能となる。
尚、前記直胴部と、前記直胴部の端部と前記空胴部の端部とを結ぶ線とのなす角度とは
、図１で示すように、該直胴部の端部を頂点として、該直胴部に沿い引いた延長線と、該
直胴部の端部と該空胴部の端部とを結ぶ線とのなす角度のことである。
The angle between the straight body portion and the line connecting the end portion of the straight body portion and the end portion of the empty body portion is 45 °.
It is preferably 85 ° or more, more preferably 55 ° or more and 80 ° or less, and further preferably 65 ° or more and 75 ° or less. By setting the angle within the above range, the catalyst group is filled in the reactor, and unsaturated aldehydes such as achlorine and / or unsaturated carboxylic acids such as acrylic acid are subjected to vapor phase catalytic oxidation of olefins such as propylene or tertiary butanol. The pressure loss is efficiently reduced, and unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid can be produced in high yield.
As shown in FIG. 1, the angle formed by the straight body portion and the line connecting the end portion of the straight body portion and the end portion of the empty body portion is the apex of the end portion of the straight body portion. It is an angle formed by an extension line drawn along the straight body portion and a line connecting the end portion of the straight body portion and the end portion of the empty body portion.
本発明の触媒群における触媒（Ａ）は、軸方向において空胴部を備える領域における内
径ｂ（以下、単に「内径ｂ」や「ｂ」ともいう。単位はｍｍ。）に対する直胴部における
外径ａ（以下、単位「外径ａ」や「ａ」ともいう。単位はｍｍ。）の比（ａ／ｂ）が２．
３以上、内径ｂ（ｍｍ）に対する直胴部長さＨ（ｍｍ）の比（Ｈ／ｂ）が１．３以上、直
胴部長さＨ（ｍｍ）が２ｍｍ～１１ｍｍ、且つ外径ａ（ｍｍ）が２ｍｍ～１１ｍｍである
ことが好ましい。前記範囲であることにより反応器への充填の際の触媒の割れを抑制する
ことができ、オレフィン又はターシャリーブタノールと酸素含有ガスと酸素含有ガスとの
気相接触酸化により対応する不飽和アルデヒド及び／又は不飽和カルボン酸を製造する際
の、圧力損失が低減され、高収率で対応する不飽和アルデヒド及び／又は不飽和カルボン
酸を製造することが可能となる。
又、前記範囲内とすることで、触媒群の振とう試験による上向き比率を制御することが
可能となる。
The catalyst (A) in the catalyst group of the present invention is the outer side of the straight body portion with respect to the inner diameter b (hereinafter, also simply referred to as “inner diameter b” or “b”; the unit is mm) in the region provided with the empty body portion in the axial direction. The ratio (a / b) of the diameter a (hereinafter, also referred to as the unit "outer diameter a" or "a"; the unit is mm) is 2.
3 or more, the ratio (H / b) of the straight body length H (mm) to the inner diameter b (mm) is 1.3 or more, the straight body length H (mm) is 2 mm to 11 mm, and the outer diameter a (mm). Is preferably 2 mm to 11 mm. Within the above range, cracking of the catalyst during filling into the reactor can be suppressed, and the corresponding unsaturated aldehyde and the corresponding unsaturated aldehyde by vapor phase catalytic oxidation of the olefin or tertiary butanol and the oxygen-containing gas and the oxygen-containing gas. The pressure loss in producing / or unsaturated carboxylic acid is reduced, and the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid can be produced in high yield.
Further, by setting it within the above range, it is possible to control the upward ratio by the shaking test of the catalyst group.
ａ／ｂは２．３５以上であることがより好ましく、２．４以上であることがさらに好ま
しく、２．４５以上であることがとりわけ好ましく、２．５以上であることが特に好まし
い。上限は特に限定されないが、触媒強度の観点より３．５であることが好ましい。
Ｈ／ｂは１．３５以上であることがより好ましく、１．４以上であることがさらに好ま
しく、１．４５以上であることがとりわけ好ましく、１．５以上であることが特に好まし
い。上限は特に限定されないが、多管式反応器等への充填時におけるブリッジング抑制効
果の観点より２．５が好ましい。
The a / b is more preferably 2.35 or more, further preferably 2.4 or more, particularly preferably 2.45 or more, and particularly preferably 2.5 or more. The upper limit is not particularly limited, but is preferably 3.5 from the viewpoint of catalyst strength.
H / b is more preferably 1.35 or more, further preferably 1.4 or more, particularly preferably 1.45 or more, and particularly preferably 1.5 or more. The upper limit is not particularly limited, but 2.5 is preferable from the viewpoint of the bridging inhibitory effect at the time of filling into a multi-tube reactor or the like.
Ｈは２ｍｍ～１０ｍｍであることがより好ましく、２．３ｍｍ～９ｍｍであることがさ
らに好ましく、２．６ｍｍ～７ｍｍであることがとりわけ好ましく、３ｍｍ～５ｍｍであ
ることが特に好ましい。
ａは２ｍｍ～１０ｍｍであることがより好ましく、３ｍｍ～９ｍｍであることがさらに
好ましく、４ｍｍ～７ｍｍであることがとりわけ好ましく、４ｍｍ～５．６ｍｍであるこ
とが特に好ましい。
H is more preferably 2 mm to 10 mm, further preferably 2.3 mm to 9 mm, particularly preferably 2.6 mm to 7 mm, and particularly preferably 3 mm to 5 mm.
a is more preferably 2 mm to 10 mm, further preferably 3 mm to 9 mm, particularly preferably 4 mm to 7 mm, and particularly preferably 4 mm to 5.6 mm.
