JP7227209B2 - 1,3-butadiene production catalyst - Google Patents
1,3-butadiene production catalyst Download PDFInfo
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- JP7227209B2 JP7227209B2 JP2020198007A JP2020198007A JP7227209B2 JP 7227209 B2 JP7227209 B2 JP 7227209B2 JP 2020198007 A JP2020198007 A JP 2020198007A JP 2020198007 A JP2020198007 A JP 2020198007A JP 7227209 B2 JP7227209 B2 JP 7227209B2
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 126
- 239000003054 catalyst Substances 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 23
- 150000003377 silicon compounds Chemical class 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000004043 oxo group Chemical group O=* 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910003849 O-Si Inorganic materials 0.000 claims description 10
- 229910003872 O—Si Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 34
- 238000000034 method Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- -1 oxides Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
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- 150000002823 nitrates Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910006728 Si—Ta Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
エタノールから１，３－ブタジエンを製造する触媒に関する。 It relates to a catalyst for producing 1,3-butadiene from ethanol.
エタノールからのブタジエン製造（ＥＴＢ）は、過去に工業実績のある技術であるが、ナフサクラッカーより得られたＣ４留分からのブタジエン抽出蒸留技術の完成に伴い競争力を失ったため、一部の地域を除いて現在では使用されていない。しかしながら、近年、アジアを中心とした自動車普及台数の伸びとクラッカー原料の軽質化に伴う世界的なブタジエン需給ギャップの拡大が懸念されており、ブタジエンを単産できるＥＴＢプロセスへの関心が高まっている。 Production of butadiene from ethanol (ETB) is a technology that has a proven track record in industry in the past. Not currently used except However, in recent years, there is concern about the widening gap between supply and demand for butadiene worldwide due to the growing number of automobiles in use, especially in Asia, and the lighter raw material for crackers.
ＥＴＢプロセスには、一段でエタノールをブタジエンに変換する一段法（Ｌｅｂｅｄｅｖ法）と、まずエタノールを脱水素してアセトアルデヒドを合成し、エタノールとアセトアルデヒドからブタジエンを合成する二段法（Ｏｓｔｒｏｍｉｓｌｅｎｓｋｙ法）がある。
・一段法
２ＣＨ3ＣＨ2ＯＨ→ＣＨ2＝ＣＨ－ＣＨ＝ＣＨ2＋２Ｈ2Ｏ＋Ｈ2
・二段法
ＣＨ3ＣＨ2ＯＨ→ＣＨ3ＣＨＯ＋Ｈ2
ＣＨ3ＣＨ2ＯＨ＋ＣＨ3ＣＨＯ→ＣＨ2＝ＣＨ－ＣＨ＝ＣＨ2＋２Ｈ2Ｏ
The ETB process includes a one-step method (Lebedev method) in which ethanol is converted to butadiene in one step, and a two-step method (Ostromislensky method) in which ethanol is first dehydrogenated to synthesize acetaldehyde and then ethanol and acetaldehyde to synthesize butadiene. .
・One-step method 2 CH 3 CH 2 OH→CH 2 =CH-CH=CH 2 +2H 2 O+H 2
・Two-step method CH3CH2OH → CH3CHO + H2
CH3CH2OH + CH3CHO → CH2 =CH—CH = CH2 + 2H2O
このような反応の際に使用されるＥＴＢ触媒として、周期律表第４族および第５族の元素をシリカに担持した触媒が知られている。Ｔａ2Ｏ5／ＳｉＯ2触媒は古くから、１，３－ブタジエン合成触媒として知られていた（特許文献１，非特許文献１～２）。しかしながら、当時のブタジエン選択率は６０％台で十分に高いとは言えなかった。 As an ETB catalyst used in such reactions, catalysts in which elements of Groups 4 and 5 of the periodic table are supported on silica are known. A Ta 2 O 5 /SiO 2 catalyst has long been known as a 1,3-butadiene synthesis catalyst (Patent Document 1, Non-Patent Documents 1 and 2). However, the butadiene selectivity at that time was on the order of 60%, which was not sufficiently high.
