WO2017047710A1 - 共役ジオレフィン製造用触媒と、その製造方法 - Google Patents
共役ジオレフィン製造用触媒と、その製造方法 Download PDFInfo
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- WO2017047710A1 WO2017047710A1 PCT/JP2016/077314 JP2016077314W WO2017047710A1 WO 2017047710 A1 WO2017047710 A1 WO 2017047710A1 JP 2016077314 W JP2016077314 W JP 2016077314W WO 2017047710 A1 WO2017047710 A1 WO 2017047710A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- producing
- weight
- reaction
- conjugated diolefin
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 224
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 150000001993 dienes Chemical class 0.000 title claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 238000000465 moulding Methods 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 12
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 7
- 239000003365 glass fiber Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 31
- 239000000835 fiber Substances 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 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
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 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 Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 77
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- 238000000034 method Methods 0.000 description 50
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 36
- 238000011156 evaluation Methods 0.000 description 27
- 239000000126 substance Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
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- 238000012360 testing method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
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- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000001913 cellulose Substances 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- -1 inorganic acid salt Chemical class 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 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
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 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
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- 229910001571 halide mineral Inorganic materials 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
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- 239000005078 molybdenum compound Substances 0.000 description 1
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- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/22—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of chromium, molybdenum or tungsten
- C08F4/24—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Definitions
- the present invention relates to a catalyst for producing a conjugated diolefin by a catalytic oxidative dehydrogenation reaction from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen, and a method for producing the same.
- butadiene which is a raw material for synthetic rubber, etc.
- the coke-like substances from the target product and / or reaction by-products are deposited or deposited on the catalyst surface, inert substances, in the reaction tube and in the post-process equipment, thereby inhibiting the flow of the reaction gas in the industrial plant.
- Patent Document 1 discloses the correlation between the rate of change in outer diameter of the catalyst and the change in strength before and after the reaction.
- tableting which is a method for forming a catalyst of Patent Document 1
- the catalyst active component is compacted so as to be densely aggregated, and a coke-like substance is generated by a side reaction inside the catalyst and And / or retention tends to occur as compared with catalysts formed by other molding methods, coke heat is likely to be accumulated inside the catalyst, yield loss and reaction runaway occur, and production of the catalyst itself
- Patent Document 2 discloses the correlation between the crushing rate in the packed catalyst and the amount of coke-like substance generation, but there is no disclosure about a catalyst or reaction conditions for suppressing the crushing rate in a long-term reaction.
- Patent Documents 3 to 9 all relate to a catalyst or a method for producing the same, wherein an organic assistant or / and an inorganic assistant having specific particle size distribution, fiber length, acid strength etc. is added.
- the evaluation method of corresponds to the powdering rate by filling and the above-mentioned evaluation of the degree of wear and tear, and the effect on the improvement of the hardness is unknown. That is, in molding catalysts, particularly supported molding catalysts, the knowledge on types and addition amounts of auxiliary agents that improve hardness among mechanical strengths is not described in Patent Document 3 to Patent Document 9 and was not known to those skilled in the art. .
- Non-Patent Document 1 control of the pore structure can be mentioned as in Non-Patent Document 1 as a method of improving the hardness other than the addition of the inorganic auxiliary.
- the failure of the catalyst is considered to be due to the stress inside the catalyst in the long-term reaction or regeneration treatment, and it can be inferred that the stress becomes high around the pores and leads to failure. That is, although it is preferable to reduce the pores in order to suppress the breakage of the catalyst, Non-Patent Document 1 is not known because there is no description for improving the hardness without adding the organic assistant at all in the support molding catalyst.
- butadiene which is the target product
- Low butadiene yield means relatively high yield of by-products, but in this case a higher performance purification system is needed to obtain pure butadiene as the final product in industrial plant
- their equipment costs will be high.
- auxiliaries to improve hardness causes undesirable side reactions. That is, there has been a demand for development of a catalyst in which the amount of butadiene produced and the amount of by-product produced are not increased and the damage to the catalyst due to long-term reaction is suppressed.
- the present invention provides a catalyst capable of improving the long-term stability of the reaction and improving the hardness in a reaction for producing a conjugated diolefin by catalytic oxidation dehydrogenation from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen. It aims at providing the manufacturing method.
- the present inventor is able to improve the hardness without reducing the yield of the conjugated diolefin which is the target product by adding a glass fiber inorganic auxiliary. It has been found that damage to the catalyst due to a long-term reaction can be significantly suppressed and the above problems can be solved, and the present invention has been completed.
- a high-hardness catalyst can be obtained which can be used in a reaction for producing a conjugated diolefin by catalytic oxidation dehydrogenation from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen, and a long period of time Since damage to the catalyst is suppressed in the reaction, a catalyst having long-term stability and a method for producing the same can be provided.
- It can be used in a reaction for producing conjugated diolefins by a catalytic oxidative dehydrogenation reaction from a mixed gas containing monoolefin of 4 or more carbon atoms and molecular oxygen, preferably catalytic oxidation from a mixed gas containing n-butene and molecular oxygen, It is a catalyst which can be used for the reaction which manufactures butadiene by dehydrogenation reaction, and its manufacturing method, and a catalyst for manufacturing conjugated diolefin of the present invention which adds glass fiber-like mineral auxiliary, and shapes it hereafter, and its manufacturing method are explained.
- n-butene refers to 1-butene, trans-2-butene, cis-2-butene, isobutylene, a single component gas, or a mixed gas containing at least one component, Butadiene is more strictly meant 1,3-butadiene.
- the glass fiber inorganic auxiliary agent used in the catalyst of the present invention is mainly by treating any naturally occurring and / or artificial inorganic substance which does not burn away even at a heat treatment of 600 ° C., at a glass transition temperature or higher. Any fibrous or rod-like auxiliary agent to be prepared, all of which are not burnt out by the main firing step described later. Since the glass fiber inorganic auxiliary agent remains even in the main firing step described later, it has a role of connecting the composite metal oxides (pre-fired powders) to each other, and the breakage is caused even when the load for breakage is generated in the catalyst. A suppressing effect is produced.
- Mohs hardness is not particularly limited as a material of the glass fiber inorganic auxiliary agent in the present invention, for example, any of sulfide minerals, oxide minerals, halide minerals, inorganic acid salt minerals, organic minerals, etc. alone or in combination is glass transition Among those heat-treated above the temperature, those having a Mohs hardness of 2 or more (the glass of the present invention) are preferable, and inorganic acid salt minerals are more preferable as raw materials of these materials, and silicate minerals are most preferable. A strand is mentioned. Moreover, it becomes suitable at the point which becomes inactive to a catalytic reaction by implementing an acid treatment, an alkali treatment, a silane treatment, etc. individually or in combination with respect to a glass fiber inorganic auxiliary agent.
