JPH044048A - Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid - Google Patents
Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acidInfo
- Publication number
- JPH044048A JPH044048A JP2101747A JP10174790A JPH044048A JP H044048 A JPH044048 A JP H044048A JP 2101747 A JP2101747 A JP 2101747A JP 10174790 A JP10174790 A JP 10174790A JP H044048 A JPH044048 A JP H044048A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- catalyst
- added
- selectivity
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000002253 acid Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 5
- 239000002002 slurry Substances 0.000 claims abstract description 34
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 15
- 229920002472 Starch Polymers 0.000 claims abstract description 14
- 239000008107 starch Substances 0.000 claims abstract description 14
- 235000019698 starch Nutrition 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 239000011733 molybdenum Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 30
- 229920000609 methyl cellulose Polymers 0.000 claims description 14
- 239000001923 methylcellulose Substances 0.000 claims description 14
- 235000010981 methylcellulose Nutrition 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001622 bismuth compounds Chemical class 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000005078 molybdenum compound Substances 0.000 claims description 3
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052716 thallium Chemical group 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical group [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Chemical group 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 31
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract description 30
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 26
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 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 18
- 239000007788 liquid Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 9
- 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 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 nitrogen-containing organic compounds Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、不飽和アルデヒド及び不飽和酸合成用触媒、
すなわちプロピレン、イソブチレン又は三級ブタノール
を分子状酸素により気相接触酸化して、アクロレイン及
びアクリル酸又はメタクロレイン及びメタクリル酸を合
成する際に使用する触媒の製造法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a catalyst for the synthesis of unsaturated aldehydes and unsaturated acids,
That is, the present invention relates to a method for producing a catalyst used when synthesizing acrolein and acrylic acid or methacrolein and methacrylic acid by subjecting propylene, isobutylene, or tertiary butanol to gas phase catalytic oxidation with molecular oxygen.
〔従来の技術]
従来、不飽和アルデヒド及び不飽和酸合成用触媒の製造
のために多数の方法が提案されている。イソブチレン又
は三級ブタノールを原料とした場合を例にとると、イソ
ブチレン又は三級ブタノールを高温気相下で接触酸化し
てメタクロレイン及びメタクリル酸を製造する際に用い
られる触媒に関して、例えば特開昭6028824号公
報、特開昭63−122642号公報等数多くの提案が
なされている。また、特開昭58−98143号公報に
はアニリン、メチルアミン、ホルムアミド等の含窒素有
機化合物の添加により触媒の成形性が改善される等の報
告があるが、一般に触媒活性、メタクロレイン及びメタ
クリル酸の選択性及び触媒寿命等の触媒性能の点で工業
的見地から更に改良が望まれている。[Prior Art] Many methods have been proposed for producing catalysts for the synthesis of unsaturated aldehydes and unsaturated acids. Taking the case where isobutylene or tertiary butanol is used as a raw material, for example, Japanese Patent Application Laid-Open No. Many proposals have been made, such as JP-A No. 6028824 and JP-A-63-122642. Furthermore, although there is a report in JP-A-58-98143 that the formability of the catalyst is improved by the addition of nitrogen-containing organic compounds such as aniline, methylamine, and formamide, it is generally Further improvements are desired from an industrial standpoint in terms of catalyst performance such as acid selectivity and catalyst life.
[発明が解決しようとする課題]
本発明は、プロピレン、イソブチレン又は三級ブタノー
ルからアクロレイン及びアクリル酸又はメタクロレイン
及びメタクリル酸を有利に合成するための触媒の新規な
製造法の提供を目的としている。[Problems to be Solved by the Invention] The present invention aims to provide a novel method for producing a catalyst for advantageously synthesizing acrolein and acrylic acid or methacrolein and methacrylic acid from propylene, isobutylene, or tertiary butanol. .
[課題を解決するための手段]
本発明は、モリブデン化合物及びビスマス化合物を混合
した混合溶液又は水性スラリーを乾燥後、前段焼成し、
得られた前段焼成物を成形又は担体に担持し、得られた
成形体又は相持体を後段焼成することにより触媒を得る
製造法において、前段焼成又は後段焼成の少なくともい
ずれかの焼成段階で、分子状酸素を0〜30容量%含有
するガス雰囲気下で250〜600℃の範囲の温度で1
〜10時間熱処理し、そして、前段焼成物100重量部
に対して、でんぷん、ポリメチルメタクリレート、硝酸
アンモニウム及び/又はメチルセルロースを0.5〜l
O重量部(好ましくは1〜5重量部)添加混合後、成形
又は担体に担持することを特徴とする不飽和アルデヒド
及び不飽和酸合成用触媒の製造法である。[Means for Solving the Problems] The present invention comprises drying a mixed solution or aqueous slurry in which a molybdenum compound and a bismuth compound are mixed, and then performing pre-baking,
In a production method in which a catalyst is obtained by molding or supporting the obtained pre-calcined product on a carrier and post-calcining the obtained molded body or carrier, in at least one of the pre-calcination and post-calcination steps, molecular 1 at a temperature in the range of 250 to 600°C in a gas atmosphere containing 0 to 30% by volume of oxygen.
Heat treated for ~10 hours, and added 0.5~l of starch, polymethyl methacrylate, ammonium nitrate, and/or methyl cellulose to 100 parts by weight of the pre-fired product.
This is a method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated acids, which comprises adding and mixing O (preferably 1 to 5 parts by weight) and then molding or supporting on a carrier.
本発明方法により得られる触媒は、一般式%式%
(式中Aはニッケル及び/又はコバルト、Xはナトリウ
ム、カリウム、ルビジウム、セシウム及び/又はタリウ
ム、Yはマグネシウム、亜鉛、マンガン、鉛及び/又は
錫、Zはリン、ホウ素、アンチモン、珪素、イオウ、チ
タン、テルル及び/又はタングステンを示し、a、b。The catalyst obtained by the method of the present invention has the general formula % (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or thallium, Y is magnesium, zinc, manganese, lead and/or or tin, Z represents phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or tungsten, a, b.
C,d、e、f、g及びhは各元素の原子比を表わし、
a=12のときb=o、旧〜3、c=0.5〜4、d=
1〜12、e=0.01〜2、f=0〜10、g=Q〜
10であり、hは前記各成分の原子価を満足するのに必
要な酸素原子数である)で表わされる組成を有すること
が好ましい。C, d, e, f, g and h represent the atomic ratio of each element,
When a=12, b=o, old~3, c=0.5~4, d=
1~12, e=0.01~2, f=0~10, g=Q~
10, and h is the number of oxygen atoms necessary to satisfy the valences of each component.
本発明方法によると、触媒寿命が長く、かつ目的生成物
を高収率で得られる触媒が再現性よく製造できる。According to the method of the present invention, it is possible to produce a catalyst with good reproducibility that has a long catalyst life and provides a high yield of the desired product.
本発明において、触媒成分である元素の原料としては、
特に限定されるものではないが、通常は酸化物又は強熱
することにより酸化物になり得る塩化物、硫酸塩、硝酸
塩、炭酸塩、アンモニウム塩又はそれらの混合物が用い
られる。In the present invention, raw materials for elements that are catalyst components include:
Although not particularly limited, oxides or chlorides, sulfates, nitrates, carbonates, ammonium salts, or mixtures thereof, which can be converted into oxides by ignition, are usually used.