更に、直胴部長さＨ（ｍｍ）に対する外径ａ（ｍｍ）の比（ａ／Ｈ）は１．４７以上で
あることが好ましく、１．５０以上であることがより好ましく、１．５３以上であること
が更に好ましく、１．５６以上であることが特に好ましい。上限は特に限定されないが、
２．５であることが好ましい。前記範囲内であることにより、オレフィン又はターシャリ
ーブタノールと酸素含有ガスとを気相で接触酸化により対応する不飽和アルデヒド及び／
又は不飽和カルボン酸を製造する際の、圧力損失が低減され、高収率で対応する不飽和ア
ルデヒド及び／又は不飽和カルボン酸を製造することが可能となる。
Further, the ratio (a / H) of the outer diameter a (mm) to the straight body portion length H (mm) is preferably 1.47 or more, more preferably 1.50 or more, and 1.53 or more. Is more preferable, and 1.56 or more is particularly preferable. The upper limit is not particularly limited,
It is preferably 2.5. Within the above range, the unsaturated aldehyde corresponding to the olefin or tertiary butanol and the oxygen-containing gas by catalytic oxidation in the gas phase and /
Alternatively, the pressure loss in producing the unsaturated carboxylic acid is reduced, and the corresponding unsaturated aldehyde and / or the unsaturated carboxylic acid can be produced in a high yield.
本発明の触媒群における触媒（Ａ）はプロピレン等のオレフィン又はターシャリーブタ
ノールを酸素含有ガスと気相接触酸化反応させて、対応する不飽和アルデヒド及び／又は
不飽和カルボン酸を製造する際に用いる触媒であって、モリブデン及びビスマスを少なく
とも含む触媒であることが好ましい。かかる２つの成分を含む触媒であれば、本発明の触
媒に適応できるが、なかでも、下記の一般式（１）で表される触媒であることが好ましい
。
The catalyst (A) in the catalyst group of the present invention is used when an olefin such as propylene or tertiary butanol is subjected to a gas phase catalytic oxidation reaction with an oxygen-containing gas to produce a corresponding unsaturated aldehyde and / or an unsaturated carboxylic acid. The catalyst is preferably a catalyst containing at least molybdenum and bismuth. Any catalyst containing these two components can be applied to the catalyst of the present invention, but among them, the catalyst represented by the following general formula (1) is preferable.
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＺｈＱｉＳｉｊＯｋ （１）
（式中、Ｘは、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＴｌからなる群から選ばれる少なくとも１種の
元素であり、Ｙは、Ｂ、Ｐ、Ａｓ及びＷからなる群から選ばれる少なくとも１種の元素で
あり、Ｚは、Ｍｇ、Ｃａ、Ｚｎ、Ｃｅ及びＳｍからなる群から選ばれる少なくとも１種の
元素であり、Ｑは、塩素などのハロゲン原子である。また、ａからｋはそれぞれの元素の
原子比を表わし、ａ＝１２のとき、ｂ＝０．５～７、ｃ＝０～１０、ｄ＝０～１０、ｅ＝
０～３、ｆ＝０～３、ｇ＝０～３、ｈ＝０～１、ｉ＝０～０．５、ｊ＝０～４０の範囲に
あり、またｋは他の元素の酸化状態を満足させる数値である。）
Mo a Bi b Co c Ni d Fe e X f Y g Z h Q i Si j Ok (1)
(In the formula, X is at least one element selected from the group consisting of Na, K, Rb, Cs and Tl, and Y is at least one element selected from the group consisting of B, P, As and W. It is an element, Z is at least one element selected from the group consisting of Mg, Ca, Zn, Ce and Sm, Q is a halogen atom such as chlorine, and a to k are the respective elements. When a = 12, b = 0.5 to 7, c = 0 to 10, d = 0 to 10, e =
It is in the range of 0 to 3, f = 0 to 3, g = 0 to 3, h = 0 to 1, i = 0 to 0.5, j = 0 to 40, and k indicates the oxidation state of other elements. It is a satisfying number. )
本発明の触媒群における触媒は例えば以下のように製造される。
まず、上記触媒の各元素成分を含有する原料化合物を、製造する組成に応じて必要な量
を水性媒体中に適宜溶解又は分散させることにより、触媒成分を含む混合溶液又はその水
性スラリーが製造される。各触媒成分の原料は、それぞれの元素を含む、硝酸塩、アンモ
ニウム塩、水酸化物、酸化物、硫酸塩、炭酸塩、ハロゲン化物、酢酸塩などが用いられる
。例えば、モリブデンとしては、パラモリブデン酸アンモニウム、三酸化モリブデン、塩
化モリブデン等が使用される。ビスマスとしては、塩化ビスマス、硝酸ビスマス、酸化ビ
スマス、次炭酸ビスマス等が使用される。
The catalyst in the catalyst group of the present invention is produced, for example, as follows.
First, a mixed solution containing the catalyst component or an aqueous slurry thereof is produced by appropriately dissolving or dispersing the raw material compound containing each elemental component of the catalyst in an aqueous medium in an amount required according to the composition to be produced. To. As the raw material of each catalyst component, nitrates, ammonium salts, hydroxides, oxides, sulfates, carbonates, halides, acetates and the like containing the respective elements are used. For example, as molybdenum, ammonium paramolybdate, molybdenum trioxide, molybdenum chloride and the like are used. As the bismuth, bismuth chloride, bismuth nitrate, bismuth oxide, bismuth subcarbonate and the like are used.