- the average fiber length of the glass fiber inorganic auxiliary agent preferably satisfies the condition represented by the following formula (A), more preferably the condition represented by the following formula (B), and the following formula (C) It is most preferable that the condition represented by) is satisfied.
- Glass fiber inorganic auxiliary agents are readily available, for example, from Central Glass Co., Ltd., Nitto Boseki Co., Ltd.
- the average particle diameter of the glass fiber inorganic auxiliary is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m.
- the average fiber length of the glass fiber inorganic auxiliary agent is preferably 10 ⁇ m to 4000 ⁇ m, and more preferably 50 ⁇ m to 500 ⁇ m.
- the average particle diameter of the composite metal oxide or the organic auxiliary agent is calculated, for example, by the following method.
- the apparatus is not particularly limited. For example, using LMS-2000e manufactured by Nishiyama Works, purified water is used as a dispersion medium to introduce various samples into the cell, and the scattered light intensity is measured to be about 4.0 to 6.0.
- the average particle size is calculated from the particle size distribution obtained by mass percentage.
- the average particle diameter of the composite metal oxide is preferably 1 ⁇ m to 500 ⁇ m, and more preferably 10 ⁇ m to 100 ⁇ m.
- the composite metal oxide in the present invention preferably satisfies the following composition formula (D).
- Mo 12 Bi a Fe b Co c Ni d X e Y f Z g (Wherein, X represents at least one element of an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium, and Y represents at least one element of an alkaline earth metal selected from magnesium, calcium, strontium, and barium)
- Z represents at least one element selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, antimony, tungsten, lead, zinc, cerium, thallium, and a, b, c, d, e and f represents an atomic ratio of bismuth, iron, cobalt, nickel, X, Y cerium and Z to molybdenum 12, respectively, and 0.3 ⁇ a ⁇ 3.5, 0.6 ⁇ b ⁇ 3.4, 5 ⁇
- the raw material of each metal element for obtaining the catalyst of the present invention is not particularly limited, but a nitrate containing at least one metal element, a nitrite, a sulfate, an ammonium salt, an organic acid salt, an acetate, a carbonate, Secondary carbonates, chlorides, inorganic acids, salts of inorganic acids, heteropoly acids, salts of heteropoly acids, hydroxides, oxides, metals, alloys, etc., or mixtures thereof can be used.
- nitrate materials preferred are preferred.
- Step (A1) Preparation and drying A mixed solution or slurry of the raw material of the catalytic active component is prepared, and after passing through steps such as precipitation method, gelation method, coprecipitation method, hydrothermal synthesis method, dry spray method, evaporation to dryness
- the dry powder of the present invention is obtained using a known drying method such as a method, drum drying method, lyophilization method and the like.
- the mixed solution or slurry may be any of water, an organic solvent, or a mixed solution thereof as a solvent, and the raw material concentration of the active component of the catalyst is not limited, and further, the temperature of the mixed solution or slurry, atmosphere, etc.
- the most preferable in the present invention is to form a mixed solution or slurry of the raw material of the active component of the catalyst under conditions of 20 ° C. to 90 ° C., introduce it into a spray dryer and the dryer outlet temperature is 70 ° C. C., the temperature of the hot air inlet, the pressure inside the spray dryer, and the flow rate of the slurry are adjusted so that the average particle size of the obtained dry powder is 10 .mu.m to 700 .mu.m.
- Step (A2) Pre-baking
- the dry powder thus obtained is pre-baked at 200 ° C. to 600 ° C. to obtain the composite metal oxide (pre-baked powder) of the present invention having an average particle diameter of 10 ⁇ m to 100 ⁇ m.
- the composite metal oxide may be referred to as a prefired powder.
- the method of firing is also not particularly limited, such as fluidized bed, rotary kiln, muffle furnace, tunnel calcining furnace, final catalyst performance, machine The appropriate range should be selected in consideration of the target strength, moldability, production efficiency, etc.
- the method most preferred in the present invention is a method in a tunnel firing furnace under an air atmosphere in a range of 300 ° C. or more and 600 ° C. or less for 1 hour to 12 hours. Further, before or after the pre-sintering in this step, addition of glass fiber-like inorganic assistants and organic assistants described later in arbitrary amounts is also included in the method for producing a catalyst of the present invention.
- Step (A3) Molding the pre-baked powder thus obtained is molded and used.
- the shape of the molded article is not particularly limited, such as spherical shape, cylindrical shape, ring shape, etc., but it should be selected in consideration of mechanical strength, a reactor, production efficiency of preparation, etc. in a catalyst finally obtained in a series of preparation.
- the molding method is also not particularly limited, but when forming the column or ring by adding a carrier, an organic auxiliary, a glass fiber inorganic auxiliary, a binder, etc. shown below to the pre-sintered powder, When forming into a sphere using a molding machine or an extrusion molding machine, a molding machine is used to obtain a molded article.
- the method of forming by adding the above-mentioned glass fiber-like inorganic auxiliary together with the pre-baked powder is preferable, and adding the above-mentioned glass fiber-like inorganic aid together with the pre-fired powder to an inert carrier.
- the method of coating by carrier granulation and carrying molding is more preferable, and it is most preferable not to add an organic auxiliary at all when coating by roller granulation.
- the material of the carrier known materials such as alumina, silica, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof can be used, and further, the particle size, water absorption, mechanical strength, and each crystal phase There is no particular limitation on the degree of crystallinity, the mixing ratio, etc., and an appropriate range should be selected in consideration of the final catalyst performance, formability, production efficiency and the like.
- the addition amount of the glass fiber inorganic auxiliary is preferably 0.1% by weight to 25% by weight, particularly preferably 0.3% by weight to 10% by weight, with respect to the weight of the pre-fired powder, and 0.5% by weight To 5% by weight is most preferred.
- the material and composition of the glass are not particularly limited, but for example, non-alkali glass such as E glass, and glass subjected to various chemical inactivation treatments such as silane treatment are by-products of the catalytic reaction. It is more preferable in that it does not give adverse effects such as production.
- the glass fiber inorganic auxiliary may be subjected to a grinding process prior to molding, and the method of grinding is not particularly limited, but for example, a ball mill, a rod mill, a SAG mill, a jet mill, an independent grinding mill, a hammer mill , Pellet mill, disc mill, roller mill, high pressure grinding roll, VSI mill, etc. alone or in combination, and the object of this grinding may be glass fiber inorganic auxiliary alone, but it is added to pre-baked powder and other forming processes It may be a mixture of the catalyst raw materials to be used.