本発明では、前段焼成又は後段焼成のいずれかの焼成段
階で、分子状酸素を0〜30容量%含有するガス雰囲気
下で250〜600℃で1〜10時間熱処理するが、そ
の際、前段焼成及び後段焼成の両方又はいずれか一方の
焼成を450℃以上で行うことが好ましい。前段焼成及
び後段焼成を450℃未満で行うと、反応に有効な触媒
が得られない場合がある。In the present invention, heat treatment is performed at 250 to 600°C for 1 to 10 hours in a gas atmosphere containing 0 to 30% by volume of molecular oxygen in either the first firing or the second firing. It is preferable that both or one of the firing and the post-stage firing be performed at 450° C. or higher. If the first stage firing and the second stage firing are performed at a temperature lower than 450°C, an effective catalyst for the reaction may not be obtained.
本発明において、前段焼成により得られた焼成物を成形
する方法としては、とくに限定されるものではないが、
通常は公知の成形法例えば、打錠機、押出成形機、転勤
造粒機等による成形法が挙げられる。この際、前段焼成
物100重量部に対して、グラファイト 0.5〜5重
量部を添加混合し、得られた混合物を成形することによ
り成形性を向上させることができる。In the present invention, the method for shaping the fired product obtained by the pre-stage firing is not particularly limited, but
Generally known molding methods include, for example, molding methods using a tablet press, an extrusion molding machine, a transfer granulator, and the like. At this time, moldability can be improved by adding and mixing 0.5 to 5 parts by weight of graphite to 100 parts by weight of the pre-fired product and molding the resulting mixture.
本発明においては、前段焼成物100重量部に対して、
でんぷん、ポリメチルメタクリレート、硝酸アンモニウ
ム及び/又はメチルセルロースを0.5〜IO重量部(
好ましくは1〜5重量部)添加混合後、成形又は担体に
担持する。この際、でんぷん、ポリメチルメタクリレー
ト、硝酸アンモニウム及び/又はメチルセルロースの添
加量が前段焼成物100重量部に対して0.5重量部未
満の場合は、添加効果が発現されない。一方、10重量
部を超える場合には、後段焼成時に焼成が生じやすくな
り、でんぷん、ポリメチルメタクリレート、硝酸アンモ
ニウム及び/又はメチルセルロースが揮散により消失す
るため、触媒の有する機械的強度が弱くなり、その結果
、工業用触媒として使用することができな(なる。In the present invention, based on 100 parts by weight of the pre-fired product,
0.5 to IO parts by weight of starch, polymethyl methacrylate, ammonium nitrate and/or methylcellulose (
After addition and mixing (preferably 1 to 5 parts by weight), it is molded or supported on a carrier. At this time, if the amount of starch, polymethyl methacrylate, ammonium nitrate and/or methyl cellulose added is less than 0.5 part by weight based on 100 parts by weight of the pre-fired product, no effect of the addition will be exhibited. On the other hand, if the amount exceeds 10 parts by weight, calcination tends to occur during the subsequent calcination, and starch, polymethyl methacrylate, ammonium nitrate and/or methylcellulose are lost by volatilization, resulting in a weakening of the mechanical strength of the catalyst. , cannot be used as an industrial catalyst.
本発明方法により得られた触媒を用いて、プロピレン、
イソブチレン又は三級ブタノールを分子状酸素により気
相接触酸化して、アクロレイン及びアクリル酸又はメタ
クロレイン及びメタクリル酸を製造するに際しては、プ
ロピレン、イソブチレン又は三級ブタノール対酸素のモ
ル比は1:0.5〜3が好ましい。原料のプロピレン、
イソブチレン又は三級ブタノールは不活性ガスで希釈し
て用いることが好ましい。酸化に用いられる分子状酸素
は純酸素ガスでも空気でもよいが、工業的には空気が有
利である。Using the catalyst obtained by the method of the present invention, propylene,
When producing acrolein and acrylic acid or methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen, the molar ratio of propylene, isobutylene or tertiary butanol to oxygen is 1:0. 5 to 3 is preferred. raw material propylene,
It is preferable to use isobutylene or tertiary butanol after diluting it with an inert gas. The molecular oxygen used for oxidation may be pure oxygen gas or air, but air is industrially advantageous.
反応圧力は常圧ないし散気圧まで用いられる。The reaction pressure used is normal pressure to diffused pressure.
反応温度は200〜450℃の範囲が好ましく、反応は
流動床でも固定床でも実施できる。The reaction temperature is preferably in the range of 200 to 450°C, and the reaction can be carried out in either a fluidized bed or a fixed bed.
[発明の効果1
本発明方法により製造した触媒を用いることにより、プ
ロピレン、イソブチレン又は三級ブタノールからアクロ
レイン及びアクリル酸又はメタクロレイン及びメタクリ
ル酸を有利に得ることができる。[Effect of the Invention 1] By using the catalyst produced by the method of the present invention, acrolein and acrylic acid or methacrolein and methacrylic acid can be advantageously obtained from propylene, isobutylene or tertiary butanol.
[実施例]
下記実施例及び比較例中の部は重量部を意味し、分析は
ガスクロマトグラフィにより行った。また、反応用原料
としてのプロピレン、インブチレン又は三級ブタノール
の反応率、生成される不飽和アルデヒド及び不飽和酸の
選択率は下記のように定義される。[Example] In the following Examples and Comparative Examples, parts mean parts by weight, and the analysis was performed by gas chromatography. Further, the reaction rate of propylene, inbutylene or tertiary butanol as a reaction raw material, and the selectivity of the unsaturated aldehyde and unsaturated acid produced are defined as follows.
仕込原料の反応率(%)
不飽和アルデヒドの選択率(%)
不飽和酸の選択率c%)
実施例1
純水1000部にパラモリブデン酸アンモニウム500
部及び硝酸タリウム25.1部を加え加熱撹拌した(A
液)。別に純水100部に濃硝酸30部を加えた後、硝
酸ビスマス114.5部を溶解した。これに硝酸第二鉄
286.0部、硝酸ニッケル274、5部、硝酸コバル
ト274.7部及び純水1200部を順次加え、完全に
溶解するまでよく撹拌した(B液)。A液にB液を加え
スラリー状とした後、三酸化アンチモン34.4部を加
え加熱撹拌した。Reaction rate of raw materials (%) Selectivity of unsaturated aldehyde (%) Selectivity of unsaturated acid c%) Example 1 500 parts of ammonium paramolybdate in 1000 parts of pure water
1 part and 25.1 parts of thallium nitrate were added and heated and stirred (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 114.5 parts of bismuth nitrate was dissolved. To this were sequentially added 286.0 parts of ferric nitrate, 274.5 parts of nickel nitrate, 274.7 parts of cobalt nitrate, and 1200 parts of pure water, and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.