近年、メソポーラスシリカにＴａを担持した触媒（非特許文献３）やゼオライトにＴａを担持したＴａ／ＳＢＡ－１５（非特許文献４）、ゼオライト骨格中にＴａを挿入したＴａＢＥＡ（非特許文献５）が１，３－ブタジエン合成触媒として報告されている。また、ＺｒＯ2／ＳｉＯ2触媒、ＨｆＯ2／ＳｉＯ2触媒も古くから、１，３－ブタジエン合成触媒として知られており（非特許文献２）、近年はそれに脱水素能を有する金属を担持した一段触媒として、Ａｇ－ＺｒＯ2－ＣｅＯ2－ＳｉＯ2（特許文献２）、ＺｎＺｒＳｉＯ2やＣｕＺｎＺｒＳｉＯ2（非特許文献６）、ＣｕＨｆＺｎＳｉＯ2（非特許文献７）等が報告されている。 In recent years, a catalyst in which Ta is supported on mesoporous silica (Non-Patent Document 3), Ta/SBA-15 in which Ta is supported on zeolite (Non-Patent Document 4), and TaBEA in which Ta is inserted into the zeolite skeleton (Non-Patent Document 5) has been reported as a 1,3-butadiene synthesis catalyst. ZrO 2 /SiO 2 catalysts and HfO 2 /SiO 2 catalysts have also long been known as 1,3-butadiene synthesis catalysts (Non-Patent Document 2), and in recent years metals having dehydrogenating ability have been supported on them. Ag--ZrO 2 --CeO 2 --SiO 2 (Patent Document 2), ZnZrSiO 2 , CuZnZrSiO 2 (Non-Patent Document 6), CuHfZnSiO 2 (Non-Patent Document 7), etc. have been reported as single-stage catalysts.
本発明では、実際的な運転条件でより効率的に１，３－ブタジエンを製造することのできる触媒および、その触媒を用いた１，３－ブタジエンの製造方法を提供することを目的としている。 An object of the present invention is to provide a catalyst capable of producing 1,3-butadiene more efficiently under practical operating conditions, and a method for producing 1,3-butadiene using the catalyst.
このような状況のもと、本発明者らは、上記課題を解決すべく鋭意検討した結果、以下の構成により、本発明を完成するに至った。
［１］周期表第４族および５族の元素（Ａ）と、担体成分である二酸化ケイ素とを含み、担体成分である二酸化ケイ素の表面に周期表第４族および５族の元素（Ａ）が担持され、前記元素（Ａ）を前記二酸化ケイ素に固定化してなり、且つ前記元素（Ａ）上の表面水酸基およびオキソ基の少なくとも一部が－Ｏ－Ｓｉ基で置換された末端－(Ａ)－Ｏ-Ｓｉ基を含むことを特徴とする、エタノールを含む原料から１，３－ブタジエンを製造する１，３－ブタジエン製造触媒。
［２］周期表第４族および５族の元素（Ａ）と、担体成分である二酸化ケイ素とを含み、且つ前記元素（Ａ）上の表面水酸基およびオキソ基の少なくとも一部が－Ｏ－Ｓｉ基で置換された末端－(Ａ)－Ｏ-Ｓｉ基を含み、
前記末端－(Ａ)－Ｏ-Ｓｉ基は、前記元素（Ａ）上にケイ素化合物のモノマーが結合した構造であることを特徴とする、エタノールを含む原料から１，３－ブタジエンを製造する１，３－ブタジエン製造触媒。
［３］加水分解性基を有するケイ素化合物中のケイ素と元素（Ａ）のモル比（加水分解性基を有するケイ素化合物中のケイ素［ｍｏｌ］／元素（Ａ）［ｍｏｌ］）が０．１から１００であることを特徴とする、［１］または［２］の１，３－ブタジエン製造触媒。
［４］二酸化ケイ素上の元素（Ａ）の密度が１～５０個／ｎｍ2の範囲であることを特徴とする、［１］～［３］の１，３－ブタジエン製造触媒。
［５］元素（Ａ）がジルコニウム、ハフニウムおよびタンタルから選ばれる少なくとも1種であることを特徴とする、［１］～［４］の１，３－ブタジエン製造触媒。
［６］29Ｓｉ－ＮＭＲのケミカルシフト値：－１１１ｐｐｍ付近の極大値のシグナル強度を１とした場合に、ケミカルシフト値：－１０５ｐｐｍでのシグナル強度が０．５５以上であることを特徴とする、［１］～［５］の１，３－ブタジエン製造触媒。
［７］［１］～［６］の１，３－ブタジエン製造触媒を用いて、エタノール単独またはエタノールとともにアセトアルデヒドを含む原料を、反応温度が３００℃以上４５０℃以下、エタノールおよびアセトアルデヒドの分圧が０．１～１．０ＭＰａＡ、重量空間速度が０．１～３０ｇ／ｇ-cat・hの範囲で、前記触媒と接触させることを特徴とする１，３－ブタジエンの製造方法。
Under such circumstances, the present inventors have made intensive studies to solve the above problems, and as a result, have completed the present invention with the following configuration.