- the organic auxiliary is an optional powder, granular, fibrous or scaly auxiliary consisting mainly of an organic substance which is burnt away by heat treatment at 200 ° C. or more and 600 ° C. or less. Some or all of them are to be burnt out, for example, polymer or polymer beads such as polyethylene glycol and various esters, dried product of super absorbent polymer or water absorbent with arbitrary water absorption, various surfactants, flour or refined Examples include various starches such as starch, and crystalline or amorphous cellulose and its derivatives.
- the average particle size of the organic assistant in the present invention is in the range of 0.001 to 1000 with respect to the average particle size of the pre-baked powder.
- the binder in the present invention is a liquid composed of a compound group having a molecular diameter in the range of 0.001 or less with respect to the average particle diameter of the pre-baked powder, for example, There is such a thing. That is, a liquid organic solvent, a dispersion of an organic substance, a water-soluble organic solvent, and a mixture of them and water in an arbitrary ratio, and there is no particular limitation, but an aqueous solution of polyhydric alcohol such as glycerin or ion exchanged water Preferably, ion-exchanged water is the most preferable from the viewpoint of formability. Since the binder contains water or an organic substance, part or all of the binder is burnt out in the main baking step described later.
- the molecular diameter of the organic substance used for the binder is sufficiently small compared to the average particle size of the pre-baked powder, so even if the binder is used for the formation of voids in the catalyst such as the organic assistant In the present inventors' findings, no significant change in hardness was confirmed even if the type of binder was changed. Moreover, it is also possible to introduce
- the amount of the binder used is preferably 2 to 60 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the pre-fired powder. Since the reaction of the present invention is an oxidative dehydrogenation and an exothermic reaction, it is possible to suppress the formation and / or retention of coke-like substances due to the heat dissipation inside the catalyst and further by the efficient diffusion of the conjugated diolefin formed. Therefore, carrier molding is the most preferred molding method.
- Step (A4) Main Firing
- the pre-fired powder or molded product obtained in this manner is preferably fired again (main firing) at 200 ° C. or more and 600 ° C. or less before being used for the reaction.
- main firing there is no particular limitation on the firing time and the atmosphere at the time of firing, and the method of firing is also not particularly limited, such as fluidized bed, rotary kiln, muffle furnace, tunnel baking furnace, etc. Final catalyst performance, mechanical strength and An appropriate range should be selected in consideration of production efficiency etc.
- the most preferable in the present invention is firing in an air atmosphere in a tunnel firing furnace in a temperature range of 300 ° C. to 600 ° C. for 1 hour to 12 hours.
- all production steps are all steps from step (A1) to step (A4) alone or in combination, from the catalyst raw material to obtaining the catalyst of the present invention.
- the molding step is a part or all of the step (A3).
- the shape and size of the catalyst obtained by the above preparation are not particularly limited, but taking into consideration the workability of filling the reaction tube and the pressure loss in the reaction tube after filling, the shape is spherical, and the average particle size is The diameter is preferably 3.0 mm to 10.0 mm, and the loading ratio of the catalytically active component is preferably 20% by weight to 80% by weight.
- the degree of wear which is an index representing mechanical strength in the present invention, is calculated by the following method. Treat 50g of catalyst sample with 25 rpm of rotation speed and 10 minutes of processing time using a tablet friability tester manufactured by Hayashi Riken Chemical Co., Ltd. as an apparatus, and after sieving the portion worn away with a standard sieve with an aperture of 1.70 mm
- the weight of the catalyst remaining on the top is measured and calculated by the following equation.
- the lower the friability value, the better the mechanical strength, and the preferred range is, for example, 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 0.5% by weight or less.
- Abrasion (% by weight) 100 ⁇ [(weight of catalyst ⁇ weight of catalyst remaining on the screen) / weight of catalyst]
- the hardness which is an index showing mechanical strength in the present invention is calculated by the following method.
- a tensile compression tester (Technograph TG5kN manufactured by Minebea Co., Ltd.)
- a dedicated attachment is connected and one catalyst is placed, and the load speed is 2 mm / min in compression mode.
- the mechanical load is applied continuously to the catalyst, and the load is evaluated 5% or more of the maximum value, or 0.1kgf or more, or when the crack is visually confirmed in the catalyst Stop and let the maximum value of the displacement-load curve be the hardness of the catalyst. This evaluation is carried out with 30 or more catalysts, and the average value is taken as hardness.
- hardness refers to hardness by a tensile compression tester, but the hardness of the present invention in a broader sense regardless of the system, damage to the catalyst due to long-term reaction such as dry hardness or Vickers hardness.
- the hardness shall be regarded as equivalent if it is within the range of hardness evaluation where a significant correlation is found.
- an index of mechanical strength in addition to the average value of hardness of a plurality of catalysts as described above, a measure of variation in hardness of a plurality of catalysts, eg, standard deviation when assuming that hardness has a normal distribution, etc.
- the Weibull coefficient etc. assuming that the Weibull distribution is taken, and the minimum value of the hardness of a plurality of catalysts are also applicable.
- the conditions for the reaction of producing conjugated diolefins from monoolefins having 4 or more carbon atoms by the catalyst of the present invention are: 1% by volume to 20% by volume of monoolefin, 5% by volume to 20% by volume of molecular weight as source gas composition
- the reaction bath temperature is in the range of 200 ° C.
- reaction pressure is from atmospheric pressure to 10 atm, and the space velocity (GHSV) of the raw material gas with respect to the molded catalyst of the present invention is in the range of 350 hr.sup.- 1 to 7000 hr.sup.- 1 .
- GHSV space velocity
- damage to the catalyst means that the mechanical strength of the catalyst itself is lowered by causing the reaction for producing a conjugated diolefin from a monoolefin having 4 or more carbon atoms to be in the presence of the catalyst for a long period of time, Is a phenomenon in which the shape changes or degrades and breaks down (broken) from a shape of a piece to a piece or even a powder, and the cause is a damage from the inside of the catalyst by the formation of a coke-like substance and / or a combustion by regeneration treatment Damage due to expansion of heat or rapid combustion gas may be considered. Failure of the catalyst leads to problems such as broken catalyst fragments accumulating in the reactor and an increase in pressure loss, undesired reactions due to the catalyst accumulated locally in the reactor, and contamination in the downstream purification system Are concerned.