上記の触媒成分を含む混合溶液又は水性スラリーは、各成分の偏在を防ぐために充分に
攪拌、混合することが好ましい。次いで、触媒成分を含む混合溶液又は水性スラリーは乾
燥して粉体とされる。乾燥は種々の方法で実施でき、例えば、噴霧乾燥機、スラリードラ
イヤー、ドラムドライヤー等による乾燥が挙げられるが、特に噴霧乾燥機による乾燥が好
ましい。
It is preferable that the mixed solution or the aqueous slurry containing the above-mentioned catalyst component is sufficiently stirred and mixed in order to prevent uneven distribution of each component. The mixed solution or aqueous slurry containing the catalyst component is then dried to form a powder. Drying can be carried out by various methods, and examples thereof include drying with a spray dryer, a slurry dryer, a drum dryer and the like, and drying with a spray dryer is particularly preferable.
その後、乾燥により得られる粉体は、リング形状に成形され、触媒が得られる。リング
形状への成形方法は必ずしも制限されるものではないが、打錠成形、押出成形等が好まし
い。特に、直胴部と、直胴部の端部と空胴部の端部とを結ぶ線とのなす角度や前記凹曲度
合いの制御が容易であるため、打錠成形が好ましい。成形に際しては、成形助剤を使用し
てもよい。好ましい成形助剤は、シリカ、グラファイト、結晶性セルロース、セルロース
、デンプン、ポリビニルアルコール、ステアリン酸である。成形助剤は、粉体１００重量
部に対して通常１重量部～５０重量部程度使用できる。また、必要によりセラミックス繊
維、ウイスカー等の無機繊維を触媒の機械的強度向上材として用いることもできる。これ
らの繊維の使用量は、粉体１００重量部に対して通常１重量部～３０重量部である。
Then, the powder obtained by drying is formed into a ring shape to obtain a catalyst. The method for forming a ring shape is not necessarily limited, but tableting molding, extrusion molding and the like are preferable. In particular, tableting molding is preferable because it is easy to control the angle formed by the straight body portion and the line connecting the end portion of the straight body portion and the end portion of the empty body portion and the degree of the concave portion. A molding aid may be used for molding. Preferred molding aids are silica, graphite, crystalline cellulose, cellulose, starch, polyvinyl alcohol and stearic acid. The molding aid can usually be used in an amount of about 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the powder. Further, if necessary, inorganic fibers such as ceramic fibers and whiskers can be used as a material for improving the mechanical strength of the catalyst. The amount of these fibers used is usually 1 part by weight to 30 parts by weight with respect to 100 parts by weight of the powder.
本発明の触媒群はリング形状以外の形状の触媒を含んでいてもよい。リング形状以外の
形状とは例えば、球状、円柱状等が挙げられる。
本発明の触媒群は、不活性充填物により希釈してオレフィン又はターシャリーブタノー
ルを気相接触酸化反応させて対応する不飽和アルデヒド及び／又は不飽和カルボン酸の製
造に使用したとしても、本発明の目的を損なわず効果を発現することができる。不活性充
填材とは気相接触酸化反応で余計な副反応を引き起こさない材料であればよく、例えば、
アルミナ、ジルコニア、チタニア、マグネシア、シリカ等の高温処理した酸化物やステア
タイト、ムライト、炭化ケイ素、窒化ケイ素などの高温焼結材料等を用いることができる
。
The catalyst group of the present invention may include a catalyst having a shape other than the ring shape. Examples of the shape other than the ring shape include a spherical shape and a columnar shape.
The catalyst group of the present invention may be used for the production of the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by diluting with an inert filler and subjecting an olefin or tertiary butanol to a gas-phase catalytic oxidation reaction. The effect can be exhibited without impairing the purpose of. The inert filler may be any material that does not cause an extra side reaction in the gas phase contact oxidation reaction, for example.
High-temperature treated oxides such as alumina, zirconia, titania, magnesia, and silica, and high-temperature sintered materials such as steatite, mullite, silicon carbide, and silicon nitride can be used.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない
限り、以下の実施例に何ら限定されるものではない。
Hereinafter, the present invention will be described in more detail 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.
＜触媒群の調製＞
酸素を除く構成成分の実験式が表１に示す組成である複合金属酸化物を以下のようにし
て製造した。なお、使用した各供給源化合物の量は、表１に示す量である。
容器に温水１０９０ｍｌを入れ、更にパラモリブデン酸アンモニウム１１０ｇを加えて
溶解させ、溶液とした。次いで、該溶液にヒュームドシリカ水分散液４０７ｇを加えて、
撹拌し、懸濁液とした（以下、「懸濁液Ａ」と称する）。該ヒュームドシリカ水分散液は
、ヒュームドシリカ５ｋｇ（比表面積５０ｍ２／ｇ）をイオン交換水２２．５Ｌに加えて
ヒュームドシリカ懸濁液とした後に、該ヒュームドシリカ懸濁液を、ホモジナイザーであ
るULTRA-TURRAX T115KT（ＩＫＡ社製）により、３０分間分散処理を行い、ヒュームドシ
リカ水分散液としたものであり、ケイ素の供給源化合物とした。
<Preparation of catalyst group>
A composite metal oxide having the composition shown in Table 1 in the empirical formula of the constituent components excluding oxygen was produced as follows. The amount of each source compound used is the amount shown in Table 1.
1090 ml of warm water was placed in a container, and 110 g of ammonium paramolybdate was further added and dissolved to prepare a solution. Then, 407 g of the fumed silica aqueous dispersion was added to the solution, and the solution was added.
