WO2015072820A1 - 제올라이트 코팅층을 갖는 비스무스 몰리브데이트계 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법 - Google Patents
제올라이트 코팅층을 갖는 비스무스 몰리브데이트계 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법 Download PDFInfo
- Publication number
- WO2015072820A1 WO2015072820A1 PCT/KR2014/011087 KR2014011087W WO2015072820A1 WO 2015072820 A1 WO2015072820 A1 WO 2015072820A1 KR 2014011087 W KR2014011087 W KR 2014011087W WO 2015072820 A1 WO2015072820 A1 WO 2015072820A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composite oxide
- bismuth molybdate
- butadiene
- producing
- based composite
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 119
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000010457 zeolite Substances 0.000 title claims abstract description 112
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 111
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000011247 coating layer Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 108
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229910052792 caesium Inorganic materials 0.000 claims description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 239000012692 Fe precursor Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 22
- 239000006227 byproduct Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011162 core material Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007569 slipcasting Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000006200 vaporizer Substances 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- B01J35/19—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/31—Chromium, molybdenum or tungsten combined with bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
Definitions
- the present invention relates to a bismuth molybdate-based composite oxide catalyst having a high pore zeolite coating layer having a high 1,3-butadiene selectivity, a method for preparing the same, and a method for preparing 1,3-butadiene using the same. will be.
- 1,3-butadiene is an intermediate of many petrochemical products in the petrochemical market, and its demand and value are gradually increasing.
- Methods for preparing such 1,3-butadiene include naphtha cracking, direct dehydrogenation of normal-butene, and oxidative dehydrogenation of normal-butene.
- the naphtha cracking process which accounts for more than 90% of the 1,3-butadiene supplied to the market, consumes not only a large amount of energy due to high reaction temperature, but also because it is not a sole process for producing 1,3-butadiene.
- other basic oils are produced in surplus.
- the oxidative dehydrogenation reaction of normal-butene which produces butadiene through oxidative dehydrogenation (ODH) of normal-butene, removes two hydrogens from normal-butene using oxygen as a reactant. It is a reaction to produce, 3-butadiene, which is very thermodynamically advantageous because stable water is produced as a product, and unlike direct dehydrogenation reaction, it is exothermic and thus yields high yield of 1,3-butadiene at low reaction temperature compared to direct dehydrogenation reaction. Can be obtained. Therefore, the process of producing 1,3-butadiene through oxidative dehydrogenation of normal-butene may be an effective single production process that can meet the increasing demand for 1,3-butadiene. Therefore, a research into a method of producing 1,3-butanediene with high selectivity by increasing the efficiency of the process through the oxidative dehydrogenation of normal-butene is being conducted.
- the inventors of the present invention have studied bismuth molybdate composite oxide catalysts having high 1,3-butadiene selectivity, and selectively pass the product by forming a microporous zeolite coating layer on the surface of the catalyst. Not only has a high 1,3-butadiene selectivity, but also by confirming that it is possible to simplify the phase of the product by gasifying the solid organic by-products, thereby facilitating the purification process of the product.
- the invention was completed.
- An object of the present invention is to provide a bismuth molybdate-based composite oxide catalyst having a microporous zeolite coating layer formed on a surface showing high 1,3-butadiene selectivity.
- Another object of the present invention is to provide a method for preparing a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed on the surface thereof.
- Still another object of the present invention is to provide a method for producing high yield 1,3-butadiene through oxidative dehydrogenation of butene using a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed on the surface thereof.
- the present invention is a bismuth molybdate-based composite oxide represented by the formula (1); And it provides a bismuth molybdate-based composite oxide catalyst for producing 1,3-butadiene comprising a zeolite coating layer having micropores formed on the surface of the bismuth molybdate-based composite oxide:
- E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium; A, b, c, d and e are each 0.001 to 1; Y is a value determined for fitting valences by other components.