[1] Contains an element (A) of Groups 4 and 5 of the periodic table and silicon dioxide as a carrier component, and an element (A) of Groups 4 and 5 of the periodic table on the surface of the silicon dioxide as a carrier component is supported, the element (A) is immobilized on the silicon dioxide, and at least part of the surface hydroxyl groups and oxo groups on the element (A) is substituted with an —O—Si group, the terminal —(A )—O—Si group, a 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol.
[2] containing an element (A) of Groups 4 and 5 of the periodic table and silicon dioxide as a carrier component, and at least a portion of the surface hydroxyl groups and oxo groups on the element (A) are —O—Si containing a terminal —(A)—O—Si group substituted with a group
1 for producing 1,3-butadiene from a raw material containing ethanol, characterized in that the terminal -(A)-O-Si group has a structure in which a silicon compound monomer is bonded to the element (A) ,3-butadiene production catalyst.
[3] The molar ratio of silicon in the silicon compound having a hydrolyzable group to the element (A) (silicon [mol] in the silicon compound having a hydrolyzable group/element (A) [mol]) is 0.1 to 100, the 1,3-butadiene production catalyst of [1] or [2].
[4] The catalyst for producing 1,3-butadiene of [1] to [3], wherein the density of element (A) on silicon dioxide is in the range of 1 to 50/nm 2 .
[5] The catalyst for producing 1,3-butadiene of [1] to [4], wherein the element (A) is at least one selected from zirconium, hafnium and tantalum.
[6] 29 Si-NMR chemical shift value: characterized in that the signal intensity at the chemical shift value: -105 ppm is 0.55 or more when the signal intensity at the maximum value near -111 ppm is 1; , a catalyst for producing 1,3-butadiene according to [1] to [5].
[7] Using the 1,3-butadiene production catalyst of [1] to [6], a raw material containing ethanol alone or ethanol together with acetaldehyde is reacted at a reaction temperature of 300 ° C. or higher and 450 ° C. or lower, and the partial pressure of ethanol and acetaldehyde is A method for producing 1,3-butadiene, wherein the catalyst is brought into contact with the catalyst at a weight hourly space velocity of 0.1 to 1.0 MPaA and a weight hourly space velocity of 0.1 to 30 g/g -cat · h .
本発明の１，３－ブタジエン製造触媒ならびにこの触媒を使用した製造方法によれば、エタノールを含む原料ガスから１，３－ブタジエンをより効率的に製造することが可能となる。 According to the catalyst for producing 1,3-butadiene of the present invention and the production method using this catalyst, it becomes possible to more efficiently produce 1,3-butadiene from a raw material gas containing ethanol.
以下、本発明を実施するための形態について説明する。
［１，３－ブタジエン製造触媒］
本発明で使用される触媒は、周期表第４族および５族の元素（Ａ）と担体成分である二酸化ケイ素を含む。触媒表面には、ケイ素や元素（Ａ）の水酸化物ないし酸化物などに由来する水酸基（－ＯＨ）およびオキソ基（＝Ｏ）が存在するが、本発明では表面水酸基およびオキソ基の少なくとも一部が加水分解性基を有するケイ素化合物と反応することによって、－Ｏ－Ｓｉ基で置換されている。なおすべての水酸基およびオキソ基が置換されていてもよく、また一部が置換されていてもよい。
EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.
