JP2015167886A - Method for producing ferritic catalyst used for the dehydrogenation of butene, ferritic catalyst used for the dehydrogenation of butene and method for producing 1,3-butadiene - Google Patents
Method for producing ferritic catalyst used for the dehydrogenation of butene, ferritic catalyst used for the dehydrogenation of butene and method for producing 1,3-butadiene Download PDFInfo
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- JP2015167886A JP2015167886A JP2014042824A JP2014042824A JP2015167886A JP 2015167886 A JP2015167886 A JP 2015167886A JP 2014042824 A JP2014042824 A JP 2014042824A JP 2014042824 A JP2014042824 A JP 2014042824A JP 2015167886 A JP2015167886 A JP 2015167886A
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- butene
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- ferrite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 133
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 85
- 150000003839 salts Chemical class 0.000 claims abstract description 61
- 239000002243 precursor Substances 0.000 claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 43
- 238000010304 firing Methods 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000859 α-Fe Inorganic materials 0.000 claims description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 150000007524 organic acids Chemical class 0.000 claims description 19
- 230000000052 comparative effect Effects 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 50
- 238000000034 method Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 40
- 239000007789 gas Substances 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 34
- 239000000047 product Substances 0.000 description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910001868 water Inorganic materials 0.000 description 21
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 150000001722 carbon compounds Chemical class 0.000 description 12
- 239000011701 zinc Substances 0.000 description 10
- 229910003321 CoFe Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000004687 hexahydrates Chemical class 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 4
- 150000004684 trihydrates Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 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 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 150000004685 tetrahydrates Chemical class 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910018380 Mn(NO3)2.6H2 O Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- MBEBBSNWIOVTHQ-UHFFFAOYSA-M copper;acetate Chemical compound [Cu+2].CC([O-])=O MBEBBSNWIOVTHQ-UHFFFAOYSA-M 0.000 description 1
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 description 1
- 239000000495 cryogel Substances 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、ブテンの脱水素に用いるフェライト系触媒の製造方法、ブテンの脱水素に用いるフェライト系触媒、及び１，３−ブタジエンの製造方法に関する。 The present invention relates to a method for producing a ferrite catalyst used for dehydrogenation of butene, a ferrite catalyst used for dehydrogenation of butene, and a method for producing 1,3-butadiene.
１，３−ブタジエンは、例えば、スチレン・ブタジエンゴム、ニトリル・ブタジエンゴム若しくはクロロプレンゴム等の合成ゴム、ＡＢＳ樹脂、アジポニトリル、クロロプレン、スルホラン、１，４−ブタンジオール、又はシクロドデカトリエンの製造において、原料又は中間体として用いられる。 In the production of 1,3-butadiene, for example, synthetic rubber such as styrene / butadiene rubber, nitrile / butadiene rubber or chloroprene rubber, ABS resin, adiponitrile, chloroprene, sulfolane, 1,4-butanediol, or cyclododecatriene, Used as raw material or intermediate.
１，３−ブタジエンは、ブテンの脱水素（酸化的脱水素）により生成する。例えば下記特許文献１には、亜鉛を含むフェライト系触媒を共沈法によって作製し、亜鉛を含むフェライト系触媒を用いたブテンの脱水素により、１，３−ブタジエンを製造する方法が開示されている。下記特許文献２には、マンガンを含むフェライト触媒を共沈法によって作製し、マンガンを含むフェライト触媒を用いたブテンの脱水素により、１，３−ブタジエンを製造する方法が開示されている。 1,3-butadiene is produced by dehydrogenation of butene (oxidative dehydrogenation). For example, Patent Document 1 below discloses a method of producing 1,3-butadiene by producing a ferrite catalyst containing zinc by a coprecipitation method and dehydrogenating butene using the ferrite catalyst containing zinc. Yes. Patent Document 2 below discloses a method of producing 1,3-butadiene by producing a ferrite catalyst containing manganese by a coprecipitation method and dehydrogenating butene using the ferrite catalyst containing manganese.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、ブテンの脱水素反応における１，３−ブタジエンの選択率を向上させることができる、ブテンの脱水素に用いるフェライト系触媒の製造方法、ブテンの脱水素に用いるフェライト系触媒、及び１，３−ブタジエンの製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and can improve the selectivity of 1,3-butadiene in the dehydrogenation reaction of butene, and is a ferrite catalyst used for dehydrogenation of butene. An object of the present invention is to provide a production method, a ferrite catalyst used for dehydrogenation of butene, and a production method of 1,3-butadiene.
本発明の一側面に係るブテンの脱水素に用いるフェライト系触媒の製造方法は、第一の金属塩と第二の金属塩とを含む溶液を、多孔質の炭素質材料に含浸させて、前駆体を調製する調製工程と、前駆体を焼成する焼成工程と、を備え、第一の金属塩は、銅又はコバルトのうち少なくともいずれかを含み、第二の金属塩は、鉄を含む。 According to an aspect of the present invention, there is provided a method for producing a ferrite-based catalyst used for dehydrogenation of butene, which comprises impregnating a porous carbonaceous material with a solution containing a first metal salt and a second metal salt, A preparation step for preparing the body and a firing step for firing the precursor, wherein the first metal salt includes at least one of copper and cobalt, and the second metal salt includes iron.
本発明の一側面においては、溶液が、有機酸を含んでもよい。 In one aspect of the invention, the solution may contain an organic acid.
本発明の一側面においては、焼成工程において、炭素質材料の少なくとも一部を焼失させてよい。 In one aspect of the present invention, at least a part of the carbonaceous material may be burned off in the firing step.
本発明の他の側面に係るブテンの脱水素に用いるフェライト系触媒の製造方法は、第一の金属塩と第二の金属塩と有機酸とを含む溶液から、前駆体を調製する調製工程と、前駆体を焼成する焼成工程と、を備え、第一の金属塩は、銅又はコバルトのうち少なくともいずれかを含み、第二の金属塩は、鉄を含む。 A method for producing a ferrite catalyst used for dehydrogenation of butene according to another aspect of the present invention includes a preparation step of preparing a precursor from a solution containing a first metal salt, a second metal salt, and an organic acid. And a firing step of firing the precursor, wherein the first metal salt includes at least one of copper and cobalt, and the second metal salt includes iron.
本発明の一側面に係るブテンの脱水素に用いるフェライト系触媒は、上記のフェライト系触媒の製造方法によって製造される。 The ferrite catalyst used for dehydrogenation of butene according to one aspect of the present invention is produced by the above-described method for producing a ferrite catalyst.
本発明の一側面に係るブテンの脱水素に用いるフェライト系触媒は、ＭＦｅ２Ｏ４（ＭはＣｕ又はＣｏのうち少なくともいずれかである。）を含み、炭素の含有率が、０〜５質量％である。 The ferrite catalyst used for dehydrogenation of butene according to one aspect of the present invention contains MFe 2 O 4 (M is at least one of Cu and Co), and the carbon content is 0 to 5 mass. %.
本発明の一側面に係るブテンの脱水素に用いるフェライト系触媒では、炭素の含有率が、０〜０．０１質量％であってよい。 In the ferrite catalyst used for dehydrogenation of butene according to one aspect of the present invention, the carbon content may be 0 to 0.01% by mass.
本発明の一側面に係る１，３−ブタジエンの製造方法は、ブテンを上記のフェライト系触媒に接触させる脱水素工程を備える。 The method for producing 1,3-butadiene according to one aspect of the present invention includes a dehydrogenation step in which butene is brought into contact with the above ferrite catalyst.
本発明によれば、ブテンの脱水素反応における１，３−ブタジエンの選択率を向上させることができる、ブテンの脱水素に用いるフェライト系触媒の製造方法、ブテンの脱水素に用いるフェライト系触媒、及び１，３−ブタジエンの製造方法が提供される。 According to the present invention, it is possible to improve the selectivity of 1,3-butadiene in butene dehydrogenation, a method for producing a ferrite catalyst used for butene dehydrogenation, a ferrite catalyst used for butene dehydrogenation, And a method for producing 1,3-butadiene.
以下では、本発明の好適な実施形態について詳細に説明する。本発明は下記の実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiment.
（ブテンの脱水素に用いるフェライト系触媒の製造方法）
本実施形態に係るフェライト系触媒の製造方法は、以下の第一の製法又は第二の製法である。第一の製法又は第二の製法によって得られるフェライト系触媒は、ブテンの脱水素反応（酸化的脱水素反応）において１，３−ブタジエンを選択的に生成させる活性に優れる。以下では、１，３−ブタジエンを選択的に生成させる活性を、単に「活性」と記す。
(Manufacturing method of ferrite catalyst used for dehydrogenation of butene)
The manufacturing method of the ferrite-type catalyst which concerns on this embodiment is the following 1st manufacturing methods or 2nd manufacturing methods. The ferrite catalyst obtained by the first production method or the second production method is excellent in the activity of selectively producing 1,3-butadiene in the butene dehydrogenation reaction (oxidative dehydrogenation reaction). Hereinafter, the activity for selectively producing 1,3-butadiene is simply referred to as “activity”.
［第一の製法］
第一の製法は、以下の調製工程と焼成工程とを備える。
[First production method]
The first production method includes the following preparation step and firing step.
＜調製工程＞
調製工程では、銅又はコバルトのうち少なくともいずれかを含む第一の金属塩を用いる。第一の金属塩は、例えば、硝酸銅（ＩＩ）（Ｃｕ（ＮＯ３）２）、硝酸銅（ＩＩ）の水和物（例えば、三水和物又は六水和物）、塩化銅（Ｉ）（ＣｕＣｌ）、塩化銅（ＩＩ）（ＣｕＣｌ２）、塩化銅（ＩＩ）の水和物（例えば、三水和物又は六水和物）、酢酸銅（Ｉ）（ＣＨ３ＣＯＯＣｕ）、酢酸銅（ＩＩ）（（ＣＨ３ＣＯＯ）２Ｃｕ）、酢酸銅（ＩＩ）の水和物（例えば、一水和物）、硝酸コバルト（ＩＩ）（Ｃｏ（ＮＯ３）２）、硝酸コバルト（ＩＩ）の水和物（例えば、三水和物又は六水和物）、硝酸コバルト（ＩＩＩ）（Ｃｏ（ＮＯ３）３）、塩化コバルト（ＩＩ）（ＣｏＣｌ２）、塩化コバルト（ＩＩ）の水和物（例えば、三水和物又は六水和物）、塩化コバルト（ＩＩＩ）（ＣｏＣｌ３）、酢酸コバルト（ＩＩ）（（ＣＨ３ＣＯＯ）２Ｃｏ）、又は酢酸コバルト（ＩＩ）の水和物（例えば、四水和物）であってよい。複数種の第一の金属塩を用いてよい。銅を含む第一の金属塩とコバルトを含む第一の金属塩とを併用してもよい。上記の第一の金属塩（特に、硝酸銅又は硝酸コバルト）は、焼成工程において分解し易く、焼成工程後に得られるフェライト系触媒に残存し難い傾向がある。
<Preparation process>
In the preparation step, a first metal salt containing at least one of copper and cobalt is used. The first metal salt is, for example, copper (II) nitrate (Cu (NO 3 ) 2 ), copper (II) nitrate hydrate (eg trihydrate or hexahydrate), copper chloride (I ) (CuCl), copper (II) chloride (CuCl 2 ), hydrated copper chloride (eg, trihydrate or hexahydrate), copper (I) acetate (CH 3 COOCu), acetic acid Copper (II) ((CH 3 COO) 2 Cu), copper acetate (II) hydrate (eg, monohydrate), cobalt nitrate (II) (Co (NO 3 ) 2 ), cobalt nitrate (II ) Hydrate (eg, trihydrate or hexahydrate), cobalt nitrate (III) (Co (NO 3 ) 3 ), cobalt chloride (II) (CoCl 2 ), cobalt chloride (II) water hydrate (e.g., trihydrate or hexahydrate), cobalt chloride (III) (CoCl 3), cobalt acetate (II ((CH 3 COO) 2 Co ), or a hydrate of cobalt acetate (II) (e.g., tetrahydrate) may be. Multiple types of first metal salts may be used. A first metal salt containing copper and a first metal salt containing cobalt may be used in combination. Said 1st metal salt (especially copper nitrate or cobalt nitrate) tends to decompose | disassemble in a baking process, and there exists a tendency which does not remain | survive easily in the ferrite catalyst obtained after a baking process.
