JP2016536138A - 多成分系複合金属酸化物触媒の製造方法 - Google Patents
多成分系複合金属酸化物触媒の製造方法 Download PDFInfo
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- JP2016536138A JP2016536138A JP2016544305A JP2016544305A JP2016536138A JP 2016536138 A JP2016536138 A JP 2016536138A JP 2016544305 A JP2016544305 A JP 2016544305A JP 2016544305 A JP2016544305 A JP 2016544305A JP 2016536138 A JP2016536138 A JP 2016536138A
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- metal oxide
- bismuth
- oxide catalyst
- composite metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 86
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 105
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000002184 metal Substances 0.000 claims abstract description 102
- 238000000975 co-precipitation Methods 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000000376 reactant Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 154
- 239000002243 precursor Substances 0.000 claims description 88
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 74
- 150000002500 ions Chemical class 0.000 claims description 41
- 150000001768 cations Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims description 26
- 239000011733 molybdenum Substances 0.000 claims description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052797 bismuth Inorganic materials 0.000 claims description 23
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 23
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052730 francium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 33
- 239000001301 oxygen Substances 0.000 abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- 229910004625 Ce—Zr Inorganic materials 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 3
- 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 3
- 239000002585 base Substances 0.000 description 3
- 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 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CBRVNNFPYLQDQN-UHFFFAOYSA-N zirconium(4+) tetranitrate hexahydrate Chemical compound O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zr+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] CBRVNNFPYLQDQN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QDOAVFZGLCBVQL-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi].[Bi] QDOAVFZGLCBVQL-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- B01J23/85—Chromium, molybdenum or tungsten
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- 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
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- C07C2523/24—Chromium, molybdenum or tungsten
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- 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
Abstract
Description
本出願は、2014年6月10日付韓国特許出願第10-2014-0070222号及び2015年6月4日付韓国特許出願第10-2015-0079139号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示されている全ての内容は本明細書の一部として含まれる。
[MoaBibCcDdEeOf] (1)