The mixture was stirred to prepare a suspension (hereinafter referred to as "suspension A"). The fumed silica aqueous dispersion is prepared by adding 5 kg of fumed silica (specific surface area 50 m 2 / g) to 22.5 L of ion-exchanged water to form a fumed silica suspension, and then adding the fumed silica suspension. A homogenizer ULTRA-TURRAX T115KT (manufactured by IKA) was used to carry out a dispersion treatment for 30 minutes to prepare a fumed silica aqueous dispersion, which was used as a silicon source compound.
別の容器に純水１２７ｍｌを入れ、更に硝酸第二鉄１５．１ｇ、硝酸コバルト６５．７
ｇ及び硝酸ニッケル５２．５ｇを加えて、加温して溶解させた（以下、「溶液Ｂ」と称す
る）。溶液Ｂを懸濁液Ａに添加し、均一になるように攪拌し、加熱乾燥し、固形物を得た
。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した。
Put 127 ml of pure water in another container, and further add 15.1 g of ferric nitrate and 65.7 g of cobalt nitrate.
g and 52.5 g of nickel nitrate were added, and the mixture was heated and dissolved (hereinafter referred to as “solution B”). Solution B was added to suspension A, stirred to be uniform, and dried by heating to obtain a solid substance. The solid was then heat treated in an air atmosphere at 300 ° C. for 1 hour.
更に、別の容器に純水１１０ｍｌ、アンモニア水１２ｍｌを入れ、パラモリブデン酸ア
ンモニウム１９．２ｇを加えて溶解し、「溶液Ｃ」とした。次いで、溶液Ｃにホウ砂１．
７ｇ及び硝酸カリウム０．５ｇを加えて溶解し、「溶液Ｄ」とした。前記熱処理した固形
物１５０ｇを溶液Ｄに添加し、均一になるように混合した。次いでＮａを０．５３％固溶
した次炭酸ビスマス１７．４ｇを加えて３０分間混合した後、水分を除去するため加熱乾
燥し、乾燥品を得た。該乾燥品を粉砕し、得られた粉体を打錠成型し、密度１．２７ｇ／
ｃｍ３のリング形状の成形品とした。該成形品を空気雰囲気下、５１５℃で２時間焼成し
て得られたリング形状の触媒を用いて以下に示す触媒群を調製した。
Further, 110 ml of pure water and 12 ml of aqueous ammonia were placed in another container, and 19.2 g of ammonium paramolybdate was added and dissolved to obtain "Solution C". Then, borax in solution C 1.
7 g and 0.5 g of potassium nitrate were added and dissolved to obtain "Solution D". 150 g of the heat-treated solid was added to the solution D and mixed so as to be uniform. Next, 17.4 g of subcarbonated bismuth in which Na was dissolved in 0.53% was added and mixed for 30 minutes, and then heat-dried to remove water to obtain a dried product. The dried product is crushed, and the obtained powder is tablet-molded to have a density of 1.27 g /.
A ring-shaped molded product of cm 3 was used. The catalyst group shown below was prepared using a ring-shaped catalyst obtained by firing the molded product at 515 ° C. for 2 hours in an air atmosphere.
（実施例１）
実施例１の触媒群を構成するすべての触媒は、図１に示すように底面部がなく、外径：
５ｍｍ、内径：２ｍｍ、直胴部長さ：３ｍｍ、空胴部長さ：４ｍｍであった。また、両方
の端部において、直胴部の端部から空胴部の端部までが直線状であった。更に、両方の端
部において、直胴部と、直胴部の端部と空胴部の端部とを結ぶ線とのなす角度、すなわち
、直胴部に沿い引いた延長線と、該直胴部の端部と該空胴部の端部とを結ぶ線とのなす角
度はいずれも７２°であった。触媒組成、圧力損失、プロピレンの気相接触酸化反応結果
等を表１、表２にまとめた。尚、圧力損失の測定には触媒数が４０９０（アクリル樹脂製
直管９００ｍｍの高さに相当）である触媒群を使用し、プロピレンの気相接触酸化反応に
は触媒数が３２２（４０ｍｌに相当）である触媒群を使用した。
(Example 1)
As shown in FIG. 1, all the catalysts constituting the catalyst group of Example 1 have no bottom surface and have an outer diameter:
The inner diameter was 5 mm, the straight body length was 3 mm, and the empty body length was 4 mm. Further, at both ends, the portion from the end of the straight body portion to the end portion of the empty body portion was linear. Further, at both ends, the angle formed by the straight body portion and the line connecting the end portion of the straight body portion and the end portion of the empty body portion, that is, the extension line drawn along the straight body portion and the straight body portion. The angle formed by the line connecting the end of the body and the end of the air body was 72 °. The catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, etc. are summarized in Tables 1 and 2. A group of catalysts having a catalyst number of 4090 (corresponding to a height of 900 mm of an acrylic resin straight tube) was used for measuring the pressure loss, and the number of catalysts was 322 (corresponding to 40 ml) for the gas phase catalytic oxidation reaction of propylene. ) Was used.