調製工程では、鉄を含む第二の金属塩を用いる。第二の金属塩は、塩化鉄（ＩＩ）（ＦｅＣｌ２）、塩化鉄（ＩＩ）の水和物（例えば、四水和物）、塩化鉄（ＩＩＩ）（ＦｅＣｌ３）、塩化鉄（ＩＩＩ）の水和物（例えば、六水和物）、硝酸鉄（ＩＩ）（Ｆｅ（ＮＯ３）２）、硝酸鉄（ＩＩ）の水和物（例えば、六水和物又は九水和物）、硝酸鉄（ＩＩＩ）（Ｆｅ（ＮＯ３）３）、硝酸鉄（ＩＩＩ）の水和物（例えば、九水和物）、酢酸鉄（ＩＩ）（（ＣＨ３ＣＯＯ）２Ｆｅ）、又は酢酸鉄（ＩＩ）の水和物（例えば、四水和物）であってよい。複数種の第二の金属塩を用いてよい。上記の第二の金属塩（特に、硝酸鉄）は、焼成工程において分解し易く、焼成工程後に得られるフェライト系触媒に残存し難い傾向がある。 In the preparation step, a second metal salt containing iron is used. The second metal salt is iron (II) chloride (FeCl 2 ), hydrated iron chloride (eg tetrahydrate), iron (III) chloride (FeCl 3 ), iron (III) chloride. Hydrates (eg, hexahydrate), iron (II) nitrate (Fe (NO 3 ) 2 ), hydrates of iron (II) nitrate (eg, hexahydrate or nonahydrate), Iron nitrate (III) (Fe (NO 3 ) 3 ), hydrate of iron nitrate (eg, non-hydrate), iron acetate (II) ((CH 3 COO) 2 Fe), or iron acetate It may be a hydrate of (II) (eg tetrahydrate). Multiple types of second metal salts may be used. Said 2nd metal salt (especially iron nitrate) tends to decompose | disassemble in a baking process, and there exists a tendency for it not to remain | survive in the ferrite catalyst obtained after a baking process.
以下では、第一の金属塩又は第一金属塩に由来する銅イオン若しくはコバルトイオンと、第二の金属塩又は第二の金属塩に由来する鉄イオンと、を総称して、「金属種」と記す。 Hereinafter, the copper ion or cobalt ion derived from the first metal salt or the first metal salt and the iron ion derived from the second metal salt or the second metal salt are collectively referred to as “metal species”. .
調製工程では多孔質の炭素質材料を用いる。多孔質の炭素質材料は、例えば、活性炭、ミクロポーラスカーボン、メソポーラスカーボン、多孔質グラファイト（黒鉛チャート）、グラフェンの積層体、カーボンナノチューブ、カーボンクライオゲル、又はカーボンエアロゲルであってよい。多孔質の炭素質材料は、炭素以外の元素（ヘテロ元素）を含んでもよい。複数種の炭素質材料を用いてよい。 In the preparation process, a porous carbonaceous material is used. The porous carbonaceous material may be, for example, activated carbon, microporous carbon, mesoporous carbon, porous graphite (graphite chart), graphene laminate, carbon nanotube, carbon cryogel, or carbon aerogel. The porous carbonaceous material may contain elements other than carbon (hetero elements). Multiple types of carbonaceous materials may be used.
調製工程では、第一の金属塩と第二の金属塩とを含む溶液を、多孔質の炭素質材料に含浸させる。つまり、溶液中の金属種を炭素質材料に形成された多数の細孔内に侵入させる。例えば、金属種を含む溶液を攪拌した後、多孔質の炭素質材料を溶液に添加してもよい。金属種を含む溶液を、多孔質の炭素質材料に滴下してもよい。金属種を含む溶液を、多孔質の炭素質材料に噴霧してもよい。酸又は塩基を、金属種及び炭素質材料を含む溶液に添加して、溶液のｐＨを調整することにより、金属種を炭素質材料の表面又は細孔の内部に共沈させてもよい。 In the preparation step, a porous carbonaceous material is impregnated with a solution containing the first metal salt and the second metal salt. That is, the metal species in the solution is allowed to enter into a large number of pores formed in the carbonaceous material. For example, after a solution containing a metal species is stirred, a porous carbonaceous material may be added to the solution. A solution containing a metal species may be dropped on the porous carbonaceous material. The solution containing the metal species may be sprayed on the porous carbonaceous material. The metal species may be coprecipitated on the surface of the carbonaceous material or inside the pores by adding an acid or base to the solution containing the metal species and the carbonaceous material and adjusting the pH of the solution.
上記のような調製工程により、前駆体が生成する。前駆体とは、金属種と、金属種が付着した多孔質の炭素質材料と、を含む混合物であってよい。金属種が炭素質材料の外表面に付着していてよい。金属種が炭素質材料に形成された多数の細孔内に付着していてよい。金属種が炭素質材料に形成された多数の細孔内に充填されていてもよい。前駆体とは、炭素質材料と、フェライト系触媒の必須成分である金属元素と、を含む物質と言い換えてよい。また前駆体とは、焼成されることによりフェライト系触媒になる物質と言い換えてよい。 A precursor is produced | generated by the above preparation processes. The precursor may be a mixture including a metal species and a porous carbonaceous material to which the metal species are attached. Metal species may adhere to the outer surface of the carbonaceous material. Metal species may be deposited in the numerous pores formed in the carbonaceous material. The metal species may be filled in a large number of pores formed in the carbonaceous material. The precursor may be paraphrased as a substance containing a carbonaceous material and a metal element that is an essential component of the ferrite-based catalyst. The precursor may be rephrased as a substance that becomes a ferrite catalyst when fired.
ＭＦｅ２Ｏ４（ＭはＣｕ又はＣｏのうち少なくともいずれかである。）で表されるフェライト系触媒を製造する場合、溶液中の金属元素Ｍのモル数と溶液中の鉄のモル数との比が１：２となるように、第一の金属塩の量と第二の金属塩の量とを調整してよい。ただし、溶液中の金属元素Ｍのモル数と溶液中の鉄のモル数との比は、１：２に限定されない。 When producing a ferrite catalyst represented by MFe 2 O 4 (M is at least one of Cu and Co), the number of moles of the metal element M in the solution and the number of moles of iron in the solution The amount of the first metal salt and the amount of the second metal salt may be adjusted so that the ratio is 1: 2. However, the ratio between the number of moles of the metal element M in the solution and the number of moles of iron in the solution is not limited to 1: 2.
調製工程では、減圧又は加熱等の処理によって溶媒を除去し、乾燥した前駆体を調製してもよい。前駆体が、炭素質材料と、炭素質材料の表面又は細孔の内部に共沈した金属種とを有する場合、前駆体を含む溶液を濾過して、前駆体を回収してもよい。 In the preparation step, the dried precursor may be prepared by removing the solvent by a treatment such as reduced pressure or heating. When the precursor has a carbonaceous material and a metal species co-precipitated on the surface or pores of the carbonaceous material, the precursor-containing solution may be filtered to recover the precursor.
第一製法によって製造するフェライト系触媒の質量がＭｃａｔであり、調製工程に用いる多孔質の炭素質材料の質量Ｍｃａｒｂｏｎであるとき、Ｍｃａｒｂｏｎ／Ｍｃａｔは１〜３０であってよい。Ｍｃａｒｂｏｎ／Ｍｃａｔは２〜１５であってもよい。Ｍｃａｒｂｏｎ／Ｍｃａｔが１以上である場合、得られるフェライト系触媒の活性が向上し易い傾向がある。Ｍｃａｒｂｏｎ／Ｍｃａｔが３０以下である場合、得られるフェライト系触媒の失活又は劣化が抑制され易い傾向がある。調製工程に用いる多孔質の炭素質材料の質量Ｍｃａｒｂｏｎは、焼成工程において炭素質材料の全部が焼失する程度の量であってよい。なお、炭素質材料の焼失とは、例えば、炭素質材料の酸化又は燃焼による炭素質材料の分解を意味してよい。 When the mass of the ferrite-based catalyst produced by the first production method is M cat and the mass of the porous carbonaceous material M carbon used in the preparation step, M carbon / M cat may be 1 to 30. M carbon / M cat may be 2-15. When M carbon / M cat is 1 or more, the activity of the obtained ferrite catalyst tends to be improved. When M carbon / M cat is 30 or less, deactivation or deterioration of the obtained ferrite catalyst tends to be easily suppressed. The mass M carbon of the porous carbonaceous material used in the preparation step may be an amount such that all of the carbonaceous material is burned off in the firing step. The burnout of the carbonaceous material may mean, for example, decomposition of the carbonaceous material due to oxidation or combustion of the carbonaceous material.
第一の金属塩及び第二の金属塩を含む溶液を構成する溶媒は、第一の金属塩及び第二の金属塩を溶解するもの（例えば、極性溶媒）であればよい。溶媒は、例えば、水であってよく、アルコール等の非水溶媒であってもよい。 The solvent constituting the solution containing the first metal salt and the second metal salt may be any solvent that dissolves the first metal salt and the second metal salt (for example, a polar solvent). The solvent may be, for example, water or a nonaqueous solvent such as alcohol.
溶液は、有機酸を含んでもよい。有機酸は、例えば、クエン酸、アスコルビン酸、マレイン酸、フマル酸、ギ酸、酢酸又はシュウ酸であってよい。溶液が有機酸を含む場合、得られるフェライト系触媒の活性が向上する傾向がある。これらの有機酸は、溶液中において、銅イオン、コバルトイオン又は鉄イオンと錯体を形成してもよい。複数種の有機酸を用いてよい。 The solution may contain an organic acid. The organic acid may be, for example, citric acid, ascorbic acid, maleic acid, fumaric acid, formic acid, acetic acid or oxalic acid. When the solution contains an organic acid, the activity of the obtained ferrite catalyst tends to be improved. These organic acids may form complexes with copper ions, cobalt ions, or iron ions in the solution. Multiple types of organic acids may be used.