得られたスラリー状物質を130℃で乾燥させた後、空
気雰囲気下300℃で2時間前段焼成した。The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、でんぷん2部及びグラファイト2部を添加混合し、
純水を加えスラリーにした後、乾燥、粉砕し、ペレット
状に成形した。前記の成形体を空気雰囲気下500℃で
3時間後段焼成した。こうして製造された触媒の組成は
次式で表わされる。After pulverizing this pre-fired product, 2 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product,
After adding pure water to make a slurry, it was dried, crushed, and formed into pellets. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
Mo+Ji+FezNi4Con TI2 o4sb+
oh酸素の原子比率りは他の元素の原子価により自然に
決まる値であるので以下省略する。Mo+Ji+FezNi4Con TI2 o4sb+
Since the atomic ratio of oh oxygen is a value naturally determined by the valences of other elements, it will be omitted below.
この触媒をステンレス製反応管に充填し、インブチレン
5%、酸素12%、水蒸気lO%及び窒素73%(容量
%)の原料混合ガスを接触時間3.6秒で触媒層を通過
させ、360℃で反応させた。その結果、イソブチレン
の反応率90.5%、メタクロレインの選択率86.2
%、メタクリル酸の選択率3.3%であった。This catalyst was packed in a stainless steel reaction tube, and a raw material mixed gas containing 5% inbutylene, 12% oxygen, 10% water vapor, and 73% nitrogen (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds. The reaction was carried out at ℃. As a result, the reaction rate of isobutylene was 90.5%, and the selectivity of methacrolein was 86.2%.
%, and the selectivity for methacrylic acid was 3.3%.
比較例1
実施例1で前段焼成物へのでんぷんの添加を除いた他は
、実施例1と同様にして同じ組成の触媒を製造した。こ
の触媒を用い、実施例1と同様な反応条件で反応を行っ
たところ、インブチレンの反応率90.0%、メタクロ
レインの選択率84.7%、メタクリル酸の選択率3.
2%であった。Comparative Example 1 A catalyst having the same composition as in Example 1 was produced in the same manner as in Example 1, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of inbutylene was 90.0%, the selectivity of methacrolein was 84.7%, and the selectivity of methacrylic acid was 3.0%.
It was 2%.
実施例2
純水1000部にパラモリブデン酸アンモニウム500
部、硝酸セシウム13.8部及び硝酸カリウム 7.2
部を加え加熱撹拌した(A液) 別に純水100部に濃
硝酸30部を加えた後、硝酸ビスマス57.2部を溶解
した。これに硝酸第二鉄286、0部、硝酸ニッケル2
74.5部、硝酸コバルト206.0部、硝酸マグネシ
ウム60.5部、85%リンM2.2部及び純水120
0部を順次加え、完全に溶解するまでよく撹拌した(B
液)。A液にB液を加えスラリー状とした後、三酸化ア
ンチモン34.4部を加え加熱攪拌した。Example 2 500 parts of ammonium paramolybdate in 1000 parts of pure water
parts, cesium nitrate 13.8 parts and potassium nitrate 7.2 parts
(Liquid A) Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved therein. To this, 286,0 parts of ferric nitrate, 2 parts of nickel nitrate
74.5 parts, cobalt nitrate 206.0 parts, magnesium nitrate 60.5 parts, 85% phosphorus M2.2 parts, and pure water 120 parts
0 parts were added one after another and stirred well until completely dissolved (B
liquid). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.
得られたスラリー状物質を130℃で乾燥させた後、酸
素5%及び窒素95%(容量%)から成るガス雰囲気下
300℃で2時間前段焼成した。The resulting slurry material was dried at 130°C, and then pre-calcined for 2 hours at 300°C in a gas atmosphere consisting of 5% oxygen and 95% nitrogen (volume %).
この前段焼成物を粉砕した後、前段焼成物100部に対
し、ポリメチルメタクリレート1.5部及びグラファイ
ト2部を添加混合し、純水を加えスラリーにした後、乾
燥、粉砕し、ベレ・ソト状に成形した。前記の成形体を
空気雰囲気下500℃で3時間後段焼成した。こうして
製造された触媒の組成は次式で表わされる。After pulverizing this pre-fired product, 1.5 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried, pulverized, and It was formed into a shape. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
Mo+ 28IO,5Fe3N14cOJo、 3C3
O,aMg+Po、 oasbこの触媒を用いて、実施
例1と同様な反応条件で反応を行ったところ、インブチ
レンの反応率91.0%、メタクロレインの選択率86
.9%、メタクリル酸の選択率5.5%であった。Mo+ 28IO, 5Fe3N14cOJo, 3C3
O, aMg+Po, oasb When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of inbutylene was 91.0% and the selectivity of methacrolein was 86.
.. The selectivity for methacrylic acid was 5.5%.
比較例2
実施例2で前段焼成物へのポリメチルメタクリレートの
添加を除いた他は、実施例2と同様にして同じ組成の触
媒を製造した。この触媒を用い、実施例1と同様な反応
条件で反応を行ったところ、イソブチレンの反応率90
.2%、メタクロレインの選択率86.5%、メタクリ
ル酸の選択率5.5%であった。Comparative Example 2 A catalyst having the same composition as in Example 2 was produced in the same manner as in Example 2, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 90.
.. The selectivity for methacrolein was 86.5%, and the selectivity for methacrylic acid was 5.5%.
実施例3
実施例2の触媒を用い、また原料として三級ブタノール
を用いた他は実施例1と同様な反応条件で反応を行った
ところ、三級ブタノールの反IT4100%、メタクロ
レインの選択率80.2%、メタクリル酸の選択率4.
5%であった。Example 3 A reaction was carried out under the same reaction conditions as in Example 1, except that the catalyst of Example 2 was used and tertiary butanol was used as a raw material. 80.2%, selectivity for methacrylic acid4.
It was 5%.
比較例3
比較例2の触媒を用い、また原料として三級ブタノール
を用いた他は実施例1と同様な反応条件で反応を行った
ところ、三級ブタノールの反応率100%、メタクロレ
インの選択率79.5%、メタクリル酸の選択率4.2
%であった。Comparative Example 3 A reaction was carried out under the same reaction conditions as in Example 1, except that the catalyst of Comparative Example 2 was used and tertiary butanol was used as a raw material. The reaction rate of tertiary butanol was 100%, and methacrolein was selected. rate 79.5%, selectivity of methacrylic acid 4.2
%Met.
実施例4
純水1000部にパラモリブデン酸アンモニウム500
部、パラタングステン酸アンモニウム18.5部、硝酸
セシウム13.8部及び硝酸ルビジウム7.0部を加え
加熱撹拌した(A液)。別に純水100部に濃硝酸30
部を加えた後、硝酸ビスマス114.5部を溶解した。Example 4 500 parts of ammonium paramolybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate, 13.8 parts of cesium nitrate, and 7.0 parts of rubidium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid in 100 parts of pure water
114.5 parts of bismuth nitrate were dissolved.
これに硝酸第二鉄286.0部、硝酸コバルト480.
7部、硝酸亜鉛70.2部及び純水1200部を順次加
え、完全に溶解するまでよく撹拌した(B液)。A液に
B液を加えスラリー状とした後、三酸化アンチモン34
.4部を加え加熱撹拌した。To this, 286.0 parts of ferric nitrate and 480 parts of cobalt nitrate.