（実施例２）
実施例２の触媒群を構成するすべての触媒は、図１に示すように底面部がなく、外径：
５ｍｍ、内径：２ｍｍ、直胴部長さ：３ｍｍ、空胴部長さ：４ｍｍであった。また、一方
の端部において直胴部の端部から空胴部の端部までが直線状であり、他方の端部において
は直胴部の端部から空胴部の端部までが凹曲していた。すなわち、実施例２の触媒群の凹
曲割合は５０％であった。更に、直胴部の端部と空胴部の端部との間の距離は１．５９ｍ
ｍであり、直胴部の端部と空胴部の端部を結ぶ平面と該凹曲面との最大距離は０．０９ｍ
ｍであった。更に、直胴部の端部と空胴部の端部との間の距離に対する、直胴部の端部と
空胴部の端部を結ぶ面と凹曲面との最大距離との比は０．０６であった。触媒組成、圧力
損失、プロピレンの気相接触酸化反応結果等を表１、表２にまとめた。尚、圧力損失の測
定には触媒数が４０１４（アクリル樹脂製直管９００ｍｍの高さに相当）である触媒群を
用い、プロピレンの気相接触酸化反応には触媒数が３１５（４０ｍｌに相当）である触媒
群を用いた。
(Example 2)
As shown in FIG. 1, all the catalysts constituting the catalyst group of Example 2 have no bottom surface and have an outer diameter:
The inner diameter was 5 mm, the straight body length was 3 mm, and the empty body length was 4 mm. Further, at one end, the end of the straight body to the end of the empty body is linear, and at the other end, the end of the straight body to the end of the empty body is concave. Was. That is, the concave bending ratio of the catalyst group of Example 2 was 50%. Furthermore, the distance between the end of the straight body and the end of the empty body is 1.59 m.
The maximum distance between the plane connecting the end of the straight body and the end of the empty body and the concave curved surface is 0.09 m.
It was m. Further, the ratio of the maximum distance between the surface connecting the end of the straight body and the end of the air body and the concave curved surface to the distance between the end of the straight body and the end of the air body is 0. It was .06. The catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, etc. are summarized in Tables 1 and 2. A group of catalysts having a catalyst number of 4014 (corresponding to a height of 900 mm of an acrylic resin straight tube) was used for measuring the pressure loss, and the number of catalysts was 315 (corresponding to 40 ml) for the vapor phase catalytic oxidation reaction of propylene. The catalyst group was used.
（実施例３）
実施例３の触媒群を構成するすべての触媒は、図１に示すように底面部がなく、外径：
５ｍｍ、内径：２ｍｍ、直胴部長さ：３ｍｍ、空胴部長さ：４ｍｍであった。また、両方
の端部において直胴部の端部から空胴部の端部までが凹曲しているものであり、すなわち
、実施例３の触媒群の凹曲割合は１００％であった。更に、直胴部の端部と空胴部の端部
との間の距離に対する、直胴部の端部と空胴部の端部を結ぶ面と凹曲面との最大距離との
比は０．１であった。触媒組成、圧力損失、プロピレンの気相接触酸化反応結果等を表１
、表２にまとめた。尚、圧力損失の測定には触媒数が４１０８（アクリル樹脂製直管９０
０ｍｍの高さに相当）である触媒群を用い、プロピレンの気相接触酸化反応には触媒数が
３２２（４０ｍｌに相当）である触媒群を用いた。
(Example 3)
As shown in FIG. 1, all the catalysts constituting the catalyst group of Example 3 have no bottom surface and have an outer diameter:
The inner diameter was 5 mm, the straight body length was 3 mm, and the empty body length was 4 mm. Further, both ends were concave from the end of the straight body to the end of the empty body, that is, the concave ratio of the catalyst group of Example 3 was 100%. Further, the ratio of the maximum distance between the surface connecting the end of the straight body and the end of the air body and the concave curved surface to the distance between the end of the straight body and the end of the air body is 0. It was .1. Table 1 shows the catalyst composition, pressure loss, gas-phase catalytic oxidation reaction results of propylene, etc.
, Table 2. The number of catalysts is 4108 (acrylic resin straight pipe 90) for measuring pressure loss.
A catalyst group having a height of 0 mm) was used, and a catalyst group having a catalyst number of 322 (corresponding to 40 ml) was used for the vapor phase catalytic oxidation reaction of propylene.
（実施例４）
実施例４の触媒群を構成するすべての触媒は、図１に示すように底面部がなく、外径：
５ｍｍ、内径：２ｍｍ、直胴部長さ：３ｍｍ、空胴部長さ：４ｍｍであった。また、両方
の端部において直胴部の端部から空胴部の端部までが直線状又は凹曲しているものが混在
しており、凹曲しているものは直胴部の端部と空胴部の端部との間の距離に対する、直胴
部の端部と空胴部の端部を結ぶ面と凹曲面との最大距離との比は０．１であった。実施例
４の触媒群の凹曲割合は７５％であった。触媒組成、圧力損失、プロピレンの気相接触酸
化反応結果等を表１、表２にまとめた。尚、圧力損失の測定には触媒数が４０７４（アク
リル樹脂製直管９００ｍｍの高さに相当）である触媒群を用い、プロピレンの気相接触酸
化反応には触媒数が３１９（４０ｍｌに相当）である触媒群を用いた。
(Example 4)
As shown in FIG. 1, all the catalysts constituting the catalyst group of Example 4 have no bottom surface and have an outer diameter:
The inner diameter was 5 mm, the straight body length was 3 mm, and the empty body length was 4 mm. In addition, at both ends, there are some that are straight or concave from the end of the straight body to the end of the empty body, and those that are concave are the ends of the straight body. The ratio of the maximum distance between the surface connecting the end of the straight body and the end of the body and the concave curved surface to the distance between the body and the end of the body was 0.1. The concave bending ratio of the catalyst group of Example 4 was 75%. The catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, etc. are summarized in Tables 1 and 2. A group of catalysts having a catalyst number of 4074 (corresponding to a height of 900 mm of an acrylic resin straight tube) was used for measuring the pressure loss, and the number of catalysts was 319 (corresponding to 40 ml) for the gas phase catalytic oxidation reaction of propylene. The catalyst group was used.