＜焼成工程＞
焼成工程では、前駆体を焼成することにより、フェライト系触媒を生成させる。焼成工程では、乾燥した前駆体を焼成してもよい。前駆体を含む溶液を加熱することにより、溶媒を除去すると共に前駆体を焼成してもよい。
<Baking process>
In the firing step, a ferrite catalyst is generated by firing the precursor. In the firing step, the dried precursor may be fired. By heating the solution containing the precursor, the solvent may be removed and the precursor may be fired.
焼成工程では、前駆体に含まれる炭素質材料の少なくとも一部を焼失させてもよい。炭素質材料に由来する炭素が、完成したフェライト系触媒中に残存してもよい。フェライト系触媒中に残存する炭素の含有率は、例えば、フェライト触媒全体に対して５質量％以下であってよい。前駆体に含まれる炭素質材料の全部を焼失させてもよい。焼成温度が低く、焼成時間が短いほど、炭素質材料に由来する炭素が、完成後のフェライト系触媒中に残存し易い。焼成温度が高く、焼成時間が長いほど、前駆体に含まれる炭素質材料を焼失させ易い。 In the firing step, at least a part of the carbonaceous material contained in the precursor may be burned off. Carbon derived from the carbonaceous material may remain in the finished ferrite catalyst. The carbon content remaining in the ferrite catalyst may be, for example, 5% by mass or less based on the entire ferrite catalyst. All of the carbonaceous material contained in the precursor may be burned out. The lower the firing temperature and the shorter the firing time, the easier the carbon derived from the carbonaceous material will remain in the finished ferrite catalyst. The higher the firing temperature and the longer the firing time, the easier the carbonaceous material contained in the precursor is burned off.
調製工程において用いる第一の金属塩が銅を含み、フェライト系触媒として銅を含むフェライト系触媒（例えば、ＣｕＦｅ２Ｏ４）を製造する場合、焼成温度（前駆体が置かれる雰囲気の温度）は、例えば２００〜８００℃であればよい。焼成温度は、２５０〜６００℃であってもよい。焼成温度が２００℃以上である場合、ＣｕＦｅ２Ｏ４からなる単一のフェライト相が生成し易く、生成するフェライト触媒の活性が向上し易い傾向がある。焼成温度が８００℃以下である場合、金属種の凝集が抑制され、生成するフェライト触媒の活性が向上し易い傾向がある。焼成時間は、例えば１〜１０時間であればよい。 When the first metal salt used in the preparation process contains copper and a ferrite catalyst containing copper as a ferrite catalyst (for example, CuFe 2 O 4 ) is produced, the firing temperature (the temperature of the atmosphere in which the precursor is placed) is For example, what is necessary is just 200-800 degreeC. The firing temperature may be 250 to 600 ° C. When the firing temperature is 200 ° C. or higher, a single ferrite phase composed of CuFe 2 O 4 tends to be generated, and the activity of the generated ferrite catalyst tends to be improved. When the firing temperature is 800 ° C. or lower, aggregation of metal species is suppressed, and the activity of the generated ferrite catalyst tends to be improved. The firing time may be, for example, 1 to 10 hours.
第一の製法によれば、従来の亜鉛又はマンガンを含むフェライト系触媒の製造方法に比べて、より低温での焼成工程によって、ＣｕＦｅ２Ｏ４を含むフェライト系触媒を製造することができる。 According to the first production method, a ferrite catalyst containing CuFe 2 O 4 can be produced by a firing process at a lower temperature than the conventional method of producing a ferrite catalyst containing zinc or manganese.
調製工程において用いる第一の金属塩がコバルトを含み、フェライト系触媒としてコバルトを含むフェライト系触媒（例えば、ＣｏＦｅ２Ｏ４）を製造する場合、焼成温度は、例えば２００〜８００℃であればよい。焼成温度は、２５０〜６００℃であってもよい。焼成温度が２００℃以上である場合、ＣｏＦｅ２Ｏ４からなる単一のフェライト相が生成し易く、生成するフェライト触媒の活性が向上し易い傾向がある。焼成温度が８００℃以下である場合、金属種の凝集が抑制され、生成するフェライト触媒の活性が向上し易い傾向がある。焼成時間は、例えば１〜１０時間であればよい。 When the first metal salt used in the preparation step contains cobalt and a ferrite catalyst (for example, CoFe 2 O 4 ) containing cobalt as the ferrite catalyst is produced, the firing temperature may be, for example, 200 to 800 ° C. . The firing temperature may be 250 to 600 ° C. When the firing temperature is 200 ° C. or higher, a single ferrite phase composed of CoFe 2 O 4 is likely to be generated, and the activity of the generated ferrite catalyst tends to be improved. When the firing temperature is 800 ° C. or lower, aggregation of metal species is suppressed, and the activity of the generated ferrite catalyst tends to be improved. The firing time may be, for example, 1 to 10 hours.
第一製法の焼成工程では、前駆体に含まれる炭素質材料（又は有機酸）に起因する以下の現象が起こる、と推測される。
焼成工程において前駆体に含まれる炭素質材料（又は有機酸）の燃焼熱が金属種の酸化及び焼成を促進する。その結果、炭素質材料を用いない従来の製造方法よりも低い焼成温度において、結晶化度の高い単一のフェライト相が生成し易い。
調製工程において、金属種が、比表面積の大きい多孔質の炭素質材料の外表面又は細孔の内部に吸着して分散するため、炭素質材料がない場合に比べて、金属種の凝集が抑制される。また焼成工程において、フェライト相の過度の成長が、炭素質材料（又は有機酸）の介在により抑制される。これらの理由により、フェライト相の結晶子径又はフェライト系触媒の一次粒子径が小さくなり易く、フェライト系触媒の比表面積又は活性点の数が増大し易い。
ただし、炭素質材料に係るメカニズムは、上記の現象に限定されるものではない。
In the firing process of the first manufacturing method, it is presumed that the following phenomenon occurs due to the carbonaceous material (or organic acid) contained in the precursor.
The combustion heat of the carbonaceous material (or organic acid) contained in the precursor in the firing step promotes oxidation and firing of the metal species. As a result, a single ferrite phase having a high degree of crystallinity is likely to be generated at a firing temperature lower than that of a conventional manufacturing method that does not use a carbonaceous material.
In the preparation process, the metal species are adsorbed and dispersed on the outer surface of the porous carbonaceous material having a large specific surface area or inside the pores. Is done. Further, in the firing step, excessive growth of the ferrite phase is suppressed by the intervention of the carbonaceous material (or organic acid). For these reasons, the crystallite diameter of the ferrite phase or the primary particle diameter of the ferrite catalyst tends to be small, and the specific surface area or the number of active points of the ferrite catalyst tends to increase.
However, the mechanism relating to the carbonaceous material is not limited to the above phenomenon.
［第二の製法］
第二の製法は、調製工程と焼成工程とを備える。第二の製法では、多孔質の炭素質材料ではなく、有機酸を用いる。
[Second production method]
The second production method includes a preparation step and a firing step. In the second production method, an organic acid is used instead of a porous carbonaceous material.
第二の製法の調製工程では、第一の金属塩と第二の金属塩と有機酸とを含む溶液から、前駆体を調製する。第二の製法で用いる第一の金属塩、第二の金属塩、有機酸及び溶媒は、第一の製法の場合と同様であってよい。調製工程で得られる前駆体とは、金属種と、有機酸と、を含む混合物であってよい。前駆体とは、有機酸と、フェライト系触媒の必須成分である金属元素と、を含む物質と言い換えてよい。また前駆体とは、焼成されることによりフェライト系触媒になる物質と言い換えてよい。調製工程では、減圧又は加熱等の処理によって溶媒を除去し、乾燥した前駆体を調製してもよい。 In the preparation step of the second production method, a precursor is prepared from a solution containing the first metal salt, the second metal salt, and the organic acid. The first metal salt, the second metal salt, the organic acid and the solvent used in the second production method may be the same as in the first production method. The precursor obtained in the preparation step may be a mixture containing a metal species and an organic acid. The precursor may be paraphrased as a substance containing an organic acid and a metal element that is an essential component of the ferrite catalyst. The precursor may be rephrased as a substance that becomes a ferrite catalyst when fired. In the preparation step, the dried precursor may be prepared by removing the solvent by a treatment such as reduced pressure or heating.
第二の製法の焼成工程では、第一製法と同様の条件下で、前駆体を焼成することにより、フェライト系触媒を生成させる。焼成工程では、乾燥した前駆体を焼成してもよい。前駆体を含む溶液を加熱することにより、溶媒を除去すると共に前駆体を焼成してもよい。 In the firing step of the second production method, a ferrite catalyst is produced by firing the precursor under the same conditions as in the first production method. In the firing step, the dried precursor may be fired. By heating the solution containing the precursor, the solvent may be removed and the precursor may be fired.
（ブテンの脱水素に用いるフェライト系触媒）
本実施形態に係るフェライト系触媒は、上記第一の製法又は第二の製法によって製造される。本実施形態に係るフェライト系触媒は、ＭＦｅ２Ｏ４（ＭはＣｕ又はＣｏのうち少なくともいずれかである。）を含む。
(Ferrite catalyst used for dehydrogenation of butene)
The ferrite catalyst according to the present embodiment is manufactured by the first manufacturing method or the second manufacturing method. The ferrite catalyst according to the present embodiment contains MFe 2 O 4 (M is at least one of Cu and Co).
フェライト系触媒における炭素の含有率は、フェライト系触媒の全質量に対して０〜５質量％である。炭素の含有率が高過ぎる場合、触媒全体に占める触媒活性成分（フェライト相）の質量の割合（及び触媒中の格子酸素の量）が減少することとなり、フェライト系触媒の活性が高くならない。炭素の含有率は０〜１．８質量％であってよい。炭素の含有率は０〜０．５質量％であってよい。炭素の含有率は０〜０．１質量％であってよい。炭素の含有率は０〜０．０１質量％であってよい。炭素の含有率は、例えば、熱重量分析（Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ Ａｎａｌｙｓｉｓ，ＴＧ）によって測定されてよい。 The carbon content in the ferrite catalyst is 0 to 5% by mass with respect to the total mass of the ferrite catalyst. If the carbon content is too high, the ratio of the mass of the catalytically active component (ferrite phase) in the entire catalyst (and the amount of lattice oxygen in the catalyst) will decrease, and the activity of the ferrite catalyst will not increase. The content of carbon may be 0 to 1.8% by mass. The content of carbon may be 0 to 0.5% by mass. The content of carbon may be 0 to 0.1% by mass. The content of carbon may be 0 to 0.01% by mass. The carbon content may be measured by, for example, thermogravimetric analysis (TG).