7 parts of zinc nitrate, 70.2 parts of zinc nitrate, and 1200 parts of pure water were sequentially added and stirred well until completely dissolved (solution B). After adding liquid B to liquid A to make a slurry, antimony trioxide 34
.. 4 parts were added and the mixture was heated and stirred.
得られたスラリー状物質を130℃で乾燥させた後、酸
素10%及び窒素90%(容量%)から成るガス雰囲気
下300℃で2時間前段焼成した。The resulting slurry material was dried at 130° C., and then pre-calcined at 300° C. for 2 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %).
この前段焼成物を粉砕した後、前段焼成物100部に対
し、メチルセルロース3部及びグラファイト2部を添加
混合し、純水を加えスラリーにした後、乾燥、粉砕し、
リング状に成形した。After pulverizing this pre-fired product, 3 parts of methylcellulose and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried and pulverized.
It was formed into a ring shape.
前記成形体を空気雰囲気下500℃で3時間後段焼成し
た。こうして製造された触媒の組成は次式で表わされる
。The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
MOtJz+FezCoyRbo、 *C8a、 xZ
n+sb+Wo、 sこの触媒を用いて、実施例1と同
様な反応条件で反応を行ったところ、イソブチレンの反
応率96.0%、メタクロレインの選択率87.7%、
メタクリル酸の選択率4.9%であった。MOtJz+FezCoyRbo, *C8a, xZ
n+sb+Wo, s Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 1, and the reaction rate of isobutylene was 96.0%, the selectivity of methacrolein was 87.7%,
The selectivity of methacrylic acid was 4.9%.
比較例4
実施例4で前段焼成物へのメチルセルロースの添加を除
いた他は、実施例4と同様にして同じ組成の触媒を製造
した。この触媒を用い、実施例1と同様な反応条件で反
応を行ったところ、イソブチレンの反応率95.2%、
メタクロレインの選択率87.2%、メタクリル酸の選
択率4.8%であった。Comparative Example 4 A catalyst having the same composition as in Example 4 was produced in the same manner as in Example 4, except that methyl cellulose was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 95.2%,
The selectivity for methacrolein was 87.2% and the selectivity for methacrylic acid was 4.8%.
実施例5
実施例4の触媒を用いて原料として三級ブタノールを用
いた他は実施例1と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率86.9%、メタクリル酸の選択率3.1%で
あった。Example 5 A reaction was carried out using the catalyst of Example 4 under the same reaction conditions as in Example 1 except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 86.9% and 3.1%.
比較例5
比較例4の触媒を用いて原料として三級ブタノールを用
いた他は実施例1と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率85.7%、メタクリル酸の選択率2.8%で
あった。Comparative Example 5 A reaction was carried out using the catalyst of Comparative Example 4 under the same reaction conditions as in Example 1 except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein was The selectivity for methacrylic acid was 85.7% and 2.8%.
実施例6
純水1000部にパラモリブデン酸アンモニウム 50
0部、パラタングステン酸アンモニウム18、5部及び
硝酸セシウム18.4部を加え加熱撹拌した(A液)。Example 6 50 ammonium paramolybdate in 1000 parts of pure water
0 parts, 18.5 parts of ammonium paratungstate, and 18.4 parts of cesium nitrate were added and stirred with heating (Liquid A).
別に純水100部に濃硝酸30部を加えた後、硝酸ビス
マス114.5部を溶解した。これに硝酸第二鉄190
.7部、硝酸コバルト528、7部、硝酸マンガン6.
8部、10%シリカゾル141.8部及び純水1000
部を順次加え、完全に溶解するまでよく攪拌した(B液
)。A液にB液を加えスラリー状とした後、三酸化アン
チモン34.4部を加え加熱撹拌した。Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 114.5 parts of bismuth nitrate was dissolved. Add this to ferric nitrate 190
.. 7 parts, cobalt nitrate 528, 7 parts, manganese nitrate 6.
8 parts, 141.8 parts of 10% silica sol and 1000 parts of pure water
were added one by one and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.
得られたスラリー状物質を130’Cで乾燥させた後、
空気雰囲気下500℃で2時間前段焼成した。After drying the obtained slurry material at 130'C,
Preliminary firing was performed at 500° C. for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、でんぷん2.5部及びグラファイト2部を添加混合
し、純水を加えスラリーにした後、乾燥、粉砕しペレッ
ト状に成形した。After pulverizing the pre-fired product, 2.5 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to form a slurry, and the slurry was dried, crushed, and formed into pellets.
前記の成形体を空気雰囲気下400℃で5時間後段焼成
した。こうして製造された触媒の組成は次式で表わされ
る。The molded body was post-baked at 400° C. for 5 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
MO+Ji+Fe2C0y、 ycso、 nMna、
+Sb+Sl+Wo3この触媒をステンレス製反応管
に充填し、イソブチレン5%、酸素12%、水蒸気lO
%及び窒素73%(容量%)の原料混合ガスを接触時間
3.6秒で触媒層を通過させ、350℃で反応させた。MO+Ji+Fe2C0y, ycso, nMna,
+Sb+Sl+Wo3 This catalyst was packed into a stainless steel reaction tube and mixed with 5% isobutylene, 12% oxygen, and 10% water vapor.
% and nitrogen at 73% (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 350°C.
その結果、イソブチレンの反応率95.1%、メタクロ
レインの選択率87.1%、メタクリル酸の選択率4.
1%であった。As a result, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 87.1%, and the selectivity of methacrylic acid was 4.
It was 1%.
比較例6
実施例6で前段焼成物へのでんぷんの添加を除いた他は
、実施例6と同様にして同じ組成の触媒を製造した。こ
の触媒を用い、実施例6と同様な反応条件で反応を行っ
たところ、イソブチレンの反応率93.2%、メタクロ
レインの選択率87.6%、メタクリル酸の選択率4.
0%であった。Comparative Example 6 A catalyst having the same composition as in Example 6 was produced in the same manner as in Example 6, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 6, the reaction rate for isobutylene was 93.2%, the selectivity for methacrolein was 87.6%, and the selectivity for methacrylic acid was 4.
It was 0%.
実施例7
実施例6の触媒を用いて原料として三級ブタノールを用
いた他は実施例6と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率84.6%、メタクリル酸の選択率30%であ
った。Example 7 A reaction was carried out using the catalyst of Example 6 under the same reaction conditions as in Example 6, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 84.6% and 30%.
比較例7
比較例6の触媒を用いて原料として三級ブタノールを用
いた他は実施例6と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率84.0%、メタクリル酸の選択率2.5%で
あった。Comparative Example 7 A reaction was carried out using the catalyst of Comparative Example 6 under the same reaction conditions as in Example 6, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 84.0% and 2.5%.
実施例8
純水1000部にバラモリブデン酸アンモニウム500
部、パラタングステン酸アンモニウム6.2部及び硝酸
セシウム23.0部を加え加熱攪拌した(A液)。別に
純水100部に濃硝酸30部を加え、均一にした後、硝
酸ビスマス57.2部を加え溶解した。これに硝酸第二
鉄238.4部、硝酸コバルト549.3部及び純水1
200部を順次加え、完全に溶解するまでよく攪拌した
(B液)。A液にB液を加えスラリー状とした後、二酸
化アンチモン34.4部及びホウ# 4.4部を加え加
熱撹拌した。Example 8 500 parts of ammonium rosemolybdate in 1000 parts of pure water
1, 6.2 parts of ammonium paratungstate and 23.0 parts of cesium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water to make it homogeneous, and then 57.2 parts of bismuth nitrate was added and dissolved. Add to this 238.4 parts of ferric nitrate, 549.3 parts of cobalt nitrate, and 1 part of pure water.