（実施例５）
実施例５の触媒群を構成するすべての触媒は、図１に示すように底面部がなく、外径：
５ｍｍ、内径：２ｍｍ、直胴部長さ：３ｍｍ、空胴部長さ：４ｍｍであった。また、両方
の端部において直胴部の端部から空胴部の端部までが直線状又は凹曲しているものが混在
しており、凹曲しているものは直胴部の端部と空胴部の端部との間の距離に対する、直胴
部の端部と空胴部の端部を結ぶ面と凹曲面との最大距離との比は０．１であった。実施例
５の触媒群の凹曲割合は８０％であった。触媒組成、圧力損失、プロピレンの気相接触酸
化反応結果等を表１、表２にまとめた。尚、圧力損失の測定には触媒数が４０９１（アク
リル樹脂製直管９００ｍｍの高さに相当）である触媒群を用い、プロピレンの気相接触酸
化反応には触媒数が３１８（４０ｍｌに相当）である触媒群を用いた。
(Example 5)
As shown in FIG. 1, all the catalysts constituting the catalyst group of Example 5 have no bottom surface and have an outer diameter:
The inner diameter was 5 mm, the straight body length was 3 mm, and the empty body length was 4 mm. In addition, at both ends, there are some that are straight or concave from the end of the straight body to the end of the empty body, and those that are concave are the ends of the straight body. The ratio of the maximum distance between the surface connecting the end of the straight body and the end of the body and the concave curved surface to the distance between the body and the end of the body was 0.1. The concave bending ratio of the catalyst group of Example 5 was 80%. The catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, etc. are summarized in Tables 1 and 2. A group of catalysts having a catalyst number of 4091 (corresponding to a height of 900 mm of an acrylic resin straight tube) was used for measuring the pressure loss, and the number of catalysts was 318 (corresponding to 40 ml) for the vapor phase catalytic oxidation reaction of propylene. The catalyst group was used.
（比較例１）
比較例１の触媒群を構成するすべての触媒は外径：５ｍｍ、内径：２ｍｍ、直胴部長さ
：３ｍｍ、空胴部長さ：３ｍｍであり、直胴部長さと空胴部長さが同じであること、直胴
部の端部から空胴部の端部まで平坦であったこと以外は実施例１と同じ触媒を得た。触媒
組成、圧力損失、プロピレンの気相接触酸化反応結果等を表１、表２にまとめた。尚、圧
力損失の測定には触媒数が５０１４（アクリル樹脂製直管９００ｍｍの高さに相当）であ
る触媒群を用い、プロピレンの気相接触酸化反応には触媒数が３５９（４０ｍｌに相当）
である触媒群を用いた。
(Comparative Example 1)
All the catalysts constituting the catalyst group of Comparative Example 1 have an outer diameter: 5 mm, an inner diameter: 2 mm, a straight body length: 3 mm, and an empty body length: 3 mm, and the straight body length and the empty body length are the same. The same catalyst as in Example 1 was obtained except that it was flat from the end of the straight body to the end of the empty body. The catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, etc. are summarized in Tables 1 and 2. A catalyst group having a catalyst number of 5014 (corresponding to a height of 900 mm of an acrylic resin straight tube) was used for measuring the pressure loss, and a catalyst number of 359 (corresponding to 40 ml) was used for the gas phase contact oxidation reaction of propylene.
A group of catalysts was used.
＜圧力損失の測定＞
内径２６ｍｍ、長さ１０００ｍｍのアクリル樹脂製直管を直立させ、前記触媒群を９０
０ｍｍの高さまで充填して、該アクリル樹脂製直管の上部に取り付けた内径６ｍｍのＳＵ
Ｓ製配管より室温で乾燥空気を５０ＮＬ／分の流量で流通させ、ＳＵＳ製配管より分岐し
た配管に取り付けたデジタル差圧計ｔｅｓｔｏ ５０６－３で差圧を測定した（差圧Ａ）
。次いで、該リング形状の触媒をアクリル樹脂製直管より抜出して空筒とし、同様に差圧
を測定し、ブランク値とした。圧力損失は（差圧Ａ）－ブランク値として求めた。
<Measurement of pressure loss>
An acrylic resin straight pipe with an inner diameter of 26 mm and a length of 1000 mm is erected, and the catalyst group is 90.
A SU with an inner diameter of 6 mm, which is filled to a height of 0 mm and attached to the upper part of the acrylic resin straight pipe.
Dry air was circulated from the S pipe at room temperature at a flow rate of 50 NL / min, and the differential pressure was measured with the digital differential pressure gauge testo 506-3 attached to the pipe branched from the SUS pipe (differential pressure A).
.. Next, the ring-shaped catalyst was extracted from an acrylic resin straight tube to form an empty tube, and the differential pressure was measured in the same manner to obtain a blank value. The pressure loss was determined as (differential pressure A) -blank value.