フェライト系触媒が炭素を含む場合、この炭素は多孔質の炭素質材料又は有機酸に由来するものであってよい。ただし、フェライト系触媒に含まれる炭素は、活性成分（ＭＦｅ２Ｏ４）の担体ではない。また、フェライト系触媒に含まれる炭素自体は、必ずしも活性を示さない。フェライト系触媒は炭素を含まなくてもよい。つまり、フェライト系触媒は、ＣｕｘＣｏ１−ｘＦｅ２Ｏ４（ｘは０〜１である）のみからなってよい。フェライト系触媒は、ＣｕＦｅ２Ｏ４のみからなってよい。ＣｏＦｅ２Ｏ４のみからなってよい。フェライト系触媒は不可避的な微量の不純物を含有してもよい。 When the ferritic catalyst contains carbon, the carbon may be derived from a porous carbonaceous material or an organic acid. However, carbon contained in the ferrite-based catalyst is not a carrier for the active component (MFe 2 O 4 ). Moreover, the carbon itself contained in the ferrite catalyst does not necessarily show activity. The ferrite catalyst may not contain carbon. That is, the ferrite catalyst may be composed only of Cu x Co 1-x Fe 2 O 4 (x is 0 to 1). The ferrite catalyst may consist only of CuFe 2 O 4 . It may consist only of CoFe 2 O 4 . Ferrite catalysts may contain inevitable trace amounts of impurities.
（１，３−ブタジエンの製造方法）
本実施形態に係る１，３−ブタジエンの製造方法は、ブテンを上記のフェライト系触媒に接触させる脱水素工程を備える。ブテンをフェライト系触媒に接触させることにより、ブテンの酸化的脱水素反応が起こり、１，３−ブタジエンが生成する。ブテンの酸化的脱水素反応では、フェライト系触媒を構成する格子酸素が消費されてよい。ブテンの脱水素反応では、副生成物として、例えば、水素、水、一酸化炭素及び二酸化炭素が生成してもよい。ブテンの酸化的脱水素反応において、ブテン、１，３−ブタジエン、及び副生成物のいずれも気体であってよい。
(Method for producing 1,3-butadiene)
The method for producing 1,3-butadiene according to this embodiment includes a dehydrogenation step in which butene is brought into contact with the above-described ferrite catalyst. By bringing butene into contact with a ferrite-based catalyst, butene oxidative dehydrogenation occurs, and 1,3-butadiene is produced. In the oxidative dehydrogenation reaction of butene, lattice oxygen constituting the ferrite catalyst may be consumed. In the dehydrogenation reaction of butene, for example, hydrogen, water, carbon monoxide, and carbon dioxide may be generated as by-products. In the oxidative dehydrogenation reaction of butene, any of butene, 1,3-butadiene, and by-products may be a gas.
１，３−ブタジエンの製造に用いるブテンは、１−ブテン又は２−ブテンであってよい。ブテンは、１−ブテン及び２−ブテンの混合物であってよい。２−ブテンは、ｃｉｓ−２−ブテン及びｔｒａｎｓ−２−ブテンのうち一方又は両方であってよい。 The butene used for the production of 1,3-butadiene may be 1-butene or 2-butene. The butene may be a mixture of 1-butene and 2-butene. The 2-butene may be one or both of cis-2-butene and trans-2-butene.
本実施形態では、従来のフェライト系触媒を用いる場合に比べて、ブテンの脱水素反応における１，３−ブタジエンの選択率が向上する。また本実施形態では、従来のフェライト系触媒を用いる場合に比べて、より低温（例えば、２００〜３００℃）で、１，３−ブタジエンを高い選択率で生成させることができる。ＣｕＦｅ２Ｏ４を含むフェライト系触媒は、ＣｏＦｅ２Ｏ４を含むフェライト系触媒によりも、低温での活性に優れる傾向がある。 In this embodiment, the selectivity of 1,3-butadiene in the dehydrogenation reaction of butene is improved as compared with the case where a conventional ferrite catalyst is used. In the present embodiment, 1,3-butadiene can be produced at a higher selectivity at a lower temperature (for example, 200 to 300 ° C.) than in the case of using a conventional ferrite catalyst. A ferrite-based catalyst containing CuFe 2 O 4 tends to be more excellent in activity at low temperatures than a ferrite-based catalyst containing CoFe 2 O 4 .
フェライト系触媒がＣｕＦｅ２Ｏ４を含む場合、脱水素工程における反応温度は、例えば、１８０〜４５０℃、２００〜３００℃、又は２５０〜２７０℃であってよい。フェライト系触媒がＣｏＦｅ２Ｏ４を含む場合、脱水素工程における反応温度は、例えば、３５０〜５００℃、４００〜４８０℃又は４００〜４５０℃であってよい。脱水素工程における反応温度が上記範囲内にある場合、ブテンの過度の脱水素又は過度の酸化が抑制され易く、副生成物の生成が抑制され易く、１，３−ブタジエンが高い選択率で生成し易い傾向がある。なお、脱水素工程における反応温度は、例えば、脱水素工程におけるフェライト系触媒の温度（例えば、反応器内に設置される触媒層の温度）であってよい。 When the ferrite-based catalyst contains CuFe 2 O 4 , the reaction temperature in the dehydrogenation step may be, for example, 180 to 450 ° C., 200 to 300 ° C., or 250 to 270 ° C. When the ferrite-based catalyst contains CoFe 2 O 4 , the reaction temperature in the dehydrogenation step may be, for example, 350 to 500 ° C., 400 to 480 ° C., or 400 to 450 ° C. When the reaction temperature in the dehydrogenation step is within the above range, excessive dehydrogenation or excessive oxidation of butene is easily suppressed, generation of by-products is easily suppressed, and 1,3-butadiene is generated with high selectivity. It tends to be easy to do. The reaction temperature in the dehydrogenation step may be, for example, the temperature of the ferrite catalyst in the dehydrogenation step (for example, the temperature of the catalyst layer installed in the reactor).
フェライト系触媒に対するブテンの供給速度（単位時間当たりのブテンの流量）、及び脱水素反応の反応時間は、特に限定されない。ブテンの供給速度、及び反応時間は、フェライト系触媒の量、反応温度、又は目標とする１，３−ブタジエンの単位時間当たりの生産量に応じて、適宜調整すればよい。 The butene supply rate (butene flow rate per unit time) to the ferrite catalyst and the reaction time of the dehydrogenation reaction are not particularly limited. The butene supply rate and the reaction time may be appropriately adjusted according to the amount of the ferrite catalyst, the reaction temperature, or the target production amount of 1,3-butadiene per unit time.
本実施形態に係るフェライト系触媒（ＣｕＦｅ２Ｏ４）を用いたブテンの酸化的脱水素反応の進行に伴い、フェライト系触媒のＸ線回折パターンにおいて銅単体（金属銅）の構造に固有のピークが発現することを、本発明者らは実験により確認している。このことは、酸化的脱水素反応の進行に伴い、フェライト系触媒を構成する格子酸素が消費されることを示唆している。酸化的脱水素反応に用いた後のフェライト系触媒を再酸化すると、フェライト系触媒のＸ線回折パターンにおいて銅単体（金属銅）の構造に固有のピークが消失することを、本発明者らは実験により確認している。このことは、フェライト系触媒の再酸化により、フェライト系触媒中の酸素空孔に格子酸素が補充されたことを示唆している。以上の実験結果は、本実施形態に係るフェライト系触媒をブテンの酸化的脱水素反応において連続的に使用できることを示唆している。 As the oxidative dehydrogenation reaction of butene using the ferrite-based catalyst (CuFe 2 O 4 ) according to the present embodiment proceeds, peaks inherent to the structure of simple copper (metal copper) in the X-ray diffraction pattern of the ferrite-based catalyst The present inventors have confirmed through experiments that the expression of. This suggests that lattice oxygen constituting the ferrite catalyst is consumed as the oxidative dehydrogenation proceeds. The present inventors have found that, when the ferrite catalyst after being used in the oxidative dehydrogenation reaction is reoxidized, the peak inherent to the structure of the copper simple substance (metal copper) disappears in the X-ray diffraction pattern of the ferrite catalyst. Confirmed by experiment. This suggests that lattice oxygen is replenished in the oxygen vacancies in the ferrite catalyst by reoxidation of the ferrite catalyst. The above experimental results suggest that the ferrite catalyst according to the present embodiment can be continuously used in the oxidative dehydrogenation reaction of butene.
以下では実施例及び比較例により本発明をさらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
（実施例１）
［触媒の製造］
＜調製工程＞
Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ（第一の金属塩）と、Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ（第二の金属塩）と、を１２０ｍＬの純水に溶解させて、溶液を作製した。純水に添加したＣｏ（ＮＯ３）２・６Ｈ２Ｏの質量は１．７４６ｇであった。純水に添加したＦｅ（ＮＯ３）３・９Ｈ２Ｏの質量は４．８４８ｇであった。純水におけるＣｏのモル数とＦｅのモル数の比を１：２に調整した。活性炭（多孔質の炭素質材料）を上記溶液に添加した後、溶液を一晩攪拌した。活性炭の質量は、焼成工程後に得られるべきフェライト系触媒の質量の約４倍（４．００ｇ）に調整した。攪拌後の溶液を、ロータリーエバポレーターを用いて６０〜７０℃で加熱して溶液から水分を除去して、前駆体を得た。この前駆体を減圧下において７０℃で一晩加熱することにより、前駆体を乾燥させた。
Example 1
[Manufacture of catalyst]
<Preparation process>
Co (NO 3 ) 2 · 6H 2 O (first metal salt) and Fe (NO 3 ) 3 · 9H 2 O (second metal salt) are dissolved in 120 mL of pure water to obtain a solution. Produced. The mass of Co (NO 3 ) 2 · 6H 2 O added to pure water was 1.746 g. Pure water was added Fe (NO 3) 3 · 9H 2 O mass is 4.848G. The ratio of the number of moles of Co to the number of moles of Fe in pure water was adjusted to 1: 2. After adding activated carbon (porous carbonaceous material) to the solution, the solution was stirred overnight. The mass of the activated carbon was adjusted to about 4 times (4.00 g) the mass of the ferrite catalyst to be obtained after the firing step. The solution after stirring was heated at 60 to 70 ° C. using a rotary evaporator to remove moisture from the solution to obtain a precursor. The precursor was dried by heating at 70 ° C. under reduced pressure overnight.
＜焼成工程＞
焼成工程では、以下の手順で前駆体を焼成して、実施例１の触媒を得た。まず、前駆体をマッフル炉内に設置し、マッフル炉内に空気を流通させながら、マッフル炉内を３時間かけて常温から５００℃まで昇温した。さらにマッフル炉内の温度を５００℃に２時間維持した。焼成工程によって得られた触媒の質量は約１ｇであった。下記の表１では、実施例１の製造方法を「含浸法」と記す。
<Baking process>
In the firing step, the precursor was fired according to the following procedure, and the catalyst of Example 1 was obtained. First, the precursor was placed in a muffle furnace, and the temperature in the muffle furnace was raised from room temperature to 500 ° C. over 3 hours while circulating air in the muffle furnace. Further, the temperature in the muffle furnace was maintained at 500 ° C. for 2 hours. The mass of the catalyst obtained by the calcination process was about 1 g. In Table 1 below, the production method of Example 1 is referred to as “impregnation method”.