- the present invention comprises the steps of preparing a bismuth molybdate-based composite oxide represented by the formula (1); Dipping the prepared bismuth molybdate-based composite oxide in a zeolite seed solution, followed by drying and baking to form a zeolite seed layer on the surface of the bismuth molybdate composite oxide (step 2); And impregnating the zeolite seed oxide-containing bismuth molybdate composite oxide with a zeolite synthesis solution and drying the same (step 3).
- the method for preparing a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed thereon is provided. do.
- the present invention comprises the step of filling the reactor with a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed on the surface in a fixed phase (step A); And advancing an oxidative-dehydrogenation reaction while continuously passing a reactant containing a C4 mixture including normal butene into the catalyst layer of the reactor filled with the catalyst (step B).
- step A a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed on the surface in a fixed phase
- step B advancing an oxidative-dehydrogenation reaction while continuously passing a reactant containing a C4 mixture including normal butene into the catalyst layer of the reactor filled with the catalyst
- Bismuth molybdate composite oxide catalyst for producing 1,3-butadiene having a zeolite coating layer formed on a surface according to the present invention has a zeolite coating layer having micropores, so that only a gas product containing 1,3-butadiene as a target product is present. It can be selectively passed to have an effect of having a high selectivity to 1,3-butadiene.
- the organic by-products in the solid phase are attached to the catalyst surface without passing through the catalyst by the zeolite coating layer, and the attached organic by-products in the solid phase may be discharged in the form of CO x gas such as carbon dioxide by continuously supplied oxygen. It is possible to prevent the closing of the pipeline caused by the organic by-products of, and to simplify the separation process.
- the method for preparing a bismuth molybdate composite oxide catalyst having the zeolite coating layer formed thereon forms a zeolite seed layer on the surface of the bismuth molybdate composite oxide and grows a zeolite around the seed to form a zeolite coating layer.
- the zeolite coating layer can be uniformly synthesized on the surface of the catalyst core layer without separating the catalyst core layer (bismuth molybdate-based composite oxide) and the zeolite coating layer.
- the bismuth molybdate-based composite oxide catalyst and the method for preparing the zeolite-coated layer according to the present invention can be easily applied to industries that require it, in particular, the catalyst manufacturing industry and the 1,3-butadiene manufacturing industry.
- FIG. 1 schematically shows the catalysis of a bismuth molybdate composite oxide catalyst having a zeolite coating layer according to an embodiment of the present invention.
- Figure 2 schematically shows a manufacturing process of a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer according to an embodiment of the present invention.
- FIG. 3 is a morphology analysis result of the molybdate-based composite oxide catalyst having a zeolite coating layer according to an embodiment of the present invention
- Figure 3a is a scanning electron microscope analysis image
- Figure 3b is the catalyst analyzed by SEM-EDX The elemental composition of the surface is shown.
- FIG. 4 is a morphology analysis result of a bismuth molybdate-based composite oxide catalyst having no zeolite coating layer according to an embodiment of the present invention
- FIG. 4A is a scanning electron microscope analysis image
- FIG. 4B is analyzed by SEM-EDX. The elemental composition of the catalyst surface is shown.
- the present invention provides a bismuth molybdate-based composite oxide catalyst for producing 1,3-butadiene having a microporous zeolite coating layer on its surface.
- methods for preparing 1,3-butadiene include naphtha cracking process, direct dehydrogenation reaction of normal-butene, and oxidative dehydrogenation reaction of normal-butene, among which oxidative decomposition of normal-butene is performed.
- the dehydrogenation process is thermodynamically advantageous because stable water is produced as a product, and unlike the direct dehydrogenation process, it is exothermic, so that a higher yield of 1,3-butadiene can be obtained at a lower reaction temperature than the direct dehydrogenation process. It is attracting attention as an effective process.