＜プロピレンの気相接触酸化反応＞
前記触媒群４０ｍｌおよび直径５ｍｍのムライトボール５２ｍｌを混合して混合物とし
、内径１５ｍｍのステンレス鋼製ナイタージャケット付反応管に充填した。該反応管入口
よりプロピレン１０容量％、スチーム１７容量％、空気７３容量％の原料ガスを７０ｋＰ
ａにて、流通し、該触媒群との接触時間６．０秒で通過させて、プロピレンの気相接触酸
化反応を実施した。尚、該反応管はナイター浴で加熱しており、浴温は３３０℃で実施し
た。反応生成物の分析は、反応管出口より反応生成物を回収し、ガスクロマトグラフィー
を用いて、常法により実施した。
<Phistric contact oxidation reaction of propylene>
40 ml of the catalyst group and 52 ml of mullite balls having a diameter of 5 mm were mixed to form a mixture, which was filled in a reaction tube with a stainless steel night game jacket having an inner diameter of 15 mm. 70 kP of raw material gas containing 10% by volume of propylene, 17% by volume of steam, and 73% by volume of air from the inlet of the reaction tube.
In a, it was circulated and passed through the catalyst group with a contact time of 6.0 seconds, and a gas phase contact oxidation reaction of propylene was carried out. The reaction tube was heated in a night game bath, and the bath temperature was 330 ° C. The analysis of the reaction product was carried out by a conventional method using the reaction product collected from the outlet of the reaction tube and using gas chromatography.
プロピレン転化率、アクロレイン収率、アクリル酸の定義は、次の通りである。
・プロピレン転化率（モル％）＝（反応したプロピレンのモル数／供給したプロピレン
のモル数）×１００
・アクロレイン収率（モル％）＝（生成したアクロレインのモル数／供給したプロピレ
ンのモル数）×１００
アクリル酸収率（モル％）＝（生成したアクリル酸のモル数／供給したプロピレンのモ
ル数）×１００
・合計収率（モル％）＝アクロレイン収率（モル％）＋アクリル酸収率（モル％）
The definitions of propylene conversion rate, acrolein yield, and acrylic acid are as follows.
Propylene conversion rate (mol%) = (number of moles of reacted propylene / number of moles of supplied propylene) x 100
Acrolein yield (mol%) = (number of moles of acrolein produced / number of moles of supplied propylene) x 100
Acrylic acid yield (mol%) = (number of moles of produced acrylic acid / number of moles of supplied propylene) x 100
-Total yield (mol%) = acrolein yield (mol%) + acrylic acid yield (mol%)
本発明の触媒群は実施例において示されているように、該触媒群が充填された反応器に
よりプロピレンからアクロレイン及び／又はアクリル酸を製造した際に、圧力損失が低く
抑えられ、且つ、プロピレンの転化率が高く、高選択率でアクロレイン及び／又はアクリ
ル酸とし、結果として高収率でアクロレイン及び／又はアクリル酸を製造することができ
た。
As shown in Examples, the catalyst group of the present invention has a low pressure loss and propylene when acrolein and / or acrylic acid is produced from propylene by a reactor filled with the catalyst group. Acrolein and / or acrylic acid could be produced with a high conversion rate and high selectivity, and as a result, acrolein and / or acrylic acid could be produced with a high yield.
実施例における圧力損失は、触媒の充填層長さ９００ｍｍとし、簡易的に乾燥空気をガ
ス流速として５０ＮＬ／分、流通させた測定により、従来技術に対する優位性を示してい
る。尚、圧力損失は、通常、下記Ｅｒｇｕｎ式に示されるように触媒の充填層長さとガス
流速の二乗とに比例することが一般的である。アクロレイン等の不飽和アルデヒド及び／
又はアクリル酸等の不飽和カルボン酸を工業的に製造する際には固定床管型反応器が用い
られ、通常、該固定床管型反応器には２０００ｍｍ～７０００ｍｍの反応管を数千～数万
本有している（特開２０１１－２２５４７６号公報、ＷＯ２００５／００５０３７号公報
）。そのため、アクロレイン等の不飽和アルデヒド及び／又はアクリル酸等の不飽和カル
ボン酸の工業的な製造プラントにおいて、本発明の従来技術に対する圧力損失の差異は、
実施例で示した結果より２．２～７．８倍拡大する方向であり、本発明の優位性は工業的
規模となるほど大きくなることは明らかである。更に、不飽和アルデヒド及び／又は不飽
和カルボン酸の製造においては圧力損失が高い方が、コーキングが発生し、又、時間経過
とともに圧力損失の上昇とコーキングの増大が起きる。すなわち、時間を経るに従い、本
発明の従来技術に対する圧力損失の差異は広がる方向であることは明らかである。
The pressure loss in the examples is shown to be superior to the prior art by a measurement in which the length of the packed bed of the catalyst is 900 mm and dry air is simply circulated at a gas flow rate of 50 NL / min. It should be noted that the pressure loss is generally proportional to the square of the packed bed length of the catalyst and the gas flow rate as shown in the following Ergun equation. Unsaturated aldehydes such as acrolein and /
Alternatively, when unsaturated carboxylic acids such as acrylic acid are industrially produced, a fixed bed tube type reactor is used, and usually, the fixed bed tube type reactor is provided with several thousand to several 2,000 mm to 7,000 mm reaction tubes. It has 10,000 copies (Japanese Patent Laid-Open Nos. 2011-225476, WO2005 / 005037). Therefore, in an industrial production plant for unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid, the difference in pressure loss with respect to the prior art of the present invention is
It is in the direction of expanding 2.2 to 7.8 times from the results shown in the examples, and it is clear that the superiority of the present invention increases as the scale becomes industrial. Further, in the production of unsaturated aldehyde and / or unsaturated carboxylic acid, the higher the pressure loss, the more coking occurs, and the pressure loss increases and the coking increases with the passage of time. That is, it is clear that the difference in pressure loss with respect to the prior art of the present invention tends to widen over time.
