JP6958390B2 - catalyst - Google Patents
catalyst Download PDFInfo
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- JP6958390B2 JP6958390B2 JP2018012547A JP2018012547A JP6958390B2 JP 6958390 B2 JP6958390 B2 JP 6958390B2 JP 2018012547 A JP2018012547 A JP 2018012547A JP 2018012547 A JP2018012547 A JP 2018012547A JP 6958390 B2 JP6958390 B2 JP 6958390B2
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- 239000003054 catalyst Substances 0.000 title claims description 100
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 48
- 150000001299 aldehydes Chemical class 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000012808 vapor phase Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- -1 pressure loss 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
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 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
- 239000006185 dispersion Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 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
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009776 industrial production 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray 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
- 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
- 150000001253 acrylic acids Chemical class 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
- 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
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 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 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 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
- 229910052863 mullite Inorganic materials 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
- 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
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011800 void material Substances 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
Images
Description
本発明は、触媒に関する。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
用いる触媒に関する。
The present invention relates to catalysts. More specifically, the present invention relates to a catalyst used in producing the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by subjecting an olefin or tertiary butanol to a vapor 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 vapor 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こ
とが記載されている。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 heterogeneous catalytic reaction, which is formed into a hollow cylindrical body and the end face of the hollow cylindrical body is curved. Patent Document 2 describes a ring-shaped non-supported catalyst containing at least Mo, Bi and Fe as a catalyst for producing acrolein from propylene or the like, which has a specific length, outer diameter and wall thickness. It is stated that the end face is curved. Further, in
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によりオレフ
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。
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、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
いため反応の効率が低く、転化率、選択率が低下する場合がある。
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。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。
However, in these previously known catalysts, when an olefin or tertiary butanol is subjected to a vapor phase catalytic oxidation reaction in a reactor filled with the catalyst to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid, the pressure is applied. There has been a problem that the 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.
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 a catalyst having a hollow cylindrical end face curved, the catalyst surface area with respect to the catalyst volume is small and the reaction active sites are small, so that the reaction efficiency is low and the conversion rate and selectivity may decrease.
Further, in the production of unsaturated aldehydes and / or unsaturated carboxylic acids, carbides adhere to the surface of the catalyst. Adhesion (caulking) of the carbide to the catalyst surface is likely to occur due to a small amount of gas in a reaction tube having a high pressure loss in a multi-tube reactor. 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、触媒
を用いて、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を製造した場合、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, in the present invention, when an olefin or tertiary butanol is subjected to a gas-phase catalytic oxidation reaction to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid using a catalyst, the pressure loss is reduced and the amount of gas is reduced. It is an object of the present invention to provide a catalyst which can hold high and thereby suppress coking and can produce the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid in high yield.
本発明者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、直胴部と空胴部を有するリング形状の触媒を、該直胴部の長
さを、該空胴部の長さより短くし、且つ、該直胴部の端部から該空胴部の端部までが凹曲
している触媒とすることにより、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。
As a result of intensive studies to solve the above problems, the present inventor directly reacts an olefin or a tertiary butanol with a vapor-phase catalytic oxidation reaction to produce a corresponding unsaturated aldehyde and / or an unsaturated carboxylic acid. A ring-shaped catalyst having a body portion and an empty body portion has a straight body portion shorter than the length of the empty body portion, and the end portion of the straight body portion to the end portion of the empty body portion. It was found that the pressure loss can be suppressed to a low level and the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid can be produced in a high yield by using a catalyst having a concave shape. The present invention has been reached.
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、直胴部と空胴部を有す
るリング形状の触媒であって、該直胴部の長さが該空胴部の長さより短く、且つ、該直胴
部の端部から該空胴部の端部までが凹曲している触媒。
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 vapor phase catalytic oxidation reaction to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid. A catalyst in which the length of the straight body portion is shorter than the length of the empty body portion, and the end portion of the straight body portion to the end portion of the empty body portion is concave.
［２］ 前記直胴部が、前記空胴部のそれぞれの端部を含む面間にある［１］に記載の触
媒。
［３］ 前記直胴部の端部と前記空胴部の端部との長さ（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との最大距離（ｍｍ）との比が０．０１
以上０．２以下である［１］又は［２］に記載の触媒。
［４］ 前記直胴部の端部から前記空胴部の端部まで凹曲しているのが両端部である［１
］乃至［３］のいずれかに記載の触媒。
［５］ 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が
４５°〜８５°である［１］乃至［４］のいずれかに記載の触媒。
[2] The catalyst according to [1], wherein the straight body portion is located between surfaces including each end portion of the empty body portion.