- the oxidative dehydrogenation of normal-butene is a reaction in which normal-butene reacts with oxygen to produce 1,3-butadiene and water, although it has many advantages as a commercialization process. Because it is used as a side, many side reactions such as complete oxidation reaction can occur. Therefore, for an efficient process, it is necessary to develop a catalyst having high selectivity to 1,3-butadiene while maintaining high activity by controlling appropriate oxidation capacity.
- Bismuth molybdate-based composite oxide catalyst according to an embodiment of the present invention is devised to supplement the above problems, bismuth molybdate-based composite oxide represented by the formula (1); And a zeolite coating layer having micropores formed on a surface of the bismuth molybdate-based composite oxide.
- E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium; A, b, c, d and e are each 0.001 to 1; Y is a value determined for fitting valences by other components.
- E may be preferably at least one selected from the group consisting of cesium and potassium.
- the bismuth molybdate-based composite oxide catalyst for preparing 1,3-butadiene according to an embodiment of the present invention may have a structure in which a microporous zeolite coating layer is formed on a surface of the bismuth molybdate-based composite oxide core.
- the zeolite may be a zeolite in which silicon and aluminum are included together, an aluminum zeolite, or a silicon (Si) zeolite. Specifically, it may be a silicon (Si) zeolite, for example, may be a zeolite consisting of only SiO 2 . If the zeolite is a silicon zeolite, it is possible to obtain a better yield of product than other zeolites.
- the micropores of the zeolite coating layer may preferably have a diameter of 0.2 nm to 1.5 nm, the zeolite coating layer may have a thickness of 50 nm to 1000 nm. If the zeolite coating layer is less than 50 nm, the coating layer may not sufficiently cover the surface of the bismuth molybdate-based composite oxide core, and the solid organic by-products generated in the 1,3-butadiene manufacturing process using the same may be The coating layer may be easily taken out, which may cause a problem of increasing generation of organic by-products in the solid phase.
- the reactant approaches the surface of the bismuth molybdate-based composite oxide core in which an active site exists in the 1,3-butadiene manufacturing process using the same. It may not be easy, and as a result, the conversion rate of the reactants may be lowered, resulting in a problem of reduced catalytic activity.
- FIG. 1 The catalytic action of the bismuth molybdate-based composite oxide catalyst having the zeolite coating layer according to the embodiment of the present invention is schematically illustrated in FIG. 1.
- Zeolite coating layer 10 is composed of micropores, gas light containing a reactant (1, 1-butene and oxygen) and 1,3-butadiene having a particle size smaller than the pores It is possible to selectively pass only the product (3) of, thereby increasing the selectivity of the desired product.
- the solid organic by-product (2) of the product generated by dehydrogenation of butene is separated from the zeolite coating layer without being separated from the target product due to the particle size larger than the pore size of the micropores of the zeolite coating layer.
- the solid organic by-products attached to the surface (the bismuth molybdate-based composite oxide surface) and adhered to the surface are discharged in the form of COx gas compounds by continuously supplied oxygen.
- the present invention also provides a method for preparing a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer having micropores on its surface.
- the method for preparing a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer of the present invention may include preparing a bismuth molybdate-based composite oxide represented by Chemical Formula 1 (step 1); Dipping the prepared bismuth molybdate-based composite oxide in a zeolite seed solution, followed by drying and baking to form a zeolite seed on the surface of the bismuth molybdate composite oxide (step 2); And impregnating the zeolite seed-formed bismuth molybdate composite oxide into the zeolite synthesis solution and then drying (step 3).
- Step 1 is to prepare a bismuth molybdate-based composite oxide (1), which is a core material of the catalyst for preparing 1,3-butadiene having a zeolite coating layer, and the bismuth molybdate-based composite oxide may be in pellet form. .
- Each metal precursor used in the bismuth molybdate-based composite oxide of step 1 is not particularly limited and may be one conventionally used in the art.
- the precursors of nickel, sodium, potassium, rubidium and cesium are not particularly limited, but ammonium chloride, carbonate, nitrate, acetate chloride of each metal, Oxide, etc.