＜触媒の分析＞
実施例１の触媒のＸ線回折パターンを測定した。実施例１のＸ線回折パターンを図１に示す。Ｘ線回折パターンにより、実施例１の触媒がＣｏＦｅ２Ｏ４（フェライト系触媒）であることが確認された。熱重量分析の結果、実施例１のフェライト系触媒における炭素の含有率が、１．２質量％であることが確認された。
<Analysis of catalyst>
The X-ray diffraction pattern of the catalyst of Example 1 was measured. The X-ray diffraction pattern of Example 1 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Example 1 was CoFe 2 O 4 (ferrite-based catalyst). As a result of thermogravimetric analysis, it was confirmed that the carbon content in the ferrite catalyst of Example 1 was 1.2% by mass.
［１，３−ブタジエンの製造］
実施例１のフェライト系触媒２００ｍｇを反応器内に設置した。１−ブテン及びアルゴンの混合気体（原料ガス）を反応器内に供給し、１−ブテンをフェライト系触媒に接触させ、１−ブテンの脱水素反応を行った。脱水素反応の反応温度（フェライト系触媒の温度）は４００℃に調整した。酸化的脱水素反応の反応時間は８分であった。反応器内に供給される１−ブテンの流量は５ｍｌ／分に調整した。反応器内に供給されるアルゴンの流量は２５ｍｌ／分に調整した。
[Production of 1,3-butadiene]
200 mg of the ferrite-based catalyst of Example 1 was placed in the reactor. A mixed gas (raw material gas) of 1-butene and argon was supplied into the reactor, and 1-butene was brought into contact with a ferrite catalyst to carry out a dehydrogenation reaction of 1-butene. The reaction temperature of the dehydrogenation reaction (the temperature of the ferrite catalyst) was adjusted to 400 ° C. The reaction time for the oxidative dehydrogenation reaction was 8 minutes. The flow rate of 1-butene fed into the reactor was adjusted to 5 ml / min. The flow rate of argon supplied into the reactor was adjusted to 25 ml / min.
脱水素反応の生成物（生成ガス）をガスクロマトグラフィーで分析した。生成ガスは１，３−ブタジエン（Ｃ４Ｈ６）を含むことが確認された。生成ガスは、ｃｉｓ−２−ブテン、ｔｒａｎｓ−２−ブテン、一酸化炭素、二酸化炭素、水素及び水も含むことが確認された。未反応の１−ブテンもガスクロマトグラフィーによって検出された。生成ガスが含む各成分のモル分率を、各成分に由来するクロマトグラムのピーク面積の比から求めた。生成ガスが含む各炭素化合物のモル分率を下記の表２に示す。表２に記載の「ｃｉｓ−Ｃ４’」はｃｉｓ−２−ブテンを意味する。表２に記載の「ｔｒａｎｓ−Ｃ４’」はｔｒａｎｓ−２−ブテンを意味する。１−ブテンの転化率１を表２に示す。転化率１は、下記式で定義される。
転化率１（％） ＝ （１−（ｍ１／ｍ２）×１００
ｍ１は、脱水素反応の生成ガスに含まれる１−ブテンのモル数である。ｍ２は、原料ガスにおける１−ブテンのモル数である。ｍ１は、生成ガスについてのガスクロマトグラフィーに基づき求められる値である。ｍ２は、原料ガスについてのガスクロマトグラフィーに基づき求められる値である。
The product (product gas) of the dehydrogenation reaction was analyzed by gas chromatography. It was confirmed that the generated gas contained 1,3-butadiene (C 4 H 6 ). The product gas was confirmed to contain cis-2-butene, trans-2-butene, carbon monoxide, carbon dioxide, hydrogen, and water. Unreacted 1-butene was also detected by gas chromatography. The mole fraction of each component contained in the product gas was determined from the ratio of peak areas of chromatograms derived from each component. The molar fraction of each carbon compound contained in the product gas is shown in Table 2 below. “Cis-C4 ′” in Table 2 means cis-2-butene. “Trans-C4 ′” described in Table 2 means trans-2-butene. The conversion rate 1 of 1-butene is shown in Table 2. The conversion rate 1 is defined by the following formula.
Conversion rate 1 (%) = (1- (m1 / m2) × 100
m1 is the number of moles of 1-butene contained in the product gas of the dehydrogenation reaction. m2 is the number of moles of 1-butene in the raw material gas. m1 is a value determined on the basis of gas chromatography on the product gas. m2 is a value obtained based on gas chromatography for the raw material gas.
１−ブテンの転化率２を表１に示す。転化率２は、下記式で定義される。
転化率２（％） ＝ 転化率１×（１−ｍ３）
ｍ３は、生成ガスにおけるｃｉｓ−２−ブテンのモル分率と、生成ガスにおけるｔｒａｎｓ−２−ブテンのモル分率と、の和である。
Table 1 shows the conversion rate 1 of 1-butene. The conversion rate 2 is defined by the following formula.
Conversion rate 2 (%) = Conversion rate 1 x (1-m3)
m3 is the sum of the molar fraction of cis-2-butene in the product gas and the molar fraction of trans-2-butene in the product gas.
１，３−ブタジンエンの選択率を表１に示す。選択率は、下記式で定義される。
選択率（％） ＝ ｍ４／（１−ｍ３）
ｍ４は、生成ガスにおける１，３−ブタジンエンのモル分率である。
The selectivity for 1,3-butadiene is shown in Table 1. The selectivity is defined by the following formula.
Selectivity (%) = m4 / (1-m3)
m4 is the molar fraction of 1,3-butadiene in the product gas.
１，３−ブタジンエンの収率を表１に示す。収率は、下記式で定義される。
収率（％） ＝ 転化率１×ｍ４
The yield of 1,3-butadiene is shown in Table 1. The yield is defined by the following formula.
Yield (%) = Conversion 1 x m4
以下の昇温反応法（Ｔｅｍｐｅｒａｔｕｒｅ Ｐｒｏｇｒａｍｍｅｄ Ｒｅａｃｔｉｏｎ：ＴＰＲ）に基づく測定によって、１−ブテンの酸化的脱水素が実施例１のフェライト系触媒の格子酸素によって引き起されるか否かを調べた。 Whether or not oxidative dehydrogenation of 1-butene is caused by lattice oxygen of the ferrite-based catalyst of Example 1 was examined by the measurement based on the following temperature programmed reaction (TPR).
ＴＰＲに基づく測定では、実施例１のフェライト系触媒を流通型反応器内に設置した。そして、フェライト系触媒の温度を上昇させながら、１−ブテンを反応器内に供給し続け、各温度において反応器内から排出されるガスの組成を質量分析器で分析した。ＴＰＲに基づく測定の結果を図９に示す。図９の縦軸は、反応器内から排出されるガス中の各成分のモル濃度を示す対数軸である。図１０及び１１の縦軸についても同様である。 In the measurement based on TPR, the ferrite catalyst of Example 1 was installed in a flow reactor. Then, while increasing the temperature of the ferrite catalyst, 1-butene was continuously supplied into the reactor, and the composition of the gas discharged from the reactor at each temperature was analyzed with a mass spectrometer. The result of the measurement based on TPR is shown in FIG. The vertical axis in FIG. 9 is a logarithmic axis indicating the molar concentration of each component in the gas discharged from the reactor. The same applies to the vertical axis in FIGS.
（実施例２及び３）
実施例２及び３では、実施例１のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。実施例２及び３では、反応温度を表１に示す値に調整した。これらの事項以外は、実施例１と同様の方法で、実施例２及び３それぞれの１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例２及び３においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例２及び３それぞれの生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例２及び３それぞれの転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。
(Examples 2 and 3)
In Examples 2 and 3, 1-butene was dehydrogenated using the ferrite catalyst of Example 1. In Examples 2 and 3, the reaction temperature was adjusted to the values shown in Table 1. Except for these matters, the dehydrogenation reaction of 1-butene in each of Examples 2 and 3 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, in Examples 2 and 3, it was confirmed that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in each product gas of Examples 2 and 3. Table 1 shows the conversion rate 2 of each of Examples 2 and 3, and the selectivity and yield of 1,3-butadiene.
（実施例４）
［触媒の製造］
＜調製工程＞
Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ（第一の金属塩）と、Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ（第二の金属塩）と、クエン酸（有機酸）と、を３０ｍＬの純水に溶解させて、溶液を作製した。純水に添加したＣｏ（ＮＯ３）２・６Ｈ２Ｏの質量は１．７４６ｇであった。純水に添加したＦｅ（ＮＯ３）３・９Ｈ２Ｏの質量は４．８４８ｇであった。溶液におけるＣｏのモル数とＦｅのモル数の比を１：２に調整した。純水に添加したクエン酸の質量は３．４５８ｇであり、そのモル数は、第一金属塩及び第二金属塩の総モル数と等しかった。この溶液を一晩攪拌した。攪拌後の溶液を、ロータリーエバポレーターを用いて６０〜７０℃で加熱して溶液から水分を除去して、前駆体を得た。この前駆体を減圧下において７０℃で一晩加熱することにより、実施例４の前駆体を乾燥させた。
Example 4
[Manufacture of catalyst]
<Preparation process>
Co (NO 3 ) 2 · 6H 2 O (first metal salt), Fe (NO 3 ) 3 · 9H 2 O (second metal salt), and citric acid (organic acid) in 30 mL of pure A solution was prepared by dissolving in water. The mass of Co (NO 3 ) 2 · 6H 2 O added to pure water was 1.746 g. Pure water was added Fe (NO 3) 3 · 9H 2 O mass is 4.848G. The ratio of the number of moles of Co to the number of moles of Fe in the solution was adjusted to 1: 2. The mass of citric acid added to pure water was 3.458 g, and the number of moles thereof was equal to the total number of moles of the first metal salt and the second metal salt. The solution was stirred overnight. The solution after stirring was heated at 60 to 70 ° C. using a rotary evaporator to remove moisture from the solution to obtain a precursor. The precursor of Example 4 was dried by heating the precursor at 70 ° C. under reduced pressure overnight.
＜焼成工程＞
焼成工程では、以下の手順で前駆体を焼成して、実施例４の触媒を得た。まず、前駆体をマッフル炉内に設置し、マッフル炉内に空気を流通させながら、マッフル炉内を３時間かけて常温から５００℃まで昇温した。さらにマッフル炉内の温度を５００℃に２時間維持した。以上の実施例４の製造方法において、活性炭は用いなかった。表１では、実施例４の製造方法を「クエン酸法」と記す。
<Baking process>
In the calcining step, the precursor was calcined by the following procedure to obtain the catalyst of Example 4. First, the precursor was placed in a muffle furnace, and the temperature in the muffle furnace was raised from room temperature to 500 ° C. over 3 hours while circulating air in the muffle furnace. Further, the temperature in the muffle furnace was maintained at 500 ° C. for 2 hours. In the production method of Example 4 above, activated carbon was not used. In Table 1, the production method of Example 4 is referred to as “citric acid method”.