[3] The surface connecting the end of the straight body and the end of the air body and the concave portion with respect to the length (mm) of the end of the straight body and the end of the air body. The ratio to the maximum distance (mm) from the surface is 0.01
The catalyst according to [1] or [2], which is 0.2 or more and 0.2 or less.
[4] Both ends are concave from the end of the straight body to the end of the empty body [1].
] To [3].
[5] Any one of [1] to [4], wherein 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 45 ° to 85 °. The catalyst described in.
［６］ 内径ｂ（ｍｍ）に対する外径ａ（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［１］乃至［５］
のいずれかに記載の触媒。
［７］ ［１］乃至［６］のいずれかに記載の触媒の存在下、プロピレンと酸素含有ガス
を含む原料混合ガス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。
[6] The ratio (a / b) of the outer diameter a (mm) to the inner diameter b (mm) is 2.3 or more, and the inner diameter b (
The ratio (H / b) of the straight body length H (mm) to mm) is 1.3 or more, and the straight body length H (mm)
) Is 2 mm to 11 mm, and the outer diameter a (mm) is 2 mm to 11 mm [1] to [5].
The catalyst according to any of the above.
[7] A method for producing acrolein and / or acrylic acid, which is a gas-phase catalytic oxidation of a raw material mixed gas containing propylene and an oxygen-containing gas in the presence of the catalyst according to any one of [1] to [6].
本発明の触媒によれば、該触媒が充填された反応器により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した場合、圧力損失を低
減し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。
また、コーキングが起こった触媒は酸素含有ガスを流通させることで再生（デコーキン
グ）することができる。しかし、本発明のように直胴部と空洞部を有するリング形状の触
媒を、該直胴部の長さを、該空洞部の長さより短くし、且つ、該直胴部の端部から該空洞
部の端部までが凹曲している触媒とすることにより、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、該特定組成のガス
による効率の良いデコーキングを実現することができる。
According to the catalyst of the present invention, unsaturated aldehydes such as achlorine and / or acrylic acids are not present due to vapor phase catalytic oxidation of olefins such as propylene or tertiary butanol and oxygen-containing gas by a reactor filled with the catalyst. When a saturated carboxylic acid is produced, the pressure loss can be reduced and the amount of gas can be kept high. This can reduce caulking,
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.
In addition, the catalyst in which caulking has occurred can be regenerated (decoking) by circulating an oxygen-containing gas. However, in the case of a ring-shaped catalyst having a straight body portion and a hollow portion as in the present invention, the length of the straight body portion is made shorter than the length of the hollow portion, and the straight body portion is formed from the end portion of the straight body portion. By using a catalyst in which the end of the cavity is concave, the effect of reducing pressure loss is maintained even in a caulked state as compared with a catalyst having a conventional shape, and the specific composition is maintained. Efficient decoking with the gas can be realized.
以下において、本発明について詳細に説明する。
尚、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。
Hereinafter, the present invention will be described in detail.
Molybdenum (Mo), bismuth (Bi), silicon (Si), cobalt (Co), nickel (Ni), iron (Fe), sodium (Na), potassium (K), rubidium (Rb).
), Cesium (Cs), Thallium (Tl), Boron (B), Phosphorus (P), Arsenic (As),
Each element of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce), and samarium (Sm) may be described by using the element symbol in parentheses.
本発明の触媒は直胴部と空胴部を有するリング形状の触媒であって、該直胴部の長さが
、該空胴部の長さより短く、且つ、該直胴部の端部から該空胴部の端部までが凹曲してい
る触媒である。該直胴部の長さが、該空胴部の長さより短く、且つ、該直胴部の端部から
該空胴部の端部までが凹曲していることにより、該触媒を反応器に充填し、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した場合
、圧力損失を低減し、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 catalyst of the present invention is a ring-shaped catalyst having a straight body portion and an empty body portion, the length of the straight body portion is shorter than the length of the empty body portion, and the length of the straight body portion is shorter than the length of the straight body portion. It is a catalyst in which the end of the air fuselage portion is concave. The length of the straight body portion is shorter than the length of the empty body portion, and the end portion of the straight body portion to the end portion of the empty body portion is concave, so that the catalyst is used as a reactor. When an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid is produced by vapor-phase catalytic oxidation of an olefin such as propylene or tertiary butanol and an oxygen-containing gas, the pressure loss is reduced. , Unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid can be produced in high yield.