- the bismuth precursor may be bismuth nitrate
- the precursor of molybdenum may be ammonium molybdate.
- Step 1) is a step of preparing a first solution by mixing each metal precursor material in a solvent in order to mix the metal components constituting the bismuth molybdate-based composite oxide.
- the solvent may be distilled water, but is not particularly limited.
- a strong acid is additionally added to the solvent, or the bismuth precursor is separated and dissolved in a solvent containing a strong acid, and then added to the mixed solution of the other metal precursor to prepare a first solution. can do.
- the strong acid may be nitric acid, but is not limited thereto.
- step 2) in order to mix the molybdenum precursor in the first solution, a molybdenum precursor is dissolved in a solvent to prepare a second solution, and then the first solution is added to mix and react.
- the reaction may be performed while stirring, the stirring may be performed at a stirring speed of 100 rpm to 800 rpm in the temperature range of 25 °C to 80 °C.
- Step 3) is a step of obtaining a bismuth molybdate-based composite oxide by drying, molding and calcining the reactant produced after the reaction.
- the firing may be performed for 1 hour to 24 hours at a temperature of 400 °C to 600 °C, preferably may be performed for 2 to 10 hours at a temperature of 450 °C to 500 °C.
- step 2 slip casting is performed to form a zeolite seed in the bismuth molybdate-based composite oxide (1) prepared in step 1.
- slip casting used in the present invention is an application and modification of a generally known slip casting.
- a slurry is prepared by mixing seed material and water, and then the mold is immersed in the slurry for a predetermined time, and then dried and fired. Means a method for obtaining a solid molded article. At this time, the mold is not removed.
- the seed layer according to an embodiment of the present invention can be formed by using slip casting, specifically, the bismuth molybdate-based composite oxide is immersed in a zeolite seed solution (2), left for a predetermined time, and then taken out and dried. It can be formed by baking (3).
- the zeolite seed solution (2) is a slurry prepared by putting zeolite powder in distilled water, and may include 0.1 wt% to 20 wt% of zeolite based on the total weight of the seed solution.
- the drying (3) may be carried out by heat treatment for 5 to 100 hours, specifically 10 to 30 hours in the temperature range of 90 °C to 200 °C, specifically 110 °C to 150 °C.
- the firing (3) may be performed by heat treatment for 2 hours to 40 hours at 400 °C to 600 °C temperature range, specifically 400 °C to 500 °C temperature range, more specifically 450 °C to 500 °C It may be performed in the temperature range of.
- the bismuth molybdate composite oxide having the zeolite seed is soaked in a zeolite synthesis solution (4).
- the hydrothermal reaction is followed by growing the seed, drying and calcining.
- the hydrothermal reaction may be performed for 3 hours to 200 hours in the temperature range of 100 °C to 200 °C.
- the drying may be performed by heat treatment for 1 hour to 24 hours in the temperature range of 110 °C to 200 °C.
- the zeolite synthesis solution 4 is a solution containing a precursor for the synthesis of zeolite, and may include a silica precursor forming a zeolite skeleton with a zeolite structure derivative (Structure-Directing Agent, SDA).
- the synthesis solution may further include an aluminum precursor.
- the zeolite structure derivative is not particularly limited, but may be generally in the form of quaternary ammonium, and the zeolite skeleton derived by the zeolite structure derivative is MFI (ZSM-5) type, BEA (BETA) type, It may be a MOR (mdenite) type, LTA type, etc., but is not limited thereto.
- the seed is grown to form a zeolite coating layer to form a bismuth molybdate composite oxide core
- the present invention provides a method for producing 1,3-butadiene using a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer formed on the surface thereof.
- the method for preparing 1,3-butadiene of the present invention comprises the steps of: filling a reactor with a bismuth molybdate-based composite oxide catalyst having a zeolite coating layer having micropores in a fixed phase (step A); And advancing an oxidative-dehydrogenation reaction while continuously passing a reactant containing a C4 compound including normal butene through the catalyst layer of the reactor filled with the catalyst (step B).