＜フェライト系触媒の分析＞
実施例４の触媒のＸ線回折パターンを測定した。実施例４のＸ線回折パターンを図２に示す。Ｘ線回折パターンにより、実施例４の触媒がＣｏＦｅ２Ｏ４（フェライト系触媒）であることが確認された。
<Analysis of ferrite catalyst>
The X-ray diffraction pattern of the catalyst of Example 4 was measured. The X-ray diffraction pattern of Example 4 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Example 4 was CoFe 2 O 4 (ferrite-based catalyst).
［１，３−ブタジエンの製造］
実施例４のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。触媒の組成を除いて実施例１と同様の方法で、実施例４の１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例４においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例４の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例４の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。
[Production of 1,3-butadiene]
Using the ferrite-based catalyst of Example 4, 1-butene was dehydrogenated. The 1-butene dehydrogenation reaction of Example 4 was carried out in the same manner as in Example 1 except for the catalyst composition. As a result of analysis based on the same method as in Example 1, it was confirmed that the product gas of the dehydrogenation reaction also contains 1,3-butadiene in Example 4. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Example 4. Table 1 shows the conversion rate of Example 4 and the selectivity and yield of 1,3-butadiene.
（実施例５）
実施例５の触媒の製造では、第一の金属塩として、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏの代わりに、１．４５ｇのＣｕ（ＮＯ３）２・６Ｈ２Ｏを用いた。この事項を除いて実施例１と同様の方法で、実施例５の触媒を作製した。表１では、実施例５の製造方法を「含浸法」と記す。
(Example 5)
In the manufacture of the catalyst of Example 5, 1.45 g of Cu (NO 3 ) 2 · 6H 2 O was used as the first metal salt instead of Co (NO 3 ) 2 · 6H 2 O. Except for this matter, the catalyst of Example 5 was produced in the same manner as in Example 1. In Table 1, the production method of Example 5 is described as “impregnation method”.
実施例１と同様の方法で、実施例５の触媒のＸ線回折パターンを測定した。実施例５のＸ線回折パターンを図３に示す。Ｘ線回折パターンにより、実施例５の触媒がＣｕＦｅ２Ｏ４（フェライト系触媒）であることが確認された。熱重量分析の結果、実施例５のフェライト系触媒における炭素の含有率が、０．９質量％であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Example 5 was measured. The X-ray diffraction pattern of Example 5 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Example 5 was CuFe 2 O 4 (ferrite-based catalyst). As a result of thermogravimetric analysis, it was confirmed that the carbon content in the ferrite catalyst of Example 5 was 0.9 mass%.
実施例５のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。実施例５では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、実施例５の１−ブテンの酸化的脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例５においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例５の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例５の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite-based catalyst of Example 5, 1-butene was dehydrogenated. In Example 5, the reaction temperature was adjusted to the values shown in Table 1. Except for these items, the oxidative dehydrogenation of 1-butene of Example 5 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, it was also confirmed in Example 5 that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Example 5. Table 1 shows the conversion rate of Example 5 and the selectivity and yield of 1,3-butadiene.
実施例５のフェライト系触媒を用いて、実施例１と同様の方法で、ＴＰＲに基づく測定を行った。実施例５のＴＰＲに基づく測定の結果を図１０に示す。図１０に示すように、実施例５のフェライト系触媒を用いた１−ブテンの脱水素反応では、２００℃近傍から高温の領域にわたって、１，３−ブタジエン及び水の生成量が増加することが確認された。また２００℃近傍では、水素の生成量は略一定であった。このことは、２００℃程度の低温において１−ブテンの酸化的脱水素が促進されることを示唆している。また、図１０に示すように、２００℃近傍の低温では、二酸化炭素の生成量が少ないことが確認された。このことは、２００℃近傍の低温では、１−ブテンの完全酸化が抑制されていることを示唆している。 Using the ferrite-based catalyst of Example 5, measurement based on TPR was performed in the same manner as in Example 1. The result of the measurement based on the TPR of Example 5 is shown in FIG. As shown in FIG. 10, in the 1-butene dehydrogenation reaction using the ferrite catalyst of Example 5, the production amounts of 1,3-butadiene and water may increase from around 200 ° C. to a high temperature region. confirmed. In the vicinity of 200 ° C., the amount of hydrogen produced was substantially constant. This suggests that oxidative dehydrogenation of 1-butene is promoted at a low temperature of about 200 ° C. Further, as shown in FIG. 10, it was confirmed that the amount of carbon dioxide produced was small at a low temperature around 200 ° C. This suggests that complete oxidation of 1-butene is suppressed at a low temperature around 200 ° C.
（実施例６〜９）
実施例６〜９では、実施例５のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。実施例６〜９では、反応温度を表１に示す値に調整した。これらの事項以外は、実施例５と同様の方法で、実施例６〜９それぞれの１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例６〜９においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例６〜９それぞれの生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例６〜９それぞれの転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。
(Examples 6 to 9)
In Examples 6 to 9, 1-butene was dehydrogenated using the ferrite catalyst of Example 5. In Examples 6 to 9, the reaction temperature was adjusted to the values shown in Table 1. Except for these items, the dehydrogenation reaction of 1-butene in each of Examples 6 to 9 was performed in the same manner as in Example 5. As a result of analysis based on the same method as in Example 1, in Examples 6 to 9, it was confirmed that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of each of Examples 6 to 9. Table 1 shows the conversion rate 2 of each of Examples 6 to 9, and the selectivity and yield of 1,3-butadiene.
（実施例１０）
実施例１０の触媒の製造では、第一の金属塩として、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏの代わりに、１．４５ｇのＣｕ（ＮＯ３）２・６Ｈ２Ｏを用いた。また、実施例１０では、第一の金属塩及び第二の金属塩のみならず、クエン酸を純水に添加して、溶液を作製した。純水に添加したクエン酸の質量３．４５８ｇであり、そのモル数は、第一金属塩及び第二金属塩の総モル数と等しかった。これらの事項を除いて、実施例１と同様の方法で、実施例１０の触媒を作製した。表１では、実施例１０の製造方法を「含浸・クエン酸法」と記す。
(Example 10)
In the manufacture of the catalyst of Example 10, 1.45 g of Cu (NO 3 ) 2 .6H 2 O was used as the first metal salt instead of Co (NO 3 ) 2 .6H 2 O. In Example 10, not only the first metal salt and the second metal salt but also citric acid was added to pure water to prepare a solution. The mass of citric acid added to pure water was 3.458 g, and the number of moles thereof was equal to the total number of moles of the first metal salt and the second metal salt. Except for these matters, the catalyst of Example 10 was produced in the same manner as in Example 1. In Table 1, the production method of Example 10 is referred to as “impregnation / citric acid method”.
実施例１と同様の方法で、実施例１０の触媒のＸ線回折パターンを測定した。実施例５のＸ線回折パターンを図４に示す。Ｘ線回折パターンにより、実施例１０の触媒がＣｕＦｅ２Ｏ４（フェライト系触媒）であることが確認された。熱重量分析の結果、実施例１０のフェライト系触媒における炭素の含有率が、０．９質量％であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Example 10 was measured. The X-ray diffraction pattern of Example 5 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Example 10 was CuFe 2 O 4 (ferrite-based catalyst). As a result of thermogravimetric analysis, it was confirmed that the carbon content in the ferrite-based catalyst of Example 10 was 0.9% by mass.
実施例１０のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。実施例１０では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、実施例１０の１−ブテンの酸化的脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例１０においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例１０の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例１０の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite catalyst of Example 10, 1-butene was dehydrogenated. In Example 10, the reaction temperature was adjusted to the values shown in Table 1. Except for these items, the oxidative dehydrogenation of 1-butene of Example 10 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, it was confirmed in Example 10 that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Example 10. Table 1 shows the conversion rate of Example 10 and the selectivity and yield of 1,3-butadiene.
（実施例１１及び１２）
実施例１１及び１２では、実施例１０のフェライト系触媒を用いて１−ブテンの酸化的脱水素反応を行った。実施例１１及び１２では、反応温度を表１に示す値に調整した。これらの事項以外は、実施例１と同様の方法で、実施例１１及び１２それぞれの１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例１１及び１２においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例１１及び１２それぞれの生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例１１及び１２それぞれの転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。
(Examples 11 and 12)
In Examples 11 and 12, oxidative dehydrogenation of 1-butene was performed using the ferrite catalyst of Example 10. In Examples 11 and 12, the reaction temperature was adjusted to the values shown in Table 1. Except for these matters, the dehydrogenation reaction of 1-butene in each of Examples 11 and 12 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, in Examples 11 and 12, it was confirmed that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of each of Examples 11 and 12. Table 1 shows the conversion rate 2 of each of Examples 11 and 12, and the selectivity and yield of 1,3-butadiene.
（実施例１３）
実施例１３の触媒の製造では、第一の金属塩として、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏの代わりに、１．４５ｇのＣｕ（ＮＯ３）２・６Ｈ２Ｏを用いた。この事項を除いて実施例４と同様の方法で、実施例１３の触媒を作製した。表１では、実施例１３の製造方法を「クエン酸法」と記す。
(Example 13)
In the manufacture of the catalyst of Example 13, 1.45 g of Cu (NO 3 ) 2 · 6H 2 O was used as the first metal salt instead of Co (NO 3 ) 2 · 6H 2 O. A catalyst of Example 13 was produced in the same manner as in Example 4 except for this matter. In Table 1, the production method of Example 13 is described as “citric acid method”.
実施例１と同様の方法で、実施例１３の触媒のＸ線回折パターンを測定した。実施例１３のＸ線回折パターンを図５に示す。Ｘ線回折パターンにより、実施例１３の触媒がＣｕＦｅ２Ｏ４（フェライト系触媒）であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Example 13 was measured. The X-ray diffraction pattern of Example 13 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Example 13 was CuFe 2 O 4 (ferrite-based catalyst).
実施例１３のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。実施例１３では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、実施例１３の１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例１３においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例１３の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例１３の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite catalyst of Example 13, 1-butene was dehydrogenated. In Example 13, the reaction temperature was adjusted to the values shown in Table 1. Except for these items, the dehydrogenation reaction of 1-butene of Example 13 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, it was also confirmed in Example 13 that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Example 13. Table 1 shows the conversion rate of Example 13 and the selectivity and yield of 1,3-butadiene.
（実施例１４及び１５）
実施例１４及び１５では、実施例１３のフェライト系触媒を用いて１−ブテンの酸化的脱水素反応を行った。実施例１４及び１５では、反応温度を表１に示す値に調整した。これらの事項以外は、実施例１と同様の方法で、実施例１４及び１５それぞれの１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、実施例１４及び１５においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。実施例１４及び１５それぞれの生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。実施例１４及び１５それぞれの転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。
(Examples 14 and 15)
In Examples 14 and 15, the oxidative dehydrogenation of 1-butene was performed using the ferrite catalyst of Example 13. In Examples 14 and 15, the reaction temperature was adjusted to the values shown in Table 1. Except for these matters, the dehydrogenation reaction of 1-butene in each of Examples 14 and 15 was performed in the same manner as in Example 1. As a result of analysis based on the same method as in Example 1, in Examples 14 and 15, it was confirmed that the product gas of the dehydrogenation reaction contained 1,3-butadiene. Table 2 shows the molar fraction and the conversion 1 of each carbon compound contained in the product gases of Examples 14 and 15. Table 1 shows the conversion rate 2 of each of Examples 14 and 15 and the selectivity and yield of 1,3-butadiene.