200 parts were added one after another and stirred well until completely dissolved (solution B). After adding liquid B to liquid A to form a slurry, 34.4 parts of antimony dioxide and 4.4 parts of porium # were added and stirred with heating.
得られたスラリー状物質を130℃で乾燥させた後、空
気雰囲気下300℃で2時間前段焼成した。The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、硝酸アンモニウム2部を添加混合し、純水を加えス
ラリーにした後、このスラリーを多孔質の無定形シリカ
−アルミナに担持した。After pulverizing the pre-fired product, 2 parts of ammonium nitrate was added and mixed to 100 parts of the pre-fired product, pure water was added to form a slurry, and this slurry was supported on porous amorphous silica-alumina.
前記の担持体を酸素lO%及び窒素90%(容量%)か
ら成るガス雰囲気下500℃で3時間後段焼成した。こ
うして製造された触媒の担体と酸素以外の組成は次式で
表わされる。The above-mentioned support was post-baked at 500° C. for 3 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %). The composition of the catalyst thus produced except for the carrier and oxygen is represented by the following formula.
MO+Jlo、 5Fei、 5cOscso、 5s
bJo、 +Bo、 sこの触媒を用いて、実施例1と
同様な反応条件で反応を行ったところ、イソブチレンの
反応率93.0%、メタクロレインの選択率83.9%
、メタクリル酸の選択率3.7%であった。MO+Jlo, 5Fei, 5cOscso, 5s
bJo, +Bo, s Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 1, and the reaction rate of isobutylene was 93.0% and the selectivity of methacrolein was 83.9%.
, the selectivity for methacrylic acid was 3.7%.
比較例8
実施例8で前段焼成物への硝酸アンモニウムの添加を除
いた他は、実施例8と同様にして同じ組成の触媒を製造
した。この触媒を用い、実施例1と同様な反応条件で反
応を行ったところ、イソブチレンの反応率91.6%、
メタクロレインの選択率83.8%、メタクリル酸の選
択率3.5%であった。Comparative Example 8 A catalyst having the same composition as in Example 8 was produced in the same manner as in Example 8, except that ammonium nitrate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 91.6%,
The selectivity for methacrolein was 83.8% and the selectivity for methacrylic acid was 3.5%.
実施例9
実施例8の触媒を用いて原料として二級ブタノールを用
いた他は実施例1と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率79.2%、メタクリル酸の選択率3.5%で
あった。Example 9 A reaction was carried out using the catalyst of Example 8 under the same reaction conditions as in Example 1 except that secondary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein was The selectivity for methacrylic acid was 79.2% and 3.5%.
比較例9
比較例8の触媒を用いて原料として三級ブタノールを用
いた他は実施例1と同様な反応条件で反応を行ったとこ
ろ、三級ブタノールの反応率100%、メタクロレイン
の選択率78.0%、メタクリル酸の選択率3.2%で
あった。Comparative Example 9 A reaction was carried out using the catalyst of Comparative Example 8 under the same reaction conditions as in Example 1, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 78.0% and 3.2%.
実施例10
純水1000部にパラモリブデン酸アンモニウム500
部及び硝酸セシウム18.4部を加え加熱攪拌した(A
液)。別に純水100部に濃硝酸30部を加えた後、硝
酸ビスマス91.6部及び硫酸ビスマス167部を溶解
した。これに硝酸第二鉄286.0部、硝酸コバルト4
80.7部、硝酸マグネシウム60.5部及び純水12
00部を順次加え、完全に溶解するまでよ(攪拌した(
B液)。A液にB液を加えスラリー状とした後、三酸化
アンチモン34.4部を加え加熱撹拌した。Example 10 500 parts of ammonium paramolybdate in 1000 parts of pure water
and 18.4 parts of cesium nitrate were added and stirred with heating (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 91.6 parts of bismuth nitrate and 167 parts of bismuth sulfate were dissolved. To this, 286.0 parts of ferric nitrate, 4 parts of cobalt nitrate
80.7 parts, magnesium nitrate 60.5 parts and pure water 12
Add 00 parts one by one until completely dissolved (stir).
B liquid). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.
得られたスラリー状物質を噴霧乾燥機を用いて噴霧乾燥
した後、空気雰囲気下300℃で2時間前段焼成した。The obtained slurry-like material was spray-dried using a spray dryer, and then pre-baked at 300° C. for 2 hours in an air atmosphere.
この前段焼成物100部に対し、メチルセルロース2部
及びグラファイト2部を添加混合した後ベレット状に成
形した。2 parts of methylcellulose and 2 parts of graphite were added to and mixed with 100 parts of this pre-fired product, and then formed into a pellet shape.
前記の成形体を空気雰囲気下500℃で3時間後段焼成
した。こうして製造された触媒の組成は次式で表わされ
る。The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
MO+J1+FesCOyC3o4Mg+sb+so、
zこの触媒をステンレス製反応管に充填し、イソブチ
レン5%、酸素12%、水蒸気lO%及び窒素73%(
容量%)の原料混合ガスを接触時間3.6秒で触媒層を
通過させ、 355℃で反応させた。その結果、イソブ
チレンの反応率92.1%、メタクロレインの選択率8
5.9%、メタクリル酸の選択率4.8%であった。MO+J1+FesCOyC3o4Mg+sb+so,
z This catalyst was packed into a stainless steel reaction tube and mixed with 5% isobutylene, 12% oxygen, 10% water vapor and 73% nitrogen (
% by volume) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 355°C. As a result, the reaction rate of isobutylene was 92.1%, and the selectivity of methacrolein was 8.
The selectivity for methacrylic acid was 4.8%.
比較例10
実施例1Oで前段焼成物へのメチルセルロースの添加を
除いた他は、実施例10と同様にして同じ組成の触媒を
製造した。この触媒を用い、実施例10と同様な反応条
件で反応を行ったところ、イソブチレンの反応率90.
0%、メタクロレインの選択率86.6%、メタクリル
酸の選択率4.8%であった。Comparative Example 10 A catalyst having the same composition as in Example 10 was produced in the same manner as in Example 10, except that methylcellulose was not added to the pre-calcined product in Example 1O. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 90.
The selectivity for methacrolein was 86.6%, and the selectivity for methacrylic acid was 4.8%.
実施例11
純水1000部にパラモリブデン酸アンモニウム500
部、パラタングステン酸アンモニウム18.5部及び硝
酸セシウム18.4部を加え加熱撹拌した(A液)。別
に純水100部に濃硝酸30部を加えた後、硝酸ビスマ
ス57.2部を溶解した。これに硝酸第二鉄238.4
部、硝酸コバルト274.7部、硝酸ニッケル205−
9部、硝酸亜鉛35.1部、硝酸マグネシウム30.3
部及び純水1200部を順次加え、完全に溶解するまで
よく撹拌した(B液)。A液にB液を加えスラリー状と
した後、三酸化アンチモン34.4部を加え加熱攪拌し
た。Example 11 500 parts of ammonium paramolybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate and 18.4 parts of cesium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved. In this, ferric nitrate 238.4
parts, cobalt nitrate 274.7 parts, nickel nitrate 205 parts
9 parts, zinc nitrate 35.1 parts, magnesium nitrate 30.3 parts
and 1,200 parts of pure water were sequentially added thereto and stirred well until completely dissolved (Liquid B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.