前記直胴部は、前記空胴部のそれぞれの端部を含む面間にあることが好ましい。前記記
載の構造の触媒とすることにより、該触媒を反応器に充填し、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した場合、圧力損失を
低減し、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 straight body portion is preferably located between the surfaces including the respective ends of the empty body portion. By using a catalyst having the above-mentioned structure, the catalyst is filled in a reactor, and an unsaturated aldehyde such as acrolein and / or acrylic acid is formed by vapor-phase catalytic oxidation of an olefin such as propylene or tertiary butanol and an oxygen-containing gas. When unsaturated carboxylic acids such as acrolein are produced, pressure loss can be reduced and unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid can be produced in high yield.
本発明の触媒は、直胴部の長さが空胴部の長さより短く、且つ、該直胴部の端部から該
空胴部のの端部までが凹曲している触媒である（図１参照）。図１の左図が該直胴部の端
部から該空胴部の端部までが凹曲している触媒である。尚、図１の右図が該直胴部からの
凹曲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がその場合
であっても、本発明では該底面部が空胴部の端部であり、本発明の触媒に相当する。本発
明の触媒は触媒粒子体積に対する触媒粒子表面積が大きく、反応活性点が多いことより、
図１の左図のように底面部がない触媒が好ましい。
The catalyst of the present invention is a catalyst in which the length of the straight body portion is shorter than the length of the empty body portion, and the length from the end portion of the straight body portion to the end portion of the empty body portion is concave ( (See FIG. 1). The left figure of FIG. 1 shows a catalyst in which the end of the straight body portion to the end of the empty body portion are concave. In the right figure of FIG. 1, the concave curved surface from the straight body portion does not reach the empty body portion and remains at the bottom surface portion in the ring shape, but even in that case, the bottom surface portion is formed in the present invention. It is the end of the air fuselage and corresponds to the catalyst of the present invention. The catalyst of the present invention has a large surface area of catalyst particles with respect to the volume of catalyst particles and has many reaction active points.
A catalyst having no bottom surface as shown on the left side of FIG. 1 is preferable.
前記直胴部の端部と前記空胴部の端部との長さ（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した場合、圧力損失を低減し、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。
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
いるときの長さのことである。
A surface connecting the end of the straight body and the end of the air body with respect to the length (mm) of the end of the straight body and the end of the air body and the concave surface (hereinafter, the concave surface). The ratio of the maximum distance (mm) to the "concave curved surface" (sometimes referred to as "concave curved surface") (hereinafter sometimes referred to as "concave degree") is 0.01 or more and 0.
.. It is preferably 2 or less, more preferably 0.02 or more and 0.15 or less, and further preferably 0.05 or more and 0.1 or less. When it is within the above range, the reactor is filled with the catalyst, and unsaturated aldehydes such as acrolein and / or acrylic acid are not present due to vapor-phase catalytic oxidation of olefins such as propylene or tertiary butanol and oxygen-containing gas. When a saturated carboxylic acid is produced, the pressure loss can be reduced and an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid can be produced in a high yield.
As is clear from FIG. 2, 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 that of the end of the straight body and the empty body. It is the length when the surface connecting the ends and the concave curved surface are farthest apart.
前記直胴部の端部から前記空胴部の端部まで凹曲しているのが両端部であることが好ま
しい。両端部であることにより、触媒粒子の流動性が良好となり、ロート等を使用して反
応器へ触媒を充填する際に、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、更に反応器に充填後、
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
製造する場合、圧力損失を低減することができ、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。
It is preferable that both ends are concave from the end of the straight body to the end of the empty body. By having both ends, the fluidity of the catalyst particles is improved, and when the reactor is filled with the catalyst using a funnel or the like, bridging of the catalyst is suppressed in the funnel, and the catalyst is uniformly distributed in the reaction tube. By filling, the filling time can be shortened, and after filling the reactor,
When an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid is produced by vapor-phase catalytic oxidation of an olefin such as propylene or tertiary butanol and an oxygen-containing gas, pressure loss can be reduced. It is possible to produce unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid in 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°
〜８５°が好ましく、５５°〜８０°がより好ましく、６５°〜７５°が更に好ましい。
該角度を前記範囲とすることにより、触媒を反応器に充填後、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場合、圧力損失を
効率よく低減することができ、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 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 45 °.
~ 85 ° is preferable, 55 ° to 80 ° is more preferable, and 65 ° to 75 ° is further preferable.