- the oxidative-dehydrogenation reaction may be preferably performed at a space temperature of 50 h ⁇ 1 to 5000 h ⁇ 1 based on a reaction temperature of 250 ° C. to 450 ° C. and the normal butene.
- Bismuth nitrate pentahydrate, iron nitrate hexahydrate (Fe (NO 3 ) 3 ⁇ 9 (H 2 O)), cobalt nitrate hexahydrate (Co (NO 3 ) 2 ⁇ 6 (H 2 O)), potassium nitrate Rate (KNO 3 ), cesium nitrate (CsNO 3 ) was added to distilled water and mixed to prepare a first solution.
- bismuth nitrate pentahydrate which is a bismuth precursor, was added after dissolving a nitric acid solution in distilled water.
- the zeolite coating layer was formed on the surface of the pellet-type bismuth molybdate-based composite oxide core prepared in Example 1).
- the coating layer is formed by using a slip casting method to form a zeolite seed layer on the surface of the composite oxide core, and then by hydrothermally synthesizing the composite oxide core having the seed layer in a zeolite synthesis solution, followed by drying and baking. Prepared.
- the pellet-type bismuth molybdate-based composite oxide core was immersed in a zeolite seed solution (zeolite slurry, a solution containing 2% by weight of zeolite) and left for a certain time. Then, it was taken out, dried and calcined to harden. Then, the composite oxide core having the seed layer formed was immersed in a zeolite synthesis solution for 24 hours at 145 ° C. to obtain a pellet-type bismuth molybdate-based composite oxide catalyst having a zeolite coating layer.
- the schematic diagram of the formation process of a zeolite coating layer is shown in FIG.
- a pelletized bismuth molybdate composite oxide catalyst without a zeolite coating layer was prepared.
- Bismuth nitrate pentahydrate, iron nitrate hexahydrate (Fe (NO 3 ) 3 ⁇ 9 (H 2 O)), cobalt nitrate hexahydrate (Co (NO 3 ) 2 ⁇ 6 (H 2 O)), potassium nitrate Rate (KNO 3 ), cesium nitrate (CsNO 3 ) was added to distilled water and mixed to prepare a first solution.
- bismuth nitrate pentahydrate which is a bismuth precursor, was added after dissolving a nitric acid solution in distilled water.
- FIG. 3 is a morphology analysis result of the molybdate-based composite oxide catalyst having a zeolite coating layer prepared in Example
- Figure 3a is a scanning electron microscope analysis image
- Figure 3b is the elemental composition of the catalyst surface analyzed by SEM-EDX It is shown.
- FIG. 4 is a result of morphology analysis of a bismuth molybdate-based composite oxide catalyst having no zeolite coating layer prepared in Comparative Example
- FIG. 4A is a scanning electron microscope image
- FIG. 4B is a surface of the catalyst analyzed by SEM-EDX. The elemental composition is shown.
- the bismuth molybdate-based composite oxide catalyst (FIG. 3A) of the example and the bismuth molybdate-based composite oxide catalyst (FIG. 4A) of the comparative example had different surface shapes, and were specifically carried out. It was confirmed that the surface of the example bismuth molybdate-based composite oxide catalyst was covered with zeolite crystals.
- the surface element composition (FIG. 3B) of the bismuth molybdate-based composite oxide catalyst of the example was compared with the surface element composition (FIG. 4B) of the bismuth molybdate-based composite oxide catalyst of the comparative example in the SEM-EDX results. It was confirmed that the ratio of Si element on the surface of the bismuth molybdate-based composite oxide catalyst of the example significantly increased, which means that the zeolite is formed as a coating layer on the surface of the bismuth molybdate-based catalyst.
- 1-butene and oxygen were used as reactants, and additionally nitrogen and steam were introduced together.
- a metal tubular reactor was used as the reactor.