[1,3-butadiene production catalyst]
The catalyst used in the present invention contains an element (A) of Groups 4 and 5 of the periodic table and silicon dioxide as a carrier component. Hydroxy groups (--OH) and oxo groups (=O) derived from silicon, hydroxides or oxides of element (A), etc. are present on the surface of the catalyst. moieties are substituted with —O—Si groups by reacting with silicon compounds having hydrolyzable groups. All hydroxyl groups and oxo groups may be substituted, or some may be substituted.
元素（Ａ）としては、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタルなどが挙げられ、１，３－ブタジエン選択率向上の点で、元素（Ａ）がジルコニウム、ハフニウム、タンタルから選ばれる少なくとも1種であることが好ましい。 Examples of element (A) include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. From the viewpoint of improving the 1,3-butadiene selectivity, element (A) is at least one selected from zirconium, hafnium, and tantalum. Seeds are preferred.
これらの元素（Ａ）は、担体である二酸化ケイ素に、金属、酸化物、水酸化物、塩などの状態で固定される。二酸化ケイ素としては、アモルファスシリカ、シリカゾル、シリカゲル、コロイダルシリカなどが挙げられる。また、ＭＣＭ-４１、ＦＳＭ-１６、ＳＢＡ-１５などのメソポーラスシリカや、ゼオライトも使用可能である。 These elements (A) are fixed to the carrier silicon dioxide in the form of metals, oxides, hydroxides, salts, or the like. Silicon dioxide includes amorphous silica, silica sol, silica gel, colloidal silica, and the like. In addition, mesoporous silica such as MCM-41, FSM-16, SBA-15, and zeolite can also be used.
元素（Ａ）を二酸化ケイ素に固定化する方法としては、元素（Ａ）を含む塩化物塩、硝酸塩、硫酸塩、燐酸塩、アルコキシドを水や有機溶媒に溶解させ、二酸化ケイ素の粉末や成形体からなる担体に含浸させたのち、加熱、乾燥・焼成することで調製できる。含浸方法としては、公知の手法が採用でき、元素（Ａ）含む（水）溶液を噴霧法、コーティング法、またはポアフィリング法また選択吸着法などが挙げられる。また担体の二酸化ケイ素粉末の分散液に元素（Ａ）を含む塩化物塩、硝酸塩、硫酸塩、燐酸塩、アルコキシドなどを溶解させてもよい。さらに、元素（Ａ）を含む塩化物塩やアルコキシドを気化させて二酸化ケイ素担体の表面に吸着させたのちに、乾燥・焼成することによっても調製できる。 As a method for immobilizing the element (A) on silicon dioxide, chloride salts, nitrates, sulfates, phosphates, and alkoxides containing the element (A) are dissolved in water or an organic solvent, and silicon dioxide powders and compacts are prepared. It can be prepared by impregnating a carrier consisting of, followed by heating, drying and baking. As the impregnation method, a known method can be employed, and examples thereof include a spraying method, a coating method, a pore filling method, a selective adsorption method, and the like with an (aqueous) solution containing the element (A). Chloride salts, nitrates, sulfates, phosphates, alkoxides, etc. containing the element (A) may be dissolved in the dispersion of silicon dioxide powder as the carrier. Furthermore, it can also be prepared by evaporating a chloride salt or alkoxide containing the element (A) and adsorbing it on the surface of a silicon dioxide carrier, followed by drying and firing.
また、元素（Ａ）および二酸化ケイ素の前駆体を混合したのちに加熱や濃縮、水熱合成などの処理を施し、乾燥・焼成することで調製することもできる。元素（Ａ）の前駆体としてはアルコキシドや塩化物塩、硝酸塩、硫酸塩、燐酸塩、金属酸化物ゾルなどが挙げられる。また、二酸化ケイ素担体の前駆体としては、アルコキシド、ポリシロキサン、ポリシラザンなどの有機珪素化合物、珪酸塩などの有機珪酸塩など他に、シリカゾルなども使
用できる。
It can also be prepared by mixing the element (A) and a precursor of silicon dioxide, followed by heating, concentration, hydrothermal synthesis, and other treatments, followed by drying and firing. Precursors of the element (A) include alkoxides, chloride salts, nitrates, sulfates, phosphates, metal oxide sols, and the like. As a precursor for the silicon dioxide carrier, an organic silicon compound such as an alkoxide, polysiloxane, or polysilazane, an organic silicate such as a silicate, or silica sol can be used.