（比較例１）
比較例１の触媒の製造では、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏの代わりに、１．７２２ｇのＭｎ（ＮＯ３）２・６Ｈ２Ｏを用いた。この事項を除いて実施例１と同様の方法で、比較例１の触媒を作製した。表１では、比較例１の製造方法を「含浸法」と記す。
(Comparative Example 1)
In the production of the catalyst of Comparative Example 1, 1.722 g of Mn (NO 3 ) 2 .6H 2 O was used instead of Co (NO 3 ) 2 .6H 2 O. A catalyst of Comparative Example 1 was produced in the same manner as in Example 1 except for this matter. In Table 1, the production method of Comparative Example 1 is referred to as “impregnation method”.
実施例１と同様の方法で、比較例１の触媒のＸ線回折パターンを測定した。比較例１のＸ線回折パターンを図６に示す。Ｘ線回折パターンにより、比較例１の触媒がＭｎＦｅ２Ｏ４（フェライト系触媒）であることが確認された。熱重量分析の結果、比較例１のフェライト系触媒における炭素の含有率が、１．０質量％であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Comparative Example 1 was measured. The X-ray diffraction pattern of Comparative Example 1 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Comparative Example 1 was MnFe 2 O 4 (ferrite-based catalyst). As a result of thermogravimetric analysis, it was confirmed that the carbon content in the ferrite-based catalyst of Comparative Example 1 was 1.0% by mass.
比較例１のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。比較例１では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、比較例１の１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、比較例１においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。比較例１の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。比較例１の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite-based catalyst of Comparative Example 1, 1-butene was dehydrogenated. In Comparative Example 1, the reaction temperature was adjusted to the values shown in Table 1. Except for these matters, the dehydrogenation reaction of 1-butene of Comparative Example 1 was performed in the same manner as in Example 1. As a result of the analysis based on the same method as in Example 1, it was confirmed that in Comparative Example 1, the product gas of the dehydrogenation reaction also contains 1,3-butadiene. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Comparative Example 1. Table 1 shows the conversion rate 2 of Comparative Example 1 and the selectivity and yield of 1,3-butadiene.
（比較例２）
比較例２の触媒の製造では、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏの代わりに、１．７８２ｇのＺｎ（ＮＯ３）２・６Ｈ２Ｏを用いた。この事項を除いて実施例１と同様の方法で、比較例２の触媒を作製した。表１では、比較例２の製造方法を「含浸法」と記す。
(Comparative Example 2)
In the manufacture of the catalyst of Comparative Example 2, 1.782 g of Zn (NO 3 ) 2 .6H 2 O was used instead of Co (NO 3 ) 2 .6H 2 O. A catalyst of Comparative Example 2 was produced in the same manner as in Example 1 except for this matter. In Table 1, the production method of Comparative Example 2 is referred to as “impregnation method”.
実施例１と同様の方法で、比較例２の触媒のＸ線回折パターンを測定した。比較例２のＸ線回折パターンを図７に示す。Ｘ線回折パターンにより、比較例２の触媒がＺｎＦｅ２Ｏ４（フェライト系触媒）であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Comparative Example 2 was measured. The X-ray diffraction pattern of Comparative Example 2 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Comparative Example 2 was ZnFe 2 O 4 (ferrite-based catalyst).
比較例２のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。比較例２では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、比較例２の１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、比較例２においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。比較例２の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。比較例２の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite-based catalyst of Comparative Example 2, 1-butene was dehydrogenated. In Comparative Example 2, the reaction temperature was adjusted to the values shown in Table 1. Except for these items, the dehydrogenation reaction of 1-butene of Comparative Example 2 was performed in the same manner as in Example 1. As a result of the analysis based on the same method as in Example 1, it was confirmed that the product gas of the dehydrogenation reaction also contains 1,3-butadiene in Comparative Example 2. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Comparative Example 2. Table 1 shows the conversion rate 2 of Comparative Example 2 and the selectivity and yield of 1,3-butadiene.
比較例２のフェライト系触媒を用いて、実施例１と同様の方法で、ＴＰＲに基づく測定を行った。比較例２のＴＰＲに基づく測定の結果を図１１に示す。図１１に示すように、比較例２のフェライト系触媒を用いた１−ブテンの脱水素反応では、４００℃近傍から高温の領域にわたって、１，３−ブタジエンの生成量が増加すると略同時に、水素の生成量も増加することが確認された。このことは、１−ブテンの酸化的脱水素のみならず、単純脱水素が行っていることを示唆している。 Using the ferrite-based catalyst of Comparative Example 2, measurement based on TPR was performed in the same manner as in Example 1. The result of the measurement based on TPR in Comparative Example 2 is shown in FIG. As shown in FIG. 11, in the dehydrogenation reaction of 1-butene using the ferrite-based catalyst of Comparative Example 2, as the amount of 1,3-butadiene produced increases from around 400 ° C. to a high temperature region, It was confirmed that the production amount of was also increased. This suggests that not only oxidative dehydrogenation of 1-butene but also simple dehydrogenation is performed.
（比較例３）
Ｚｎ（ＮＯ３）２・６Ｈ２Ｏと、Ｆｅ（ＮＯ３）３・９Ｈ２Ｏと、を１００ｍＬの純水に溶解させて、溶液（前駆体の溶液）を作製した。純水に添加したＺｎ（ＮＯ３）２・６Ｈ２Ｏの質量は１．４９ｇであった。純水に添加したＦｅ（ＮＯ３）３・９Ｈ２Ｏの質量は４．０４ｇであった。純水におけるＺｎのモル数とＦｅのモル数の比を１：２に調整した。ＮＨ３の水溶液を上記前駆体の溶液に徐々に滴下して、前駆体の溶液のｐＨを７に調整することにより、溶液中の前駆体を共沈させた。この溶液の遠心分離により、固体状の前駆体を回収した。この前駆体を純水で洗浄した。洗浄に用いた後の純水のｐＨが７になるまで、洗浄を繰り返した。洗浄された前駆体を１００℃で一晩加熱して、乾燥した前駆体を得た。この前駆体を粉砕した。
(Comparative Example 3)
Zn (NO 3 ) 2 · 6H 2 O and Fe (NO 3 ) 3 · 9H 2 O were dissolved in 100 mL of pure water to prepare a solution (precursor solution). The mass of Zn (NO 3 ) 2 .6H 2 O added to pure water was 1.49 g. Pure water was added Fe (NO 3) 3 · 9H 2 O mass is 4.04 g. The ratio of the number of moles of Zn to the number of moles of Fe in pure water was adjusted to 1: 2. An aqueous solution of NH 3 was gradually added dropwise to the precursor solution to adjust the pH of the precursor solution to 7, thereby coprecipitating the precursor in the solution. The solid precursor was recovered by centrifugation of this solution. This precursor was washed with pure water. The washing was repeated until the pH of pure water after use for washing was 7. The washed precursor was heated at 100 ° C. overnight to obtain a dried precursor. This precursor was pulverized.
以下の手順で前駆体を焼成して、比較例３の触媒を得た。まず、粉砕された前駆体をマッフル炉内に設置し、マッフル炉内に空気を流通させながら、マッフル炉内を３時間かけて常温から５００℃まで昇温した。さらにマッフル炉内の温度を５００℃に２時間維持した。表１では、比較例３の製造方法を「共沈法」と記す。 The precursor was calcined by the following procedure to obtain a catalyst of Comparative Example 3. First, the pulverized precursor was placed in a muffle furnace, and the temperature in the muffle furnace was raised from room temperature to 500 ° C. over 3 hours while allowing air to flow through the muffle furnace. Further, the temperature in the muffle furnace was maintained at 500 ° C. for 2 hours. In Table 1, the production method of Comparative Example 3 is referred to as “coprecipitation method”.
実施例１と同様の方法で、比較例３の触媒のＸ線回折パターンを測定した。比較例３のＸ線回折パターンを図８に示す。Ｘ線回折パターンにより、比較例３の触媒がＺｎＦｅ２Ｏ４（フェライト系触媒）であることが確認された。 In the same manner as in Example 1, the X-ray diffraction pattern of the catalyst of Comparative Example 3 was measured. The X-ray diffraction pattern of Comparative Example 3 is shown in FIG. From the X-ray diffraction pattern, it was confirmed that the catalyst of Comparative Example 3 was ZnFe 2 O 4 (ferrite-based catalyst).
比較例３のフェライト系触媒を用いて１−ブテンの脱水素反応を行った。比較例３では、反応温度を表１に示す値に調整した。これらの事項を除いて実施例１と同様の方法で、比較例３の１−ブテンの脱水素反応を行った。実施例１と同様の方法に基づく分析の結果、比較例３においても、脱水素反応の生成ガスが、１，３−ブタジエンを含むことが確認された。比較例３の生成ガスが含む各炭素化合物のモル分率及び転化率１を表２に示す。比較例３の転化率２、並びに１，３−ブタジンエンの選択率及び収率を表１に示す。 Using the ferrite-based catalyst of Comparative Example 3, 1-butene was dehydrogenated. In Comparative Example 3, the reaction temperature was adjusted to the values shown in Table 1. Except for these matters, the dehydrogenation reaction of 1-butene of Comparative Example 3 was performed in the same manner as in Example 1. As a result of the analysis based on the same method as in Example 1, it was confirmed that the product gas of the dehydrogenation reaction also contains 1,3-butadiene in Comparative Example 3. Table 2 shows the molar fraction and conversion 1 of each carbon compound contained in the product gas of Comparative Example 3. Table 1 shows the conversion rate of Comparative Example 3 and the selectivity and yield of 1,3-butadiene.
（比較例４）
Ｚｎ（ＮＯ３）２・６Ｈ２Ｏの代わりにＣｏ（ＮＯ３）２・６Ｈ２Ｏを用いたこと以外は、比較例３と同様の方法で、比較例４の触媒の製造を試みた。しかし、フェライト系触媒（ＣｏＦｅ２Ｏ４）は得られなかった。
(Comparative Example 4)
An attempt was made to produce the catalyst of Comparative Example 4 in the same manner as in Comparative Example 3, except that Co (NO 3 ) 2 · 6H 2 O was used instead of Zn (NO 3 ) 2 · 6H 2 O. However, a ferrite catalyst (CoFe 2 O 4 ) was not obtained.