- the proportion of reactants and gas space velocity (GHSV) were set based on 1-butene.
- the ratio of butene: oxygen: steam: nitrogen was set to 1: 0.75: 6: 10, and the gas space velocities were constantly adjusted to 50 h ⁇ 1 and 75 h ⁇ 1 based on 1-butene according to the experimental conditions.
- the volume of the catalyst layer in contact with the reactants was fixed at 200 cc, and steam was injected into the vaporizer in the form of water, vaporized at 340 ° C. with steam, mixed with other reactants, 1-butene and oxygen, to be introduced into the reactor.
- the device was designed.
- the amount of butene was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gases, and the amount of steam was controlled using a liquid pump.
- the reaction temperature was maintained at 300 °C, 320 °C, and 340 °C, after the reaction the product was analyzed by gas chromatography.
- the product contained 1-2-3-butadiene as the desired product, trans-2-butene, cis-2-butene, and the like as organic solid by-products.
- the bismuth molybdate-based composite oxide catalyst having the zeolite coating layer of the example according to the present invention had a conversion rate of 1-butene and 1 of the same level as compared with the bismuth molybdate-based composite oxide catalyst of the comparative example.
- the selectivity of the organic by-products of the solid phase decreased with the selectivity of, 3-butadiene.
- the bismuth molybdate-based composite oxide catalyst (example) having the zeolite coating layer according to the present invention is equivalent to the conversion of reactants at the same level as compared to the bismuth molybdate-based composite oxide catalyst (comparative example) without the zeolite coating layer.
- the selectivity of the by-products was reduced to 30%. This result means that the organic by-products of the solid phase are selectively separated by the zeolite coating layer according to the present invention.
- the selectivity of CO x increased slightly compared to the bismuth molybdate-based composite oxide catalyst (example) having a zeolite coating layer compared to the bismuth molybdate-based composite oxide catalyst (comparative example) having no zeolite coating layer.
- the results suggest that some of the organic by-products in the solid phase have been converted to CO x by reacting with oxygen contained in the reactants.
Abstract
Description
구분 | 전환율(%) | S-BD(%) | S-heavy(%) | S-COx(%) | HST(℃ |
실시예 | 97.7 | 92.28 | 0.42 | 1.89 | 381.0 |
비교예 | 97.96 | 92.90 | 1.42 | 1.78 | 389.3 |
Claims (17)
- 하기 화학식 1로 표시되는 비스무스 몰리브데이트계 복합산화물; 및상기 비스무스 몰리브데이트계 복합산화물 표면에 형성된 미세기공을 갖는 제올라이트 코팅층을 포함하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매:[화학식 1]MoaBibFecCodEeOy상기 식에서, E는 니켈, 나트륨, 칼륨, 루비듐 및 세슘으로 이루어진 군으로부터 선택되는 1종 이상인 것이며;상기 a, b, c, d 및 e는 각각 0.001 내지 1이고;상기 y는 다른 성분에 의해 원자가를 맞추기 위해 정해지는 값이다.
- 청구항 1에 있어서,상기 E는 세슘 및 칼륨으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매.
- 청구항 1에 있어서,상기 제올라이트는 규소(Si)계 제올라이트인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매.
- 청구항 1에 있어서,상기 미세기공은 직경이 0.2 nm 내지 1.5 nm인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매.
- 청구항 1에 있어서,상기 제올라이트 코팅층은 50 nm 내지 1000 nm 두께를 갖는 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매.
- 청구항 1에 있어서,상기 촉매는 펠렛 형태인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매.