- the mechanical strength is a measurement obtained by evaluating the strength by any physical or mechanical load on one or more catalysts, such as the above-mentioned attrition and hardness, and the packing and pulverization ratio described in Patent Document 3 and the like. It is a generic term for the result.
- the coke-like substance is generated by at least one of a reaction raw material or a target product or a reaction by-product in a reaction for producing a conjugated diolefin, and details of its chemical composition and formation mechanism are unknown.
- a reaction raw material or a target product or a reaction by-product in a reaction for producing a conjugated diolefin and details of its chemical composition and formation mechanism are unknown.
- inert substances, or in the reaction tube or in the post-process equipment, especially in an industrial plant the flow of reaction gas is blocked, the reaction tube is blocked, and the reaction is shut down. It is assumed to be the causative substance that causes various problems.
- the reaction is generally stopped before the occurrence of blockage, and the regeneration treatment is carried out to burn and remove coke-like substances by raising the temperature of blockages such as reaction tubes and post process equipment. I do.
- generation mechanism of cork-like substance the following is assumed, for example.
- the catalyst of the present invention has a certain degree of wear, and even a certain hardness, at least before the start of the reaction, as described below.
- the degree of friability described later which is a physical property value indicating the degree of damage to the impact upon catalyst loading
- the method of evaluating mechanical strength There are the following issues. That is, since the mechanical load applied to the catalyst is low in the evaluation of the degree of friability, even a catalyst having a good degree of friability may be damaged due to a long-term reaction as described later.
- the tensile compression tester can suitably apply a high mechanical load to the subject of the present invention, and as described later, significantly confirms the correlation with the damage of the catalyst due to the long-term reaction.
- it is a physical property evaluation method more severe and suitable than evaluation of the degree of attrition which is evaluation of conventional mechanical strength.
- hardness evaluation as in the present invention is a physical property evaluation method showing correlation with catalyst breakage due to long-term reaction. Is also not known to those skilled in the art as described above.
- the degree of friability is determined by the types and amounts of various strength improvers and binders added at the time of molding, or a combination thereof, the atomic ratio of the catalyst composition, the phase form of each crystal phase and the ratio thereof, and the compounding process and the drying process. It is known that it is influenced by various preparation processes such as the diameter, geometrical structure and aggregation form of secondary particles of the catalytically active component to be % By weight or less is preferred. On the other hand, there is no known document specifically showing shaping catalysts such as the present invention for the knowledge for improving the hardness, and as described above, the type and amount of the organic assistant and / or the glass fibrous inorganic assistant The inventors have confirmed that this can be achieved by adjusting.
- Example 1 (Preparation of catalyst 1) Eight hundred parts by weight of ammonium heptamolybdate was completely dissolved in 3000 parts by weight of pure water heated to 80 ° C. (mother liquor 1). Next, 11 parts by weight of cesium nitrate was dissolved in 124 ml of pure water and added to the mother liquor 1. Next, 275 parts by weight of ferric nitrate, 769 parts by weight of cobalt nitrate and 110 parts by weight of nickel nitrate were dissolved in 612 ml of pure water heated to 60 ° C. and added to the mother liquor 1.
- Example 2 (Preparation of catalyst 2) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of silane-treated glass fiber (average fiber diameter: 11 ⁇ m, average) with respect to the pre-baked powder obtained in Example 1
- a catalyst was prepared under the same conditions as Catalyst 1 except that a fiber length: 100 ⁇ m) was added, to obtain a catalyst 2 of the present invention.
- the degree of wear of Catalyst 2 was 0.19% by weight, and the hardness was 3.2 kgf (31.4 N).
- Example 3 (Preparation of catalyst 3) A catalyst was prepared under the same conditions as Catalyst 1 except that 3% by weight of silane-treated glass fiber (average fiber diameter: 11 ⁇ m, average fiber length: 150 ⁇ m) was added to the pre-baked powder obtained in Example 1 Were prepared to obtain a catalyst 3 of the present invention.
- the degree of wear of Catalyst 3 was 0.42% by weight, and the hardness was 15.5 kgf (151.9 N).
- Example 4 (Preparation of catalyst 4) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of glass fibers (average fiber diameter: 11 ⁇ m, average fiber length) with respect to the pre-fired powder obtained in Example 1
- a catalyst was prepared under the same conditions as Catalyst 1 except that 30 ⁇ m was added, to obtain Catalyst 4 of the present invention.
- the degree of wear of the catalyst 4 was 0.13% by weight, and the hardness was 2.7 kgf (26.5 N).
- Example 5 (Preparation of catalyst 5) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of silane-treated glass fiber (average fiber diameter: 11 ⁇ m, average) with respect to the pre-baked powder obtained in Example 1
- a catalyst was prepared under the same conditions as Catalyst 1 except that a fiber length: 50 ⁇ m was added, to obtain a catalyst 5 of the present invention.
- the friability of the catalyst 5 was 0.56% by weight, and the hardness was 2.9 kgf (28.4 N).
- Example 6 (Preparation of catalyst 6) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of glass fibers (average fiber diameter: 11 ⁇ m, average fiber length) with respect to the pre-fired powder obtained in Example 1
- a catalyst was prepared under the same conditions as Catalyst 1 except that 3000 ⁇ m) was added to obtain Catalyst 6 of the present invention.
- the degree of wear of the catalyst 6 was 0.15% by weight, and the hardness was 2.5 kgf (24.5 N).
- Example 7 (Preparation of catalyst 7) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of glass fibers (average fiber diameter: 10 ⁇ m, average fiber length: relative to the pre-fired powder obtained in Example 1 A catalyst was prepared under the same conditions as Catalyst 1 except that 300 ⁇ m was added, to obtain Catalyst 7 of the present invention. The degree of wear of the catalyst 7 was 0.27% by weight, and the hardness was 4.1 kgf (40.2 N).
- Example 8 (Preparation of catalyst 8) 5% by weight of crystalline cellulose (average particle diameter: 89.3 ⁇ m) and 3% by weight of glass fibers (average fiber diameter: 10 ⁇ m, average fiber length: relative to the pre-fired powder obtained in Example 1 A catalyst was prepared under the same conditions as catalyst 1 except that 1500 ⁇ m was added, to obtain catalyst 8 of the present invention. The degree of wear of the catalyst 8 was 0.29% by weight, and the hardness was 2.7 kgf (26.5 N).
- Comparative Example 1 (Preparation of catalyst 9) Crystalline cellulose (average particle diameter: 89.3 ⁇ m) of 5% by weight to the pre-fired powder obtained in Example 1 is added and sufficiently mixed.