（比較例５）
Ｚｎ（ＮＯ３）２・６Ｈ２Ｏの代わりにＣｕ（ＮＯ３）２・６Ｈ２Ｏを用いたこと以外は、比較例３と同様の方法で、比較例５の触媒の製造を試みた。しかし、フェライト系触媒（ＣｕＦｅ２Ｏ４）は得られなかった。
(Comparative Example 5)
Zn (NO 3) 2 · 6H 2 O Cu (NO 3) instead of except for the use of 2 · 6H 2 O in a similar manner as in Comparative Example 3 was tried the preparation of catalyst of Comparative Example 5. However, a ferrite catalyst (CuFe 2 O 4 ) was not obtained.
上記表１に記載の「Ｃｏ」は、ＣｏＦｅ２Ｏ４を意味する。表１に記載の「Ｃｕ」は、ＣｕＦｅ２Ｏ４を意味する。表１に記載の「Ｍｎ」は、ＭｎＦｅ２Ｏ４を意味する。表１に記載の「Ｚｎ」は、ＺｎＦｅ２Ｏ４を意味する。 “Co” described in Table 1 above means CoFe 2 O 4 . “Cu” described in Table 1 means CuFe 2 O 4 . “Mn” shown in Table 1 means MnFe 2 O 4 . “Zn” listed in Table 1 means ZnFe 2 O 4 .
表１に示すように、全実施例の１，３−ブタジエンの選択率は、全比較例の１，３−ブタジエンの選択率よりも高いことが確認された。 As shown in Table 1, it was confirmed that the selectivity of 1,3-butadiene in all Examples was higher than the selectivity of 1,3-butadiene in all Comparative Examples.
比較例２及び３は、活性炭を用いた含浸法によって得られたＺｎＦｅ２Ｏ４の活性は、活性炭を用いない共沈法によって得られたＺｎＦｅ２Ｏ４の活性に劣ることを示している。 Comparative Examples 2 and 3 show that the activity of ZnFe 2 O 4 obtained by the impregnation method using activated carbon is inferior to the activity of ZnFe 2 O 4 obtained by the coprecipitation method not using activated carbon.
本発明に係るフェライト系触媒は、ブテンの酸化的脱水素により１，３−ブタジエンを高い選択率で生成させるための触媒（脱水素触媒）として好適である。 The ferrite catalyst according to the present invention is suitable as a catalyst (dehydrogenation catalyst) for producing 1,3-butadiene with high selectivity by oxidative dehydrogenation of butene.
Claims (8)
前記前駆体を焼成する焼成工程と、
を備え、
前記第一の金属塩は、銅又はコバルトのうち少なくともいずれかを含み、
前記第二の金属塩は、鉄を含む、
ブテンの脱水素に用いるフェライト系触媒の製造方法。 A preparation step of preparing a precursor by impregnating a porous carbonaceous material with a solution containing a first metal salt and a second metal salt;
A firing step of firing the precursor;
With
The first metal salt includes at least one of copper and cobalt,
The second metal salt includes iron,
A method for producing a ferrite catalyst used for dehydrogenation of butene.
請求項１に記載のフェライト系触媒の製造方法。 The solution comprises an organic acid;
The method for producing a ferrite catalyst according to claim 1.
請求項１又は２に記載のフェライト系触媒の製造方法。 In the firing step, at least a part of the carbonaceous material is burned away.
The manufacturing method of the ferrite catalyst of Claim 1 or 2.
前記前駆体を焼成する焼成工程と、
を備え、
前記第一の金属塩は、銅又はコバルトのうち少なくともいずれかを含み、
前記第二の金属塩は、鉄を含む、
ブテンの脱水素に用いるフェライト系触媒の製造方法。 A preparation step of preparing a precursor from a solution containing a first metal salt, a second metal salt, and an organic acid;
A firing step of firing the precursor;
With
The first metal salt includes at least one of copper and cobalt,
The second metal salt includes iron,
A method for producing a ferrite catalyst used for dehydrogenation of butene.
ブテンの脱水素に用いるフェライト系触媒。 Manufactured by the method for producing a ferrite-based catalyst according to any one of claims 1 to 4,
Ferrite catalyst used for dehydrogenation of butene.
炭素の含有率が、０〜５質量％である、
ブテンの脱水素に用いるフェライト系触媒。 MFe 2 O 4 (M is at least one of Cu and Co),
The carbon content is 0 to 5% by mass.
Ferrite catalyst used for dehydrogenation of butene.
請求項６に記載のフェライト系触媒。 The carbon content is 0 to 0.01% by mass,
The ferrite catalyst according to claim 6.
１，３−ブタジエンの製造方法。 A dehydrogenation step of bringing butene into contact with the ferrite-based catalyst according to any one of claims 5 to 7,
A method for producing 1,3-butadiene.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017164542A1 (en) | 2016-03-24 | 2017-09-28 | (주) 엘지화학 | Catalyst for oxidative dehydrogenation reaction, and preparation method therefor |
| KR20180080814A (en) | 2017-01-05 | 2018-07-13 | 주식회사 엘지화학 | Catalyst for oxidative dehydrogenation and method of preparing the same |
| KR20180088273A (en) | 2017-01-26 | 2018-08-03 | 주식회사 엘지화학 | Ferrite catalyst for oxidative dehydrogenation, method for preparing the same and method of preparing butadiene using the same |
| JP2018525216A (en) * | 2016-03-28 | 2018-09-06 | エルジー・ケム・リミテッド | Method for producing zinc ferrite catalyst |
| KR20190030916A (en) | 2017-09-15 | 2019-03-25 | 주식회사 엘지화학 | Binder-mixtured catalyst for oxidative dehydrogenation reaction, method for preparing the same catalyst and method for preparing butadiene |
| KR20190107920A (en) | 2018-03-13 | 2019-09-23 | 주식회사 엘지화학 | Method for preparing ferrite-based coating catalysts and method for butadiene using the same |
| US10926246B2 (en) | 2016-03-18 | 2021-02-23 | Lg Chem, Ltd. | Method of preparing catalyst for oxidative dehydrogenation |
| WO2021060681A1 (en) * | 2019-09-27 | 2021-04-01 | 주식회사 엘지화학 | Method for preparing zinc ferrite-based catalyst and zinc ferrite-based catalyst prepared thereby |
| US11660584B2 (en) | 2017-04-12 | 2023-05-30 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation, method of preparing catalyst, and method of performing oxidative dehydrogenation using catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5088001A (en) * | 1974-09-11 | 1975-07-15 | ||
| US4658074A (en) * | 1965-05-28 | 1987-04-14 | Petro-Tex Chemical Corporation | Catalytic oxidative dehydrogenation process |
| JPH11171552A (en) * | 1997-12-03 | 1999-06-29 | Adooru:Kk | Metal ferrite and production thereof |
| CN102527387A (en) * | 2011-12-26 | 2012-07-04 | 南京理工大学 | Copper ferrite-graphene nano complex and preparation method thereof |
| CN102974357A (en) * | 2011-09-06 | 2013-03-20 | 北京中石润达科技发展有限公司 | Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof |
-
2014
- 2014-03-05 JP JP2014042824A patent/JP6195246B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4658074A (en) * | 1965-05-28 | 1987-04-14 | Petro-Tex Chemical Corporation | Catalytic oxidative dehydrogenation process |
| JPS5088001A (en) * | 1974-09-11 | 1975-07-15 | ||
| JPH11171552A (en) * | 1997-12-03 | 1999-06-29 | Adooru:Kk | Metal ferrite and production thereof |
| CN102974357A (en) * | 2011-09-06 | 2013-03-20 | 北京中石润达科技发展有限公司 | Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof |
| CN102527387A (en) * | 2011-12-26 | 2012-07-04 | 南京理工大学 | Copper ferrite-graphene nano complex and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| K. S. MARTIROSYAN ET AL.: "Carbon Combustion and Magnetic Properties of Cobalt Ferrite Nanoparticles", IEEE TRANSACTIONS ON MAGNETICS, vol. 43, JPN6017015218, 2007, pages 3118-3120. * |
| W. RONALD CARES ET AL.: "Ferrite Spinels as Catalysts in the Oxidative Dehydrogenation of Butenes", JOURNAL OF CATALYSIS, vol. 23, JPN6017015219, 1971, pages 193-203. * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10926246B2 (en) | 2016-03-18 | 2021-02-23 | Lg Chem, Ltd. | Method of preparing catalyst for oxidative dehydrogenation |
| WO2017164542A1 (en) | 2016-03-24 | 2017-09-28 | (주) 엘지화학 | Catalyst for oxidative dehydrogenation reaction, and preparation method therefor |
| KR20170110894A (en) | 2016-03-24 | 2017-10-12 | 주식회사 엘지화학 | Catalyst for oxidative dehydrogenation and method of preparing the same |
| US10543478B2 (en) | 2016-03-24 | 2020-01-28 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation and method of preparing the same |
| US10456775B2 (en) | 2016-03-28 | 2019-10-29 | Lg Chem, Ltd. | Method of preparing zinc ferrite catalyst |
| CN108698038A (en) * | 2016-03-28 | 2018-10-23 | 株式会社Lg化学 | The preparation method of iron acid zinc catalyst |
| JP2018525216A (en) * | 2016-03-28 | 2018-09-06 | エルジー・ケム・リミテッド | Method for producing zinc ferrite catalyst |
| KR20180080814A (en) | 2017-01-05 | 2018-07-13 | 주식회사 엘지화학 | Catalyst for oxidative dehydrogenation and method of preparing the same |
| KR20180088273A (en) | 2017-01-26 | 2018-08-03 | 주식회사 엘지화학 | Ferrite catalyst for oxidative dehydrogenation, method for preparing the same and method of preparing butadiene using the same |
| US10843173B2 (en) | 2017-01-26 | 2020-11-24 | Lg Chem, Ltd. | Ferrite catalyst for oxidative dehydrogenation, method of preparing ferrite catalyst, and method of preparing butadiene using ferrite catalyst |
| US11660584B2 (en) | 2017-04-12 | 2023-05-30 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation, method of preparing catalyst, and method of performing oxidative dehydrogenation using catalyst |
| KR20190030916A (en) | 2017-09-15 | 2019-03-25 | 주식회사 엘지화학 | Binder-mixtured catalyst for oxidative dehydrogenation reaction, method for preparing the same catalyst and method for preparing butadiene |
| KR20190107920A (en) | 2018-03-13 | 2019-09-23 | 주식회사 엘지화학 | Method for preparing ferrite-based coating catalysts and method for butadiene using the same |
| WO2021060681A1 (en) * | 2019-09-27 | 2021-04-01 | 주식회사 엘지화학 | Method for preparing zinc ferrite-based catalyst and zinc ferrite-based catalyst prepared thereby |
| CN113164927A (en) * | 2019-09-27 | 2021-07-23 | 株式会社Lg化学 | Method for preparing zinc ferrite catalyst and zinc ferrite catalyst prepared thereby |
| CN113164927B (en) * | 2019-09-27 | 2023-11-28 | 株式会社Lg化学 | Method for preparing zinc ferrite catalyst and zinc ferrite catalyst prepared by same |
| US11865522B2 (en) | 2019-09-27 | 2024-01-09 | Lg Chem, Ltd. | Method for preparing zinc ferrite-based catalyst and zinc ferrite-based catalyst prepared thereby |
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