前記式で、Cは、2価又は3価正イオン金属元素で、Dは、1価正イオン金属元素で、Eは、4価正イオン金属元素であり、aは5から20、bは0.1から2、cは1から5、dは1から10、eは0.1から1の実数であり、fは他の成分により原子価を合わせるために定まる値である。
[MoaBibCcDdEeOf] (1)
前記式で、Cは、2価又は3価正イオン金属元素で、Dは、1価正イオン金属元素で、Eは、4価正イオン金属元素であり、aは5から20、bは0.1から2、cは1から5、dは1から10、eは0.1から1の実数であり、fは他の成分により原子価を合わせるために定まる値である。
[CegZr(1-g)] (2)
[MoaBibCcDdEeOf] (1)
1次共沈及び2次共沈段階を含む2段階共沈工程を通じた製造方法で6成分系ビスマス-モリブデン複合金属酸化物触媒を製造した。
硝酸鉄九水和物(Fe(NO3)3・9H2O)と硝酸カリウム(KNO3)を蒸溜水に溶解させて鉄及びカリウム前駆体混合溶液を製造した。これと分離して、硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を硝酸塩水溶液に溶解させてビスマス前駆体溶液を製造し、ここに前記鉄及びカリウム前駆体混合溶液を滴下して第1溶液を製造した。その後、モリブデン酸アンモニウム四水和物((NH4)6(Mo7O24)・4H2O)を蒸溜水に溶解させて準備したモリブデン前駆体溶液に前記第1溶液を徐々に滴下し、共沈して第2溶液を製造した。前記第2溶液内に金属成分の共沈が十分になされるようにするため、前記第2溶液を100℃を維持しつつ2時間の間撹拌して熟成させた。熟成が完了した第2溶液を真空蒸発(vacuum evaporation)し、水分及びその他の液体成分を除去して固体を収得し、これを180℃で8時間の間乾燥した後、空気雰囲気において450℃で8時間焼成して4成分系ビスマス-モリブデン複合金属酸化物触媒[Mo10Bi1Fe3K1O37]を製造した。
硝酸鉄九水和物(Fe(NO3)3・9H2O)、硝酸カリウム(KNO3)、硝酸セリウム六水和物(Ce(NO3)3・6H2O)及び硝酸ジルコニウム六水和物(ZrO(NO3)2・6H2O)を蒸溜水に溶解させ、鉄、カリウム、セリウム及びジルコニウム前駆体混合溶液を製造した。このとき、前記硝酸セリウム六水和物及び硝酸ジルコニウム六水和物は、最終的に製造された触媒内にセリウム及びジルコニウムが0.65:0.35のモル比率を有するように添加した。これと分離して、硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を硝酸塩水溶液に溶解させてビスマス前駆体溶液を製造し、ここに前記鉄及びカリウム前駆体混合溶液を滴下して第1溶液を製造した。その後、モリブデン酸アンモニウム四水和物((NH4)6(Mo7O24)・4H2O)を蒸溜水に溶解させて準備したモリブデン前駆体溶液に前記第1溶液を徐々に滴下し、共沈して第2溶液を製造した。前記第2溶液内に金属成分の共沈が十分になされるようにするため、前記第2溶液を100℃を維持しつつ2時間の間撹拌して熟成させた。熟成が完了した第2溶液を真空蒸発(vacuum evaporation)し、水分及びその他の液体成分を除去して固体を収得し、これを180℃で8時間の間乾燥した後、空気雰囲気において450℃で8時間焼成して6成分系ビスマス-モリブデン複合金属酸化物触媒[Mo10Bi1Fe3K1Ce0.1Zr0.05O37]を製造した。
前記実施例で製造した6成分系ビスマス-モリブデン複合金属酸化物触媒と、比較例1で製造した4成分系ビスマス-モリブデン複合金属酸化物触媒との構造的特徴を比較分析するためにX線回折分析(XRD)を実施し、結果を図2に示した。X線回折分析は、Bruker AXS D4 Endeavor XRD(電圧40kV、電流40mA、Cu-target tube、波長1.5418Å、LynxEye position sensitive detector(3.7゜slit))を用い、FDS 0.5を利用して、2 theta 10゜から100゜まで0.02゜毎に87.5秒の間隔で測定した。
前記実施例と比較例1及び比較例2で製造した各触媒の活性を比較分析するため、1-ブテンの転換率、1,3-ブタジエンの収率、1,3-ブタジエンの選択度、重質油(heavies)の選択度及びCOxの選択度を下記の方法で測定した。
Claims (19)
2) モリブデン前駆体溶液に前記第1溶液を滴下し、1次共沈して第2溶液を製造する段階;
3) 前記第2溶液の熟成工程中に4価正イオン金属前駆体を含む第3溶液を滴下し、2次共沈して第4溶液を製造する段階; 及び
4) 前記第4溶液を乾燥後焼成する段階
を含む、下記化学式(1)で表される多成分系ビスマス-モリブデン複合金属酸化物触媒の製造方法:
[MoaBibCcDdEeOf] (1)
前記式で、
Cは、2価又は3価正イオン金属元素で、
Dは、1価正イオン金属元素で、
Eは、4価正イオン金属元素であり、
aは5から20、bは0.1から2、cは1から5、dは1から10、eは0.1から1の実数であり、fは他の成分により原子価を合わせるために定まる値である。
4価正イオン金属元素前駆体溶液に塩基性溶液を滴下し、pH 5から9に滴定して共沈溶液を製造する段階; 及び
前記共沈溶液を30分から24時間の間撹拌して熟成させる段階により製造したものであることを特徴とする請求項1に記載の多成分系ビスマス-モリブデン複合金属酸化物触媒の製造方法。
[CegZr(1-g)] (2)
前記式で、gは0.5から1の実数である。
前記Ce及びZrは、0.5から0.75:0.25から0.5のモル比率を有することを特徴とする請求項1から9のいずれか一項に記載の多成分系ビスマス-モリブデン複合金属酸化物触媒の製造方法。
[MoaBibCcDdEeOf] (1)
前記式で、
Cは、2価又は3価正イオン金属元素で、
Dは、1価正イオン金属元素で、
Eは、4価正イオン金属元素であり、
aは5から20、bは0.1から2、cは1から5、dは1から10、eは0.1から1の実数であり、fは他の成分により原子価を合わせるために定まる値である。
[CegZr(1-g)] (2)
前記式で、gは0.5から1の実数である。
前記Ce及びZrは0.5から0.75:0.5から0.25のモル比率を有することを特徴とする請求項12から14のいずれか一項に記載の多成分系ビスマス-モリブデン複合金属酸化物触媒。
ノルマルブテンを含むC4化合物を含有する反応物を、前記触媒が充填された反応器の触媒層に連続的に通過させつつ酸化的-脱水素化反応を進めさせる段階を含む1,3-ブタジエンの製造方法。
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