By setting the angle within the above range, after filling the reactor with a catalyst, unsaturated aldehydes such as acrolein and / or acrylic acid can be produced by vapor-phase catalytic oxidation of olefins such as propylene or tertiary butanol and oxygen-containing gas. When producing an unsaturated carboxylic acid, the pressure loss can be efficiently reduced, and an unsaturated aldehyde such as acrolein and / or an unsaturated carboxylic acid such as acrylic acid can be produced in a 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.
本発明の触媒は、内径ｂ（ｍｍ）に対する外径ａ（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場合、圧力損失を低減す
ることがで、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。
In the catalyst of the present invention, the ratio (a / b) of the outer diameter a (mm) to the inner diameter b (mm) is 2.3 or more, and the ratio (H / b) of the straight body length H (mm) to the inner diameter b (mm). It is preferable that b) is 1.3 or more, the straight body length H (mm) is 2 mm to 11 mm, and the outer diameter a (mm) is 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 / or unsaturated by vapor-phase catalytic oxidation of the olefin or tertiary butanol and the oxygen-containing gas. When producing a carboxylic acid, reducing the pressure loss makes it possible to produce the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid in high yield.
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、多管式反応器への充填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。
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。
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 3.5 is preferable from the viewpoint of catalyst strength.
The 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 in filling the multi-tube reactor.
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が好
ましい。前記範囲内であることにより、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を気相で接触酸化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場合、圧力損失を低減することができ、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可能となる。
Further, the ratio (a / H) of the outer diameter a (mm) to the straight body length H (mm) is preferably 1.47 or more, more preferably 1.50 or more, and more preferably 1.53 or more. Is more preferable, and 1.56 or more is particularly preferable. The upper limit is not particularly limited, but 2.5 is preferable. Within the above range, pressure loss is reduced when an olefin such as propylene or tertiary butanol and an oxygen-containing gas are catalytically oxidized in a gas phase to produce a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid. It is possible to produce the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid in high yield.
本発明の触媒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）で表される触媒が好ましく適用できる。
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。）
The catalyst of the present invention is a catalyst used in producing the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by subjecting an olefin such as propylene or tertiary butanol to a vapor phase catalytic oxidation reaction, and contains at least molybdenum and bismuth. It is preferably a catalyst containing.
Any catalyst containing these two components can be applied to the catalyst of the present invention, and among them, the catalyst represented by the following general formula (1) is preferably applicable.
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. )
本発明の触媒は例えば次のように製造される。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所要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 of the present invention is produced, for example, as follows. A mixed solution containing a catalyst component or an aqueous slurry thereof is produced by appropriately dissolving or dispersing a required amount of a raw material compound containing each element component of the catalyst in an aqueous medium according to the composition to be produced. .. 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好まし
くは充分に攪拌、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するが、該乾燥は種々の方法で実施できる。例えば、通常の噴霧
乾燥機、スラリードライヤー、ドラムドライヤー等が挙げられ、特に噴霧乾燥機による乾
燥が好ましい。
The mixed solution or aqueous slurry containing the above catalyst components is preferably 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, which can be carried out by various methods. For example, a normal spray dryer, a slurry dryer, a drum dryer and the like can be mentioned, and drying with a spray dryer is particularly preferable.
上記乾燥により得られる粉体は、次いでリング形状に成形される。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、好ましくは打錠成形、押出成形等が挙げられ
る。特に、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
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。
The powder obtained by the above drying is then formed into a ring shape. The method for forming the ring shape is not necessarily limited, but preferably, tableting molding, extrusion molding and the like can be mentioned. 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 concaveness. 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 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 mechanical strength improving material for the catalyst. The amount of these fibers used is usually 1 to 30 parts by weight with respect to 100 parts by weight of the powder.
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.