得られたスラリー状物質を130℃で乾燥させた後、空
気雰囲気下300℃で2時間前段焼成した。The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、ポリメチルメタクリレート2部及びグラファイト2
部を添加混合した後、ペレット状に成形した。After pulverizing this pre-fired product, 2 parts of polymethyl methacrylate and 2 parts of graphite are added to 100 parts of the pre-fired product.
After addition and mixing, the mixture was molded into pellets.
前記の成形体を空気雰囲気下500℃で3時間後段焼成
した。こうして製造された触媒の組成は次式で表わされ
る。The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
MO+Jlo、 5Fez、 5cOJlicsa、
nano、 sMgo、 ssb+Wa、 3この触媒
を用いて、実施例10と同様な反応条件で反応を行った
ところ、イソブチレンの反応率96.1%、メタクロレ
インの選択率86.9%、メタクリル酸の選択率4,8
%であった。MO+Jlo, 5Fez, 5cOJlicsa,
nano, sMgo, ssb+Wa, 3 Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 10, and the reaction rate of isobutylene was 96.1%, the selectivity of methacrolein was 86.9%, and the selectivity of methacrylic acid was 96.1%. Selection rate 4,8
%Met.
比較例11
実施例11で前段焼成物へのポリメチルメタクリレート
の添加を除いた他は、実施例11と同様にして同じ組成
の触媒を製造した。この触媒を用い、実施例10と同様
な反応条件で反応を行ったところ、イソブチレンの反応
率95.1%、メタクロレインの選択率86.2%、メ
タクリル酸の選択率4.8%であった。Comparative Example 11 A catalyst having the same composition as in Example 11 was produced in the same manner as in Example 11, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 86.2%, and the selectivity of methacrylic acid was 4.8%. Ta.
実施例12
純水1000部にパラモリブデン酸アンモニウム500
部及び硝酸タリウム18.9部を加え加熱撹拌した(A
液)。別に純水100部に濃硝酸30部を加えた後、硝
酸ビスマス57.2部を溶解した。これに硝酸第二鉄2
38.4部、硝酸コバルト274.7部、硝酸ニッケル
240.2部、硝酸鉛7.8部、硝酸マンガン6.8部
及び純水1200部を順次加え、完全に溶解するまでよ
く撹拌した(B液)、A液にB液を加えスラリー状とし
た後、三酸化アンチモン34.4部及びテルル# 27
.1部を加え加熱撹拌した。Example 12 500 parts of ammonium paramolybdate in 1000 parts of pure water
and 18.9 parts of thallium nitrate were added and heated and stirred (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved. In this, ferric nitrate 2
38.4 parts of cobalt nitrate, 274.7 parts of nickel nitrate, 7.8 parts of lead nitrate, 6.8 parts of manganese nitrate, and 1200 parts of pure water were added in sequence and stirred well until completely dissolved ( Solution B), after adding Solution B to Solution A to make a slurry, 34.4 parts of antimony trioxide and tellurium #27
.. 1 part was added and the mixture was heated and stirred.
得られたスラリー状物質を130℃で乾燥させた後、空
気雰囲気下300℃で2時間前段焼成した。The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、メチルセルロース1部、ポリメチルメタクリレート
145部及びグラファイト2部を添加混合し、純水を加
えた後、クローバ状に押出成形した。前記の成形体を空
気雰囲気下500℃で3時間後段焼成した。こうして製
造された触媒の組成は次式で表わされる。After pulverizing the pre-fired product, 1 part of methyl cellulose, 145 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, and after adding pure water, it was extruded into a clover shape. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
Mo+Jio、 sFe*、 5Co4Nis、 s
Tj2 o、 sMno、 +Pbo、 +Sb+Te
a、 s
この触媒を用いて、実施例10と同様な反応条件で反応
を行ったところ、イソブチレンの反応率91.7%、メ
タクロレインの選択率87.3%、メタクリル酸の選択
率4.3%であった。Mo+Jio, sFe*, 5Co4Nis, s
Tj2 o, sMno, +Pbo, +Sb+Te
a, s When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 91.7%, the selectivity of methacrolein was 87.3%, and the selectivity of methacrylic acid was 4. It was 3%.
比較例12
実施例12で前段焼成物へのメチルセルロース及びポリ
メチルメタクリレートの添加を除いた他は、実施例12
と同様にして同じ組成の触媒を製造した。この触媒を用
い、実施例10と同様な反応条件で反応を行ったところ
、インブチレンの反応率90.5%、メタクロレインの
選択率87.1%、メタクリル酸の選択率4.1%であ
った。Comparative Example 12 Example 12 except that methyl cellulose and polymethyl methacrylate were not added to the pre-fired product in Example 12.
A catalyst with the same composition was produced in the same manner as above. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of inbutylene was 90.5%, the selectivity of methacrolein was 87.1%, and the selectivity of methacrylic acid was 4.1%. there were.
比較例13
実施例12において、後段焼成の温度を300℃と変え
た他は、実施例12と同様にして同じ組成の触媒を製造
した。この触媒を用い、実施例10と同様な反応条件で
反応を行ったところ、イソブチレンの反応率93.0%
、メタクロレインの選択率84,8%、メタクリル酸の
選択率3.0%であった。Comparative Example 13 A catalyst having the same composition as in Example 12 was produced in the same manner as in Example 12, except that the temperature of the post-stage calcination was changed to 300°C. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 93.0%.
The selectivity for methacrolein was 84.8%, and the selectivity for methacrylic acid was 3.0%.
実施例13
純水1000部にバラモリブデン酸アンモニウム500
部及び硝酸ルビジウム13,9部を加え加熱撹拌した(
A液)。別に純水100部に濃硝酸30部を加えた後、
硝酸ビスマス57.2部を溶解した。これに硝酸第二鉄
238.4部、硝酸コバルト274、7部、硝酸ニッケ
ル240.2部及び純水1200部を順次加え、完全に
溶解するまでよく撹拌した(B液)。A液にB液を加え
スラリー状とした後、酸化スズ15.9部、二酸化チタ
ン9.4部及び二酸化アンチモン34.4部を加え加熱
撹拌した。Example 13 500 parts of ammonium rosemolybdate in 1000 parts of pure water
and 13.9 parts of rubidium nitrate were added and stirred with heating (
A liquid). Separately, after adding 30 parts of concentrated nitric acid to 100 parts of pure water,
57.2 parts of bismuth nitrate was dissolved. To this were sequentially added 238.4 parts of ferric nitrate, 274.7 parts of cobalt nitrate, 240.2 parts of nickel nitrate, and 1200 parts of pure water, and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 15.9 parts of tin oxide, 9.4 parts of titanium dioxide, and 34.4 parts of antimony dioxide were added and stirred with heating.