- a catalyst was prepared under the same conditions as Catalyst 1 except that 40 wt% of a wt% glycerol solution was used based on the pre-calcined powder, to obtain a catalyst 9 for comparison.
- the degree of wear of the catalyst 9 was 0.31% by weight, and the hardness was 1.6 kgf (15.7 N).
- Comparative example 2 (Preparation of catalyst 10) Add 5% by weight of crystalline cellulose (average particle size: 89.3 ⁇ m) and 3% by weight of talc (average particle size: 57 ⁇ m) with respect to the pre-fired powder obtained in Example 1 and sufficiently After mixing, a catalyst was prepared under the same conditions as catalyst 1 except that a 33 wt% glycerol solution was used as a binder in a rolling granulation method and 40 wt% with respect to the pre-baked powder, and a catalyst for comparison 10 I got The degree of wear of the catalyst 10 was 0.20% by weight, and the hardness was 1.4 kgf (13.7 N).
- Comparative example 3 (Preparation of catalyst 11) A catalyst was prepared under the same conditions as catalyst 1 except that 3% by weight of talc (average particle diameter: 57 ⁇ m) was added to the pre-calcined powder obtained in Example 1, and catalyst 11 for comparison was prepared Obtained. The degree of wear of the catalyst 11 was 0.24% by weight, and the hardness was 1.9 kgf (18.6 N).
- Comparative example 4 (Preparation of catalyst 12) A catalyst was prepared under the same conditions as Catalyst 1 except that no auxiliary agent was added to the pre-calcined powder obtained in Example 1, and Catalyst 12 for comparison was obtained. The degree of wear of the catalyst 12 was 0.48% by weight, and the hardness was 2.3 kgf (22.5 N).
- Test Example 1 Coke precipitation reaction
- the liquid component and the gas component were separated by a condenser, and each component in the gas component was quantitatively analyzed by a gas chromatograph equipped with a hydrogen flame ionization detector and a heat conduction detector. Each data obtained by gas chromatograph was factor corrected to calculate 1-butene conversion and butadiene selectivity. The butadiene selectivity at TOS 280 hours was 88.1%.
- the same quantitative analysis as in the coke deposition reaction was conducted, and it was determined that the burning of the coke-like substance was completed when the amounts of CO 2 and CO in the gas at the outlet of the reaction tube became zero.
- Test example 2 Evaluation of failure rate by long-term test was performed under the same reaction conditions except that the catalyst to be evaluated in Catalyst 1 was Catalyst 3 obtained in Example 3. The failure rate of the catalyst 3 was 0.12% by weight. The butadiene selectivity at TOS 280 hours was 88.3%.
- Comparative test example 1 In Test Example 1, evaluation of failure rate by long-term test was performed under the same reaction conditions except that the catalyst to be evaluated was the catalyst 9 obtained in Comparative Example 1. The failure rate of the catalyst 9 was 1.55% by weight. The butadiene selectivity at TOS 280 hours was 87.1%.
- Comparative test example 2 In Test Example 1, evaluation of failure rate by long-term test was performed under the same reaction conditions except that the catalyst to be evaluated was the catalyst 11 obtained by Comparative Example 3. The failure rate of the catalyst 11 was 1.86% by weight. The butadiene selectivity at TOS 280 hours was 86.6%.
- Comparative test example 3 Evaluation of failure rate by long-term test was performed under the same reaction conditions except that the catalyst to be evaluated in Test Example 1 was the catalyst 12 obtained in Comparative Example 4. The failure rate of the catalyst 12 was 1.16% by weight. The butadiene selectivity at TOS 280 hours was 87.4%.
- Table 1 shows the results of the degree of wear, hardness and breakage rate according to the examples, comparative examples, test examples and comparative test examples.
- the hardness is improved by the addition of the glass fiber inorganic auxiliary according to the present invention, and the hardness of the catalyst can be further remarkably improved by not adding the organic auxiliary.
- the failure rate due to long-term reaction can be significantly suppressed, suggesting that the catalyst of the present invention can improve the long-term stability of the reaction.