（実施例１）
＜触媒の調製＞
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。
(Example 1)
<Catalyst preparation>
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 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 prepare a fumed silica suspension, and then adding the fumed silica suspension. It was dispersed for 30 minutes with a homogenizer ULTRA-TURRAX T115KT (manufactured by IKA) 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 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 product. 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℃で焼成を２時間
行ってリング形状の触媒を得た。触媒の形状は、図１左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であり、両端面共に
、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、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。触媒の片端部は、直胴部の端部から空胴部の端部までが直線状であり
、他方の片端部は直胴部の端部から空胴部の端部までが凹曲しており、直胴部の端部と空
胴部の端部との長さは１．５９ｍｍ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０．０９ｍｍであった。直胴部の端部と空胴部の端部との長さに対
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。
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 prepare "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 molded product was calcined at 515 ° C. for 2 hours in an air atmosphere to obtain a ring-shaped catalyst. As shown on the left side of FIG. 1, the shape of the catalyst has no bottom surface, an outer diameter: 5 mm, an inner diameter: 2 mm, a straight body length: 3 mm, and an empty body length: 4 mm. , The angle formed by the line connecting the end of the straight body and the end of the empty body, that is, the extension line drawn along the straight body, and the end of the straight body and the end of the empty body. The angle formed by the line connecting the parts was 72 °. One end of the catalyst is linear from the end of the straight body to the end of the empty body, and the other end is concave from the end of the straight body to the end of the empty body. The length between the end of the straight body and the end of the air body is 1.59 mm, and the maximum distance between the flat surface connecting the end of the straight body and the end of the air body and the concave curved surface. Was 0.09 mm. The ratio of the length between the end of the straight body and the end of the air body to 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 is 0.06. there were. Tables 1 and 2 summarize the catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, and the like.
＜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、前記触媒を９００
ｍｍ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ＳＵＳ
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 is 900.
A SUS with an inner diameter of 6 mm, which is filled to a height of mm and attached to the upper part of the acrylic resin straight pipe.
Dry air was circulated from the manufactured pipe at room temperature at a flow rate of 50 NL / min, and the differential pressure was measured with a 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 a straight pipe made of acrylic resin to form an empty cylinder, 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７０ｋＰａ
にて、流通し、該触媒との接触時間６．０秒で通過させて、プロピレンの酸化反応を実施
した。尚、該反応管はナイター浴で加熱しており、浴温は３２０℃、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。
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％）
<Vapor-phase contact oxidation reaction of propylene>
40 ml of the catalyst and 52 ml of mullite balls having a diameter of 5 mm were mixed to prepare a mixture.
A reaction tube with a stainless steel night game jacket having an inner diameter of 15 mm was filled. 70 kPa 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.
The catalyst was allowed to pass through the catalyst with a contact time of 6.0 seconds to carry out an oxidation reaction of propylene. The reaction tube was heated in a night game bath, and the bath temperatures were 320 ° C. and 330 ° C. The reaction product was analyzed by collecting the reaction product from the outlet of the reaction tube and using gas chromatography by a conventional method.
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%)
（実施例２）
製造したリング形状の触媒粒子は、図１左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。該触媒粒子それぞれ
は、両端部の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、直胴部の端
部と空胴部の端部との長さは１．５９ｍｍ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０．１０ｍｍであった。直胴部の端部と空胴部の端部との長
さに対する、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０．０
６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。
(Example 2)
As shown on the left side of FIG. 1, the produced ring-shaped catalyst particles have no bottom surface and have an outer diameter of 5 mm.
The inner diameter was 2 mm, the length of the straight body was 3 mm, and the length of the empty body was 4 mm. Each of the catalyst particles has a concave shape from the end of the straight body portion at both ends to the end portion of the empty body portion, and is the length between the end portion of the straight body portion and the end portion of the empty body portion. Was 1.59 mm, and the maximum distance between the flat surface connecting the end of the straight body and the end of the empty body and the concave curved surface was 0.10 mm. The ratio of the ratio of the length between the end of the straight body to the end of the air body to 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 is 0.0.
It was 6. Tables 1 and 2 summarize the catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, and the like.
（比較例１）
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と同様にして触媒を得た。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。
(Comparative Example 1)
Outer diameter: 5 mm, inner diameter: 2 mm, straight body length: 3 mm, empty body length: 3 mm, the straight body length and the empty body length are the same, and from the end of the straight body to the empty body A catalyst was obtained in the same manner as in Example 1 except that it was flat to the end. Tables 1 and 2 summarize the catalyst composition, pressure loss, gas phase contact oxidation reaction results of propylene, and the like.
本発明の触媒は実施例１において示されているように、該触媒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場合、圧力損失を低く抑
え、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。
尚、実施例１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）。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。
As shown in Example 1, when acrolein and / or acrylic acid is produced from propylene by a reactor filled with the catalyst, the catalyst of the present invention keeps the pressure loss low and the conversion rate of propylene. Acrolein and / or acrylic acid could be produced with high selectivity and, as a result, acrolein and / or acrylic acid could be produced with high yield.