（ΔＰ：圧力損失、Ｌ：充填層長さ、ρ：ガス密度、ｕ：ガス流速、Ｄｐ：粒子径、ε：
空隙率、Ｒｅｐ：レイノルズ数）
(ΔP: pressure loss, L: packed bed length, ρ: gas density, u: gas flow velocity, Dp: particle size, ε:
Porosity , Rep: Reynolds number)
１ 内径
２ 外径
３ 直胴部長さ
４ 直胴部と、直胴部の端部と空胴部の端部とを結ぶ線とのなす角度
５ 直胴部の端部と空胴部の端部との間の距離
６ 直胴部の端部と空胴部の端部を結ぶ平面と凹曲面との最大距離
７ 空胴部の長さ
Ａ 直胴部
Ｂ 空胴部
Ｃ 空胴部の端部
1
Claims (4)
デヒド及び／又は不飽和カルボン酸を製造する際に用いる、直胴部及び空胴部を有するリ
ング形状の触媒を２００以上含む触媒群であって、下記（１）及び（２）を満たす触媒群
。
（１）該直胴部の長さが該空胴部の長さより短く、該直胴部が該空胴部の一方の端部を含
む面と他方の端部を含む面との間にあり、且つ、少なくとも一方の端部において該直胴部
の端部から該空胴部の端部までが直線状である及び／又は凹曲している触媒（Ａ）を含む
。
（２）該触媒群の振とう試験による上向き比率が５０％以下である。
（触媒群の振とう試験による上向き比率の測定法）
触媒群中、無作為に抽出したリング形状の触媒１００個をステンレス角バット（幅２９
６ｍｍ、奥行２３１ｍｍ、高さ４９ｍｍ）に入れ、該ステンレス角バットをデジタルシェ
ーカーFLK-L330-D（アズワン株式会社製）に装着し、往復振とう幅１０ｍｍで、振とう速
度３５０往復／分により１分間振とうさせた後、該リング形状の触媒１００個に対して、
空胴部が上を向いている触媒の個数を上向き比率とする。 A catalyst containing 200 or more ring-shaped catalysts having a straight body portion and an empty body portion used in producing the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by subjecting an olefin or tertiary butanol to a gas-phase catalytic oxidation reaction. A group of catalysts satisfying the following (1) and (2).
(1) The length of the straight body portion is shorter than the length of the empty body portion, and the straight body portion is located between the surface including one end of the empty body portion and the surface including the other end portion. And includes the catalyst (A), which is linear and / or concave from the end of the straight body to the end of the empty body at at least one end.
(2) The upward ratio of the catalyst group in the shaking test is 50 % or less.
(Measurement method of upward ratio by shaking test of catalyst group)
100 ring-shaped catalysts randomly selected from the catalyst group are placed in a stainless square bat (width 29).
6 mm, depth 231 mm, height 49 mm), the stainless square bat is attached to the digital shaker FLK-L330-D (manufactured by AS ONE Corporation), the reciprocating shaking width is 10 mm, and the shaking speed is 350 reciprocations / minute. After shaking for a minute, for 100 of the ring-shaped catalysts,
The number of catalysts with the empty body facing upward is defined as the upward ratio.
る、前記直胴部の端部と前記空胴部の端部を結ぶ面と前記直線状部又は凹曲した面との最
大距離（ｍｍ）との比が０以上０．２以下である請求項１に記載の触媒群。 The surface of the catalyst (A) connecting the end portion of the straight body portion and the end portion of the empty body portion with respect to the distance (mm) between the end portion of the straight body portion and the end portion of the empty body portion. The catalyst group according to claim 1, wherein the ratio of the catalyst group to the maximum distance (mm) from the linear portion or the concave surface is 0 or more and 0.2 or less.
直線状である及び／又は凹曲している請求項１又は２に記載の触媒群。 The catalyst according to claim 1 or 2, wherein the end of the straight body portion to the end portion of the empty body portion is linear and / or concave at both ends of the catalyst (A). group.
るアクロレイン及び／又はアクリル酸の製造方法。 A method for producing acrolein and / or acrylic acid that undergoes gas-phase catalytic oxidation of propylene in the presence of the catalyst group according to any one of claims 1 to 3.
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|---|---|---|---|---|
| JP2001293376A (en) | 2000-02-25 | 2001-10-23 | Basf Ag | Shaped catalyst |
| JP2004082099A (en) | 2002-06-27 | 2004-03-18 | Mitsubishi Rayon Co Ltd | Filling method of solid catalyst |
| WO2009147965A1 (en) | 2008-06-02 | 2009-12-10 | 日本化薬株式会社 | Catalyst and method of producing unsaturated aldehyde and unsaturated carboxylic acid |
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|---|---|---|---|---|
| DE2914683A1 (en) * | 1979-04-11 | 1980-10-16 | Basf Ag | VANADIUM AND TITANIUM AND / OR ZIRCONIZED CARRIER CATALYST |
| DE3445289A1 (en) * | 1984-12-12 | 1986-06-19 | Basf Ag, 6700 Ludwigshafen | SHAPED CATALYST FOR HETEROGENIC CATALYZED REACTIONS |
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| JP2001293376A (en) | 2000-02-25 | 2001-10-23 | Basf Ag | Shaped catalyst |
| JP2004082099A (en) | 2002-06-27 | 2004-03-18 | Mitsubishi Rayon Co Ltd | Filling method of solid catalyst |
| WO2009147965A1 (en) | 2008-06-02 | 2009-12-10 | 日本化薬株式会社 | Catalyst and method of producing unsaturated aldehyde and unsaturated carboxylic acid |
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