- catalyst 9 had a good degree of friability, damage to the catalyst due to long-term reaction was observed.
- hardness evaluation is a physical property evaluation method for long-term stability of reaction that is more severe and suitable than evaluation of damage degree in that correlation with damage to catalyst due to long-term reaction can be significant. It can be concluded that That is, although not known to those skilled in the art, it is apparent from the present invention that hardness is suitable as a physical property evaluation method having correlation with damage due to a long-term reaction, not abrasion loss which is a conventional evaluation method of mechanical strength. Became.
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Abstract
Description
成形触媒に関する、一般的な機械的強度の向上のための方法としては、以下の文献が公知である。
(1)炭素原子数4以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するための触媒であって、複合金属酸化物とガラス繊維状無機助剤を成形することを特徴とする共役ジオレフィン製造用成形触媒、
(2)下記式(A)の条件を満たすことを特徴とする、(1)に記載の共役ジオレフィン製造用成形触媒:
R(=La/Dc)≦45 (A)
(式中、Laはガラス繊維状無機助剤の平均繊維長であり、Dcは複合金属酸化物の平均粒径である。)、
(3)有機助剤を含有しない、(1)または(2)に記載の共役ジオレフィン製造用成形触媒、
(4)複合金属酸化物が、下記組成式(D)を満たす、(1)から(3)のいずれか1項に記載の共役ジオレフィン製造用成形触媒、
Mo12BiaFebCocNidXeYfZg・・・・(D)
(式中、Xはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも1種の元素を示し、Yはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも1種の元素を示し、Zはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、セリウム、タリウムから選ばれる少なくとも1種の元素を示し、a、b、c、d、e及びfは各々モリブデン12に対するビスマス、鉄、コバルト、ニッケル、X、Y及びZの原子比を示し、0.3<a<3.5、0.6<b<3.4、5<c<8、0<d<3、0<e<0.5、0≦f≦4.0、0≦g≦2.0の範囲にあり、gは他の元素の酸化状態を満足させる数値である。)、
(5)炭素原子数4以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するための触媒であって、複合金属酸化物とガラス繊維状無機助剤を担体に担持したことを特徴とする、(1)から(4)のいずれか1項に記載の共役ジオレフィン製造用担持成形触媒、
(6)複合金属酸化物の各金属を含有する化合物を含む混合溶液またはスラリーを20℃以上90℃以下の条件化で調製し、次いで該混合物を乾燥、予備焼成し、ガラス繊維状無機助剤と共に成形し、本焼成する工程を含む、(1)から(5)のいずれか1項に記載の共役ジオレフィン製造用成形触媒の製造方法、
(7)予備焼成の温度が200℃以上600℃以下であり、本焼成温度が200℃以上600℃以下である、(6)に記載の共役ジオレフィン製造用成形触媒の製造方法、
(8)担体に複合金属酸化物とガラス繊維状無機助剤をバインダーとともにコーティングする成形工程を有し、かつ触媒活性成分の担持率が20重量%以上80重量%以下であり、触媒の平均粒径が3.0mm以上10.0mm以下である、(6)または(7)に記載の共役ジオレフィン製造用担持成形触媒の製造方法、
(9)全製造行程において、有機助剤を使用しない、(6)から(8)のいずれか一項に記載の成形触媒の製造方法、
に関する。
R(=La/Dc)≦45 (A)
0.5≦R(=La/Dc)≦20 (B)
1≦R(=La/Dc)≦10 (C)
(式中、Laはガラス繊維状無機助剤の平均繊維長であり、Dcは複合金属酸化物の平均粒径である。)
装置として特に制限はないが、例えば西山製作所社製LMS-2000eを用い、分散媒として精製水を用いてセルに各種サンプルを導入し、散乱光強度を4.0から6.0程度として測定し、質量百分率で得た粒径分布より平均粒径を算出する。
複合金属酸化物の平均粒径は、1μmから500μmが好ましく、10μmから100μmがより好ましい。
Mo12BiaFebCocNidXeYfZg・・・・(D)
(式中、Xはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも1種の元素を示し、Yはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも1種の元素を示し、Zはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、セリウム、タリウムから選ばれる少なくとも1種の元素を示し、a、b、c、d、e及びfは各々モリブデン12に対するビスマス、鉄、コバルト、ニッケル、X、Yセリウム及びZの原子比を示し、0.3<a<3.5、0.6<b<3.4、5<c<8、0<d<3、0<e<0.5、0≦f≦4.0、0≦g≦2.0の範囲にあり、gは他の元素の酸化状態を満足させる数値である。)
触媒活性成分の原料の混合溶液またはスラリーを調製し、沈殿法、ゲル化法、共沈法、水熱合成法等の工程を経た後、乾燥噴霧法、蒸発乾固法、ドラム乾燥法、凍結乾燥法等の公知の乾燥方法を用いて、本発明の乾燥粉体を得る。この混合溶液またはスラリーは、溶媒として水、有機溶剤、またはこれらの混合溶液のいずれでも良く、触媒の活性成分の原料濃度も制限はなく、更に、この混合溶液またはスラリーの液温、雰囲気等の調合条件および乾燥条件について特に制限はないが、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、20℃から90℃の条件化で触媒の活性成分の原料の混合溶液またはスラリーを形成させ、これを噴霧乾燥器に導入して乾燥器出口温度が70℃から150℃、得られる乾燥粉体の平均粒径が10μmから700μmとなるよう熱風入口温度、噴霧乾燥器内部の圧力、およびスラリーの流量を調節する方法である。また、本工程の混合溶液またはスラリーの調製から前記乾燥までにおいて、後述するガラス繊維状無機助剤または/および有機助剤を任意の量で添加することも本発明の触媒の製造方法に属するものとする。
こうして得られた乾燥粉体を200℃以上600℃以下で予備焼成し、平均粒径が10μmから100μmである本発明の複合金属酸化物(予備焼成粉体)を得ることができる。本発明においては、複合金属酸化物を予備焼成粉体と呼ぶことがある。この予備焼成の条件に関しても、焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度、成形性や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、トンネル焼成炉において300℃以上600℃以下の範囲で1時間から12時間、空気雰囲気下による方法である。また、本工程の予備焼成前または予備焼成後において、後述するガラス繊維状無機助剤および有機助剤を任意の量で添加することも本発明の触媒の製造方法に属するものとする。
本発明においては、こうして得られた予備焼成粉体を、成形して使用する。成形品の形状は球状、円柱状、リング状など特に制限されないが、一連の調製で最終的に得られる触媒における機械的強度、反応器、調製の生産効率等を考慮して選択するべきである。成形方法についても特に制限はないが、以下に示す担体や有機助剤、ガラス繊維状無機助剤、バインダー等を予備焼成粉体に添加して円柱状、リング状に成形する際には打錠成形機や押出成形機などを用い、球状に成形する際には造粒機などを用いて成形品を得る。このうち本発明において、予備焼成粉体と共に、上記ガラス繊維状無機助剤を添加して成形する方法が好ましく、不活性な担体に予備焼成粉体と共に、上記ガラス繊維状無機助剤を添加して転動造粒法によりコーティングさせ担持成形する方法がさらに好ましく、転動造粒法によりコーティングする際、有機助剤を全く添加しないことが最も好ましい。
担持率(重量%)=(成形に使用した予備焼成粉体の重量)/{(成形に使用した予備焼成粉体の重量)+(成形に使用した担体の重量)}×100