得られたスラリー状物質を130℃で乾燥させた後、空
気雰囲気下300℃で2時間前段焼成した。The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.
この前段焼成物を粉砕した後、前段焼成物100部に対
し、でんぷん3部及びグラファイト2部を添加混合し、
純水を加えた後、棒状に押出成形した。After pulverizing this pre-fired product, 3 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product,
After adding pure water, it was extruded into a rod shape.
前記の成形体を酸素5%及び窒素95%(容量%)から
成るガス雰囲気下500℃で2時間、更に空気雰囲気下
問温度で2時間後段焼成した。The molded body was fired at 500° C. for 2 hours in a gas atmosphere consisting of 5% oxygen and 95% nitrogen (volume %), and then for 2 hours at room temperature in an air atmosphere.
こうして製造された触媒の組成は次式で表わされる。The composition of the catalyst thus produced is expressed by the following formula.
MO+Jlo、Fex、 acOJla、 5Rbo4
sb+Tla、 5sno、 sこの触媒をステンレス
製反応管に充填し、イソブチレン5%、酸素12%、水
蒸気lO%及び窒素73%(容量%)の原料混合ガスを
接触時間3.6秒で触媒層を通過させ、 365℃で反
応させた。その結果、インブチレンの反応率92,3%
、タクロレインの選択率87.1%、メタクリル酸の選
択率5.5%であった。MO+Jlo, Fex, acOJla, 5Rbo4
sb+Tla, 5sno, s This catalyst was packed into a stainless steel reaction tube, and a raw material mixed gas of 5% isobutylene, 12% oxygen, 10% steam, and 73% nitrogen (volume %) was applied to the catalyst layer for a contact time of 3.6 seconds. The mixture was allowed to pass through and reacted at 365°C. As a result, the reaction rate of inbutylene was 92.3%.
, the selectivity for tacrolein was 87.1%, and the selectivity for methacrylic acid was 5.5%.
比較例14
実施例13で前段焼成物へのでんぷんの添加を除いた他
は、実施例13と同様にして同じ組成の触媒を製造した
。この触媒を用い、実施例13と同様な反応条件で反応
を行ったところ、イソブチレンの反応率91,3%、メ
タクロレインの選択率86.8%、メタクリル酸の選択
率5.3%であった。Comparative Example 14 A catalyst having the same composition as in Example 13 was produced in the same manner as in Example 13, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 13, the reaction rate for isobutylene was 91.3%, the selectivity for methacrolein was 86.8%, and the selectivity for methacrylic acid was 5.3%. Ta.
実施例14
実施例2に準じて触媒を製造した。得られたスラリー状
物質を130℃で乾燥させた後、酸素5%及び窒素95
%(容量%)から成るガス雰囲気下300℃で2時間前
段焼成した。Example 14 A catalyst was produced according to Example 2. After drying the resulting slurry at 130°C, 5% oxygen and 95% nitrogen
The pre-stage firing was carried out at 300° C. for 2 hours under a gas atmosphere consisting of % (volume %).
この前段焼成物を粉砕した後、前段焼成物100部に対
し、ポリメチルメタクリレート 1.5部及びグラファ
イト2部を添加混合し、純水を加えスラリーにした後、
乾燥、粉砕しペレット状に成形した。前記の成形体を空
気雰囲気下500℃で3時間後段焼成した。こうして製
造された触媒の組成は次式で表わされる。After pulverizing this pre-fired product, 1.5 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, and pure water was added to make a slurry.
It was dried, crushed and formed into pellets. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
M(1+Jlo、 +1Feo、 9CO3,yNao
、 l512この触媒を用いて、プロピレン5%、酸素
12%、水蒸気lO%及び窒素73%(容量%)の原料
混合ガスを接触時間3.6秒で触媒層を通過させ、31
0℃で反応させた。その結果、プロピレンの反応率98
.5%、アクロレインの選択率89.4%、アクリル酸
の選択率5.0%であった。M(1+Jlo, +1Feo, 9CO3,yNao
, 1512 Using this catalyst, a raw material mixed gas of 5% propylene, 12% oxygen, 10% water vapor and 73% nitrogen (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds, and 31
The reaction was carried out at 0°C. As a result, the reaction rate of propylene was 98
.. The selectivity for acrolein was 89.4%, and the selectivity for acrylic acid was 5.0%.
比較例15
実施例14で前段焼成物へのポリメチルメタクリレート
の添加を除いた他は、実施例14と同様にして同じ組成
の触媒を製造した。この触媒を用い、実施例14と同様
な反応条件で反応を行ったところ、プロピレンの反応率
98,0%、アクロレインの選択率89.0%、アクリ
ル酸の選択率48%であった。Comparative Example 15 A catalyst having the same composition as in Example 14 was produced in the same manner as in Example 14, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 14, the reaction rate of propylene was 98.0%, the selectivity of acrolein was 89.0%, and the selectivity of acrylic acid was 48%.
実施例15
実施例4に準じて触媒を製造した。得られたスラリー状
物質を 130℃で乾燥させた後、酸素lO%及び窒素
90%(容量%)から成るガス雰囲気下300℃で2時
間前段焼成した。Example 15 A catalyst was produced according to Example 4. The obtained slurry-like material was dried at 130° C., and then pre-calcined at 300° C. for 2 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %).
この前段焼成物を粉砕した後、前段焼成物100部に対
し、メチルセルロース3部及びグラファイト2部を添加
混合し、純水を加えスラリーにした後、乾燥、粉砕し、
リング状に成形した。After pulverizing this pre-fired product, 3 parts of methylcellulose and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried and pulverized.
It was formed into a ring shape.
前記の成形体を空気雰囲気下500℃で3時間後段焼成
した。こうして製造された触媒の組成は次式で表わされ
る。The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.
Mo+ zBl+4Fer、 zcOsKo、 l51
2110. にの触媒を用い、実施例14と同様な反応
条件で反応を行ったところ、プロピレンの反応率98.
8%、アクロレインの選択率88.3%、アクリル酸の
選択率6.3%であった。Mo+ zBl+4Fer, zcOsKo, l51
2110. When the reaction was carried out under the same reaction conditions as in Example 14 using the following catalyst, the conversion rate of propylene was 98.
The selectivity for acrolein was 88.3%, and the selectivity for acrylic acid was 6.3%.
比較例16
実施例15で前段焼成物へのメチルセルロースの添加を
除いた他は、実施例15と同様にして同じ組成の触媒を
製造した。この触媒を用い、実施例14と同様な反応条
件で反応を行ったところ、プロピレンの反応率98.3
%、アクロレインの選択率87.5%、アクリル酸の選
択率6.2%であった。Comparative Example 16 A catalyst having the same composition as in Example 15 was produced in the same manner as in Example 15, except that methylcellulose was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 14, the conversion rate of propylene was 98.3.
%, acrolein selectivity was 87.5%, and acrylic acid selectivity was 6.2%.