- 1) 하기 화학식 1로 표시되는 비스무스 몰리브데이트계 복합산화물을 제조하는 단계;2) 상기 제조된 비스무스 복합산화물에 제올라이트 시드 용액을 부어 방치한 후 건조 및 소성하여 비스무스 몰리브데이트 복합산화물 표면에 제올라이트 시드를 형성시키는 단계; 및3) 상기 제올라이트 시드가 형성된 비스무스 몰리브데이트 복합산화물을 제올라이트 합성 용액에 함침시켜 시드를 성장시키고 건조하는 단계를 포함하는 표면에 미세기공을 갖는 제올라이트 코팅층이 형성된 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법:[화학식 1]MoaBibFecCodEeOy상기 식에서, E는 니켈, 나트륨, 칼륨, 루비듐 및 세슘으로 이루어진 군으로부터 선택되는 1종 이상인 것이며;상기 a, b, c, d 및 e는 각각 0.001 내지 1이고;상기 y는 다른 성분에 의해 원자가를 맞추기 위해 정해지는 값.
- 청구항 7에 있어서,상기 단계 1)의 비스무스 몰리브데이트계 복합산화물은,비스무스 전구체; 철 전구체; 코발트 전구체; 및 니켈, 나트륨, 칼륨, 루비듐 및 세슘 중 1종 이상의 금속 전구체를 포함한 제1 용액을 제조하는 단계;몰리브덴 전구체가 용해되어 있는 제2 용액에 상기 제1 용액을 첨가하여 혼합하고 반응시키는 단계; 및상기 반응 후 건조하고 성형 및 소성시키는 단계에 의하여 제조되는 것인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 제올라이트는 규소(Si)계 제올라이트인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 미세기공은 직경이 0.2 nm 내지 1.5 nm인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 단계 2)의 건조는 90℃ 내지 200℃ 온도범위에서 5 시간 내지 100 시간 동안 열처리하여 수행하는 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 단계 2)의 소성은 400℃ 내지 600℃온도범위에서 2 시간 내지 40 시간 동안 열처리하여 수행하는 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 단계 3)의 건조는 110℃ 내지 200℃의 온도범위에서 1 시간 내지 24 시간 동안 열처리하여 수행하는 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 제올라이트 코팅층은 50 nm 내지 1000 nm의 두께를 갖도록 형성되는 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 7에 있어서,상기 촉매는 펠렛 형태인 것을 특징으로 하는 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매의 제조방법.
- 청구항 1의 1,3-부타디엔 제조용 비스무스 몰리브데이트계 복합산화물 촉매를 반응기에 고정상으로 충진시키는 단계; 및노르말 부텐을 포함하는 C4 화합물을 함유하는 반응물을 상기 촉매가 충진된 반응기의 촉매층에 연속적으로 통과시키면서 산화적-탈수소화 반응을 진행시키는 단계를 포함하는 1,3-부타디엔의 제조방법.
- 청구항 16에 있어서,상기 산화적-탈수소화 반응은 250℃ 내지 450℃의 반응온도 및 상기 노르말 부텐을 기준으로 50 h-1 내지 5000 h-1의 공간속도에서 수행하는 것을 특징으로 하는 1,3-부타디엔의 제조방법.
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US14/427,207 US9925525B2 (en) | 2013-11-18 | 2014-11-18 | Bismuth molybdate-based catalyst having zeolite coating layer, method of preparing the same, and method of preparing 1,3-butadiene using the same |
CN201480053834.7A CN105592922A (zh) | 2013-11-18 | 2014-11-18 | 具有沸石涂层的基于钼酸铋的催化剂、其制备方法以及用该催化剂制备1,3-丁二烯的方法 |
JP2016546726A JP6265354B2 (ja) | 2013-11-18 | 2014-11-18 | ゼオライトコーティング層を有するビスマスモリブデート系触媒、この製造方法、及びこれを利用した1,3−ブタジエンの製造方法 |
EP14862509.8A EP3072586B1 (en) | 2013-11-18 | 2014-11-18 | Bismuth molybdate-based catalyst having zeolite coating layer, method for producing same, and method for preparing 1,3-butadiene using same |
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KR1020140160918A KR101742360B1 (ko) | 2013-11-18 | 2014-11-18 | 제올라이트 코팅층을 갖는 비스무스 몰리브데이트계 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법 |
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