このようにして得られた予備焼成粉体または成形品は、反応に使用する前に200℃以上600℃以下で再度焼成(本焼成)することが好ましい。本焼成に関しても、焼成時間や焼成時の雰囲気について特に制限はなく、焼成の手法も流動床、ロータリーキルン、マッフル炉、トンネル焼成炉など特に制限はなく、最終的な触媒の性能、機械的強度や生産効率等を考慮して適切な範囲を選択されるべきである。このうち本発明において最も好ましいのは、トンネル焼成炉において300℃以上600℃以下の温度範囲で1時間から12時間、空気雰囲気下による焼成である。
磨損度(重量%)=100×〔(触媒重量-ふるい上に残った触媒重量)/触媒重量〕
ブタジエン収率(モル%)=(生成したブタジエンのモル数/供給したn-ブテンのモル数)×100
TOS=混合ガス流通時間(時間)
(触媒1の調製)
ヘプタモリブデン酸アンモニウム800重量部を80℃に加温した純水3000重量部に完全溶解させた(母液1)。次に、硝酸セシウム11重量部を純水124mlに溶解させて、母液1に加えた。次に、硝酸第二鉄275重量部、硝酸コバルト769重量部及び硝酸ニッケル110重量部を60℃に加温した純水612mlに溶解させ、母液1に加えた。続いて硝酸ビスマス165重量部を60℃に加温した純水175mlに硝酸(60重量%)42重量部を加えて調製した硝酸水溶液に溶解させ、母液1に加えた。この母液1をスプレードライ法にて乾燥し、得られた乾燥粉体を440℃、5時間の条件で予備焼成した。こうして得られた予備焼成粉体(平均粒径:63.2μm、仕込み原料から計算される原子比はMo:Bi:Fe:Co:Ni:Cs=12:1.7:1.8:7.0:1.0:0.15)に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のシラン処理したガラス繊維(平均繊維径:11μm、平均繊維長:150μm)を添加し、十分混合した後、転動造粒法にてバインダーとして33重量%グリセリン溶液を予備焼成粉体に対して33重量%用い、不活性の担体(シリカアルミナ)に、担持率が50重量%となるように球状に担持成形した。こうして得られた球状成形品を、500℃、5時間の条件で焼成し、本発明の触媒1を得た。触媒1の磨損度は0.20重量%、硬度は4.5kgf(44.0N)であった。
(触媒2の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のシラン処理したガラス繊維(平均繊維径:11μm、平均繊維長:100μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒2を得た。触媒2の磨損度は0.19重量%、硬度は3.2kgf(31.4N)であった。
(触媒3の調製)
実施例1で得られた予備焼成粉体に対して3重量%分のシラン処理したガラス繊維(平均繊維径:11μm、平均繊維長:150μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒3を得た。触媒3の磨損度は0.42重量%、硬度は15.5kgf(151.9N)であった。
(触媒4の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のガラス繊維(平均繊維径:11μm、平均繊維長:30μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒4を得た。触媒4の磨損度は0.13重量%、硬度は2.7kgf(26.5N)であった。
(触媒5の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のシラン処理したガラス繊維(平均繊維径:11μm、平均繊維長:50μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒5を得た。触媒5の磨損度は0.56重量%、硬度は2.9kgf(28.4N)であった。
(触媒6の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のガラス繊維(平均繊維径:11μm、平均繊維長:3000μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒6を得た。触媒6の磨損度は0.15重量%、硬度は2.5kgf(24.5N)であった。
(触媒7の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のガラス繊維(平均繊維径:10μm、平均繊維長:300μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒7を得た。触媒7の磨損度は0.27重量%、硬度は4.1kgf(40.2N)であった。
(触媒8の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のガラス繊維(平均繊維径:10μm、平均繊維長:1500μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、本発明の触媒8を得た。触媒8の磨損度は0.29重量%、硬度は2.7kgf(26.5N)であった。
(触媒9の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)を添加し、十分混合した後、転動造粒法にてバインダーとして33重量%グリセリン溶液を予備焼成粉体に対して40重量%用いた以外は、触媒1と同じ条件で触媒を調製し、比較用の触媒9を得た。触媒9の磨損度は0.31重量%、硬度は1.6kgf(15.7N)であった。
(触媒10の調製)
実施例1で得られた予備焼成粉体に対して5重量%分の結晶性セルロース(平均粒径:89.3μm)および3重量%分のタルク(平均粒径:57μm)を添加し、十分混合した後、転動造粒法にてバインダーとして33重量%グリセリン溶液を予備焼成粉体に対して40重量%用いた以外は、触媒1と同じ条件で触媒を調製し、比較用の触媒10を得た。触媒10の磨損度は0.20重量%、硬度は1.4kgf(13.7N)であった。
(触媒11の調製)
実施例1で得られた予備焼成粉体に対して3重量%分のタルク(平均粒径:57μm)を添加した以外は、触媒1と同じ条件で触媒を調製し、比較用の触媒11を得た。触媒11の磨損度は0.24重量%、硬度は1.9kgf(18.6N)であった。
(触媒12の調製)
実施例1で得られた予備焼成粉体に対して助剤を全く添加しなかった以外は、触媒1と同じ条件で触媒を調製し、比較用の触媒12を得た。触媒12の磨損度は0.48重量%、硬度は2.3kgf(22.5N)であった。
(コーク析出反応)
実施例1で得られた触媒1を以下の方法により反応評価した。触媒53mlをステンレス鋼反応管に充填し、ガス体積比率が1-ブテン:酸素:窒素:水蒸気=1:1:7:1の混合ガスを用い、常圧下、GHSV1200hr-1の条件で、1-ブテン転化率=80.0±1.0%を保持できるよう反応浴温度を変化させてTOS300時間まで反応し、コーク状物質を触媒上に析出させた。反応管出口で、コンデンサーにより液成分とガス成分を分離し、ガス成分中の各成分を各々水素炎イオン化検出器と熱伝導検出器が装着されたガスクロマトグラフで定量分析した。ガスクロマトグラフにより得られた各データはファクター補正し、1-ブテン転化率およびブタジエン選択率を算出した。TOS280時間におけるブタジエン選択率は88.1%であった。
コーク析出反応の後、触媒上に析出したコーク状物質を燃焼させる目的で、反応浴温度を400℃としてガス体積比率が酸素:窒素=1:3の混合ガスを用い、常圧下、空間速度400hr-1でTOS10時間程度、コーク状物質を燃焼させた。コーク析出反応と同様の定量分析を行い、反応管出口ガス中のCO2およびCOの生成量がゼロになった時点でコーク状物質の燃焼が完了したと判断した。
コーク燃焼反応の後、反応管より反応後の触媒を抜出し、3.35mmの篩にて分級した。篩の下に落ちた欠片状および粉状にまで破損した触媒を触媒片として秤量し、以下式により算出した触媒1の長期試験による破損率は、0.91重量%であった。
破損率(重量%)=触媒片の重量(g)/コーク析出反応前の充填触媒重量(g)×100
試験例1において、評価する触媒を実施例3により得られた触媒3とした以外は、同じ反応条件で長期試験による破損率の評価を行った。触媒3の破損率は、0.12重量%であった。TOS280時間におけるブタジエン選択率は88.3%であった。
試験例1において、評価する触媒を比較例1により得られた触媒9とした以外は、同じ反応条件で長期試験による破損率の評価を行った。触媒9の破損率は、1.55重量%であった。TOS280時間におけるブタジエン選択率は87.1%であった。
試験例1において、評価する触媒を比較例3により得られた触媒11とした以外は、同じ反応条件で長期試験による破損率の評価を行った。触媒11の破損率は、1.86重量%であった。TOS280時間におけるブタジエン選択率は86.6%であった。
試験例1において、評価する触媒を比較例4により得られた触媒12とした以外は、同じ反応条件で長期試験による破損率の評価を行った。触媒12の破損率は、1.16重量%であった。TOS280時間におけるブタジエン選択率は87.4%であった。
Claims (9)
- 炭素原子数4以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するための触媒であって、複合金属酸化物とガラス繊維状無機助剤を成形することを特徴とする共役ジオレフィン製造用成形触媒。
- 下記式(A)の条件を満たすことを特徴とする、請求項1に記載の共役ジオレフィン製造用成形触媒:
R(=La/Dc)≦45 (A)