Claims (1)
含有する混合溶液又は水性スラリーを乾燥後、前段焼成
し、得られた前段焼成物を成形又は担体に担持し、得ら
れた成形体又は担持体を後段焼成することにより、モリ
ブデン及びビスマスを含む多成分系の不飽和アルデヒド
及び不飽和酸合成用触媒を得る製造法において、前段焼
成又は後段焼成の少なくともいずれかの焼成段階で、分
子状酸素を 0〜30容量%含有するガス雰囲気下で250〜600
℃の範囲の温度で1〜10時間熱処理し、そして前段焼
成物100重量部に対して、でんぷん、ポリメチルメタ
クリレート、硝酸アンモニウム及び/又はメチルセルロ
ースを0.5〜10重量部添加混合後、成形又は担体に
担持することを特徴とする不飽和アルデヒド及び不飽和
酸合成用触媒の製造法。 2、触媒の組成が一般式、 MoaBibFecAdXeYfZgOh (式中Aはニッケル及び/又はコバルト、Xはナトリウ
ム、カリウム、ルビジウム、セシウム及び/又はタリウ
ム、Yはマグネシウ ム、亜鉛、マンガン、鉛及び/又は錫、Zはリン、ホウ
素、アンチモン、珪素、イオウ、チタン、テルル及び/
又はタングステンを示し、a、b、c、d、e、f、g
及びhは各元素の原子比を表わし、a=12のときをb
=0.01〜3、c=0.5〜4、d=1〜12、e=
0.01〜2、f=0〜10、g=0〜10であり、h
は前記各成分の原子価を満足するのに必要な酸素原子数
である)で表わされることを特徴とする第1請求項記載
の方法。 3、モリブデン化合物及びビスマス化合物を成分として
含有する混合溶液又は水性スラリーを乾燥後、前段焼成
し、得られた前段焼成物100重量部に対して、でんぷ
ん、ポリメチルメタクリレート、硝酸アンモニウム及び
/又はメチルセルロースを0.5〜10重量部添加混合
後、成形又は担体に担持し、得られた成形体又は担持体
を後段焼成し、そして前段焼成又は後段焼成の少なくと
もいずれかの焼成段階で、分子状酸素を0〜30容量%
含有するガス雰囲気下で250〜600℃の範囲の温度
で1〜10時間熱処理することにより得られる一般式 MoaBibFecAdXeYfZgOh (式中Aはニッケル及び/又はコバルト、Xはナトリウ
ム、カリウム、ルビジウム、セシウム及び/又はタリウ
ム、Yはマグネシウ ム、亜鉛、マンガン、鉛及び/又は錫、Zはリン、ホウ
素、アンチモン、珪素、イオウ、チタン、テルル及び/
又はタングステンを示し、a、b、c、d、e、f、g
及びhは各元素の原子比を表わし、a=12のときb=
0.01〜3、c=0.5〜4、d=1〜12、e=0
.01〜2、f=0〜10、g=0〜10であり、hは
前記各成分の原子価を満足するのに必要な酸素原子数で
ある)で表わされる触媒を用い、プロピレン、イソブチ
レン又は三級ブタノールを分子状酸素により気相接触酸
化することを特徴とする不飽和アルデヒド及び不飽和酸
の合成法。[Scope of Claims] 1. After drying a mixed solution or aqueous slurry containing a molybdenum compound and a bismuth compound as components, pre-baking is carried out, and the obtained pre-baked product is molded or supported on a carrier, and the obtained molded body is obtained. Alternatively, in a production method for obtaining a multi-component unsaturated aldehyde and unsaturated acid synthesis catalyst containing molybdenum and bismuth by post-calcining the support, in at least one of the pre-calcination and post-calcination, molecular 250 to 600 in a gas atmosphere containing 0 to 30% by volume of oxygen.
℃ for 1 to 10 hours, and 0.5 to 10 parts by weight of starch, polymethyl methacrylate, ammonium nitrate, and/or methyl cellulose are added and mixed to 100 parts by weight of the pre-baked product, and then molded or formed into a carrier. A method for producing a catalyst for the synthesis of unsaturated aldehydes and unsaturated acids, characterized in that the catalyst is supported on an unsaturated aldehyde and an unsaturated acid. 2. The composition of the catalyst is the general formula, MoaBibFecAdXeYfZgOh (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or thallium, Y is magnesium, zinc, manganese, lead and/or tin, Z is phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or
or tungsten, a, b, c, d, e, f, g
and h represent the atomic ratio of each element, and when a=12, b
=0.01~3, c=0.5~4, d=1~12, e=
0.01-2, f=0-10, g=0-10, h
2. The method according to claim 1, wherein: is the number of oxygen atoms necessary to satisfy the valence of each component. 3. After drying the mixed solution or aqueous slurry containing a molybdenum compound and a bismuth compound as components, perform pre-baking, and add starch, polymethyl methacrylate, ammonium nitrate and/or methyl cellulose to 100 parts by weight of the obtained pre-baked product. After adding and mixing 0.5 to 10 parts by weight, it is molded or supported on a carrier, and the obtained molded body or carrier is later fired, and in at least one of the first firing and the second firing, molecular oxygen is added. 0-30% by volume
General formula MoaBibFecAdXeYfZgOh (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or or thallium, Y is magnesium, zinc, manganese, lead and/or tin, Z is phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or
or tungsten, a, b, c, d, e, f, g
and h represent the atomic ratio of each element, and when a=12, b=
0.01-3, c=0.5-4, d=1-12, e=0
.. 01 to 2, f = 0 to 10, g = 0 to 10, and h is the number of oxygen atoms necessary to satisfy the valence of each component). A method for synthesizing unsaturated aldehydes and unsaturated acids, characterized by gas phase catalytic oxidation of tertiary butanol with molecular oxygen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2101747A JPH044048A (en) | 1990-04-19 | 1990-04-19 | Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2101747A JPH044048A (en) | 1990-04-19 | 1990-04-19 | Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH044048A true JPH044048A (en) | 1992-01-08 |
Family
ID=14308839
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2101747A Pending JPH044048A (en) | 1990-04-19 | 1990-04-19 | Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid |
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JP (1) | JPH044048A (en) |
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JP2002239386A (en) * | 2001-02-20 | 2002-08-27 | Mitsubishi Rayon Co Ltd | Reaction tube, method for manufacturing catalyst, method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
WO2003057366A1 (en) * | 2001-12-28 | 2003-07-17 | Mitsubishi Rayon Co., Ltd. | Method for preparing catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid, catalyst prepared by the method, and method for synthesis of unsaturated aldehyde and unsaturated carboxylic acid using the catalyst |
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-
1990
- 1990-04-19 JP JP2101747A patent/JPH044048A/en active Pending
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WO2002066160A1 (en) * | 2001-02-20 | 2002-08-29 | Mitsubishi Rayon Co., Ltd. | Reaction tube, process for producing catalyst and process for producing unsaturated aldehyde and unsaturated carboxylic acid |
JP2002239386A (en) * | 2001-02-20 | 2002-08-27 | Mitsubishi Rayon Co Ltd | Reaction tube, method for manufacturing catalyst, method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
US6919478B2 (en) | 2001-02-20 | 2005-07-19 | Mitsubishi Rayon Co., Ltd. | Reaction tube, process for producing catalyst and process for producing unsaturated aldehyde and unsaturated carboxylic acid |
US7387982B2 (en) | 2001-12-28 | 2008-06-17 | Mitsubishi Rayon Co., Ltd. | Method of producing catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and catalyst prepared by this method |
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