The pressure loss in Example 1 is shown to be superior to the prior art by a measurement in which the packed layer length of the catalyst is 900 mm and dry air is simply circulated at a gas flow rate of 50 NL / min. The pressure loss is generally proportional to the square of the packed layer length of the catalyst and the gas flow rate as shown in the following Ergun equation. A fixed bed tube reactor is used in the industrial production of unsaturated aldehydes such as acrolein and / or unsaturated carboxylic acids such as acrylic acid, and the fixed bed tube reactor is usually 2000 mm to 7000 mm. It has thousands to tens of thousands of reactor tubes (Japanese Patent Laid-Open No. 2011-225476). 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 from the prior art of the present invention is 2.2 from the results shown in Examples.
It is clear that the superiority of the present invention will increase as the scale increases in the industrial scale.
（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:
Void ratio, Re p: Reynolds number)
１ 内径
２ 外径
３ 直胴部長さ
４ 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
５ 直胴部の端部と空胴部の端部との長さ
６ 直胴部の端部と空胴部の端部を結ぶ面と凹曲部との最大距離
７ 空胴部の長さ
Ａ 直胴部
Ｂ 空胴部
Ｃ 空胴部の端部
1 Inner diameter 2
Claims (7)
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、直胴部と空胴部を有するリン
グ形状の触媒であって、
該直胴部の長さが該空胴部の長さより短く、且つ、該直胴部の端部から該空胴部の端部
までが凹曲している触媒。 A ring-shaped catalyst having a straight body and an empty body, 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 unsaturated carboxylic acid.
A catalyst in which the length of the straight body portion is shorter than the length of the empty body portion, and the end portion of the straight body portion to the end portion of the empty body portion is concave.
前記空胴部の端部を結ぶ面と該凹曲した面との最大距離（ｍｍ）との比が０．０１以上０
．２以下である請求項１又は２に記載の触媒。 The surface connecting the end of the straight body and the end of the air body and the concave surface with respect to the length (mm) of the end of the straight body and the end of the air body. The ratio to the maximum distance (mm) is 0.01 or more and 0
.. 2. The catalyst according to claim 1 or 2, which is 2 or less.
至３のいずれか１項に記載の触媒。 The catalyst according to any one of claims 1 to 3, wherein both ends are concave from the end of the straight body to the end of the empty body.
〜８５°である請求項１乃至４のいずれか１項に記載の触媒。 The angle between the straight body and the line connecting the end of the straight body and the end of the empty body is 45 °.
The catalyst according to any one of claims 1 to 4, wherein the temperature is ~ 85 °.
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２
ｍｍ〜１１ｍｍ、且つ外径ａ（ｍｍ）が２ｍｍ〜１１ｍｍである請求項１乃至５のいずれ
か１項に記載の触媒。 The ratio (a / b) of the outer diameter a (mm) to the inner diameter b (mm) is 2.3 or more, and the inner diameter b (mm).
The ratio (H / b) of the straight body length H (mm) to the straight body length H (mm) is 1.3 or more, and the straight body length H (mm) is 2.
The catalyst according to any one of claims 1 to 5, wherein the catalyst has an outer diameter of 2 mm to 11 mm and an outer diameter of a (mm) of 2 mm to 11 mm.
む原料混合ガス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。 A method for producing acrolein and / or acrylic acid, which is a gas-phase catalytic oxidation of a raw material mixed gas containing propylene and an oxygen-containing gas in the presence of the catalyst according to any one of claims 1 to 6.
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| CN201880021054.2A CN110461468B (en) | 2017-03-27 | 2018-03-26 | Catalyst and catalyst group |
| CA3058093A CA3058093A1 (en) | 2017-03-27 | 2018-03-26 | Catalyst and catalyst group |
| PCT/JP2018/012233 WO2018181226A1 (en) | 2017-03-27 | 2018-03-26 | Catalyst and catalyst group |
| RU2019130056A RU2735682C1 (en) | 2017-03-27 | 2018-03-26 | Catalyst and catalyst group |
| EP18776404.8A EP3603805B1 (en) | 2017-03-27 | 2018-03-26 | Catalyst and catalyst group |
| TW107110521A TWI680801B (en) | 2017-03-27 | 2018-03-27 | Catalyst and Catalyst Group |
| US16/580,327 US11628425B2 (en) | 2017-03-27 | 2019-09-24 | Catalyst and catalyst group |
| ZA2019/06363A ZA201906363B (en) | 2017-03-27 | 2019-09-26 | Catalyst and catalyst group |
| US18/174,695 US20230219070A1 (en) | 2017-03-27 | 2023-02-27 | Catalyst and catalyst group |
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| JPH06145093A (en) * | 1992-11-11 | 1994-05-24 | Mitsui Toatsu Chem Inc | Production of methacrolein |
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