(式中、Laはガラス繊維状無機助剤の平均繊維長であり、Dcは複合金属酸化物の平均粒径である。)。 - 有機助剤を含有しない、請求項1または請求項2に記載の共役ジオレフィン製造用成形触媒。
- 複合金属酸化物が、下記組成式(D)を満たす、請求項1から請求項3のいずれか1項に記載の共役ジオレフィン製造用成形触媒、
Mo12BiaFebCocNidXeYfZg・・・・(D)
(式中、Xはリチウム、ナトリウム、カリウム、ルビジウム、セシウムから選ばれるアルカリ金属の少なくとも1種の元素を示し、Yはマグネシウム、カルシウム、ストロンチウム、バリウムから選ばれるアルカリ土類金属の少なくとも1種の元素を示し、Zはランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロビウム、アンチモン、タングステン、鉛、亜鉛、セリウム、タリウムから選ばれる少なくとも1種の元素を示し、a、b、c、d、e及びfは各々モリブデン12に対するビスマス、鉄、コバルト、ニッケル、X、Y及びZの原子比を示し、0.3<a<3.5、0.6<b<3.4、5<c<8、0<d<3、0<e<0.5、0≦f≦4.0、0≦g≦2.0の範囲にあり、gは他の元素の酸化状態を満足させる数値である。)。 - 炭素原子数4以上のモノオレフィンと分子状酸素を含む混合ガスから接触酸化脱水素反応により共役ジオレフィンを製造するための触媒であって、複合金属酸化物とガラス繊維状無機助剤を担体に担持したことを特徴とする、請求項1から請求項4のいずれか1項に記載の共役ジオレフィン製造用担持成形触媒。
- 複合金属酸化物の各金属を含有する化合物を含む混合溶液またはスラリーを20℃以上90℃以下の条件化で調製し、次いで該混合物を乾燥、予備焼成し、ガラス繊維状無機助剤と共に成形し、本焼成する工程を含む、請求項1から請求項5のいずれか1項に記載の共役ジオレフィン製造用成形触媒の製造方法。
- 予備焼成の温度が200℃以上600℃以下であり、本焼成温度が200℃以上600℃以下である、請求項6に記載の共役ジオレフィン製造用成形触媒の製造方法。
- 担体に複合金属酸化物とガラス繊維状無機助剤をバインダーとともにコーティングする成形工程を有し、かつ触媒活性成分の担持率が20重量%以上80重量%以下であり、触媒の平均粒径が3.0mm以上10.0mm以下である、請求項6または請求項7に記載の共役ジオレフィン製造用担持成形触媒の製造方法。
- 全製造行程において、有機助剤を使用しない、請求項6から請求項8のいずれか一項に記載の成形触媒の製造方法。
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PCT/JP2016/077314 WO2017047710A1 (ja) | 2015-09-16 | 2016-09-15 | 共役ジオレフィン製造用触媒と、その製造方法 |
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US (1) | US20180208685A1 (ja) |
EP (1) | EP3351301A4 (ja) |
JP (1) | JP6731927B2 (ja) |
KR (1) | KR20180055840A (ja) |
CN (1) | CN108025293A (ja) |
WO (1) | WO2017047710A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11648536B2 (en) | 2017-11-28 | 2023-05-16 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation of butene and method for producing the same |
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JP2010516441A (ja) * | 2007-01-19 | 2010-05-20 | ビーエーエスエフ ソシエタス・ヨーロピア | その活物質が多元素酸化物である触媒成形体を製造する方法 |
JP2013202459A (ja) * | 2012-03-27 | 2013-10-07 | Mitsubishi Chemicals Corp | 複合金属酸化物触媒及び共役ジエンの製造方法 |
WO2013161703A1 (ja) * | 2012-04-23 | 2013-10-31 | 日本化薬株式会社 | 成型触媒の製造方法および該成型触媒を用いるジエンまたは不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
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JP5388897B2 (ja) * | 2010-02-26 | 2014-01-15 | 株式会社日本触媒 | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒および該触媒を用いた不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
WO2012036038A1 (ja) * | 2010-09-17 | 2012-03-22 | 株式会社日本触媒 | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒および該触媒を用いる不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
KR20150003214A (ko) * | 2012-04-23 | 2015-01-08 | 닛뽄 가야쿠 가부시키가이샤 | 부타디엔의 제조용 촉매, 그 촉매의 제조 방법 및 그 촉매를 이용한 부타디엔의 제조 방법 |
WO2014175113A1 (ja) * | 2013-04-25 | 2014-10-30 | 日本化薬株式会社 | 不飽和アルデヒドおよび/または不飽和カルボン酸製造用触媒、該触媒の製造方法、および該触媒を用いた不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
-
2016
- 2016-09-15 KR KR1020187009421A patent/KR20180055840A/ko unknown
- 2016-09-15 CN CN201680053574.2A patent/CN108025293A/zh active Pending
- 2016-09-15 EP EP16846581.3A patent/EP3351301A4/en not_active Withdrawn
- 2016-09-15 JP JP2017539978A patent/JP6731927B2/ja active Active
- 2016-09-15 US US15/759,416 patent/US20180208685A1/en not_active Abandoned
- 2016-09-15 WO PCT/JP2016/077314 patent/WO2017047710A1/ja active Application Filing
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JP2010516441A (ja) * | 2007-01-19 | 2010-05-20 | ビーエーエスエフ ソシエタス・ヨーロピア | その活物質が多元素酸化物である触媒成形体を製造する方法 |
JP2013202459A (ja) * | 2012-03-27 | 2013-10-07 | Mitsubishi Chemicals Corp | 複合金属酸化物触媒及び共役ジエンの製造方法 |
WO2013161703A1 (ja) * | 2012-04-23 | 2013-10-31 | 日本化薬株式会社 | 成型触媒の製造方法および該成型触媒を用いるジエンまたは不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 |
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Cited By (1)
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US11648536B2 (en) | 2017-11-28 | 2023-05-16 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation of butene and method for producing the same |
Also Published As
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EP3351301A4 (en) | 2019-05-22 |
JPWO2017047710A1 (ja) | 2018-07-05 |
EP3351301A1 (en) | 2018-07-25 |
CN108025293A (zh) | 2018-05-11 |
US20180208685A1 (en) | 2018-07-26 |
KR20180055840A (ko) | 2018-05-25 |
JP6731927B2 (ja) | 2020-07-29 |
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