元素（Ａ）を二酸化ケイ素に固定化した触媒は、加水分解性基を有するケイ素化合物によって処理される。加水分解性基を有するケイ素化合物とは、珪素原子に１～４個の加水分解性基が結合したものである。加水分解性基としては，例えば，水素，ハロゲン原子，アルコキシ基，アシルオキシ基，ケトキシメート基，アミノ基，アミド基，酸アミド基，アミノオキシ基，メルカプト基，アルケニルオキシ基などが挙げられる。 加水分解性基を有するケイ素化合物はたとえば下記式（１）で表される。
ＳｉＹnＲ(4-n) ・・・（１）
A catalyst in which element (A) is immobilized on silicon dioxide is treated with a silicon compound having a hydrolyzable group. A silicon compound having a hydrolyzable group is one in which 1 to 4 hydrolyzable groups are bonded to a silicon atom. Examples of hydrolyzable groups include hydrogen, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. A silicon compound having a hydrolyzable group is represented, for example, by the following formula (1).
SiYnR (4-n) (1)
式中、Ｙは、それぞれ独立に加水分解性基であり、Ｒは炭素数が１～２０の置換又は非置換の炭化水素基である。ｎは、１～４の整数である。炭素数が１～２０の置換又は非置換の炭化水素基は、特に限定されず、例えば、メチル基、エチル基、プロピル基などの炭素数が１～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基などが挙げられる。なお２個以上のＹまたはＲが結合する場合、これらは互いに同一であっても相違してもよい。さらに加水分解性基を有するケイ素化合物は、少なくとも一部が重縮合した部分重縮合物であってもよい。 In the formula, each Y is independently a hydrolyzable group, and R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n is an integer of 1-4. The substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl Examples include an aryl group and an aralkyl group having 7 to 20 carbon atoms. When two or more Y or R are bonded, they may be the same or different. Furthermore, the silicon compound having a hydrolyzable group may be a partial polycondensate in which at least a part thereof is polycondensed.
処理は、水、有機溶媒などにこれらの加水分解性基を有するケイ素化合物を溶かし、元素（Ａ）を二酸化ケイ素に固定化した物質を加えて処理を行っても良いし、加水分解性基を有するケイ素化合物を気化させて、元素（Ａ）を二酸化ケイ素に固定化した物質の表面に吸着させて処理を行っても良い。これらの処理によって、元素（Ａ）を二酸化ケイ素に固定化した物質の表面水酸基や、元素（Ａ）が周期表第５族金属である場合には元素（Ａ）上のオキソ基は、ケイ素化合物の加水分解性基と縮合反応し、元素（Ａ)上やその周辺に－Ｏ－Ｓｉ結合を生成すると考えられる。 The treatment may be carried out by dissolving the silicon compound having these hydrolyzable groups in water, an organic solvent, etc., and adding a substance in which the element (A) is immobilized on silicon dioxide, or by removing the hydrolyzable group. The treatment may be performed by vaporizing the silicon compound possessed and adsorbing the element (A) on the surface of the substance immobilized on silicon dioxide. By these treatments, the surface hydroxyl groups of the substance in which the element (A) is immobilized on silicon dioxide, and the oxo groups on the element (A) when the element (A) is a group 5 metal of the periodic table are converted into silicon compounds. is condensed with the hydrolyzable group of the element (A) to form an --O--Si bond on or around the element (A).
ゼオライト中の金属の配位状態がＬｅｗｉｓ酸性や反応性に影響を与えることが、近年明らかになってきている。Ｓｎを導入したゼオライト（ＳｎＢＥＡ）では、２種類の活性サイト（－Ｓｉ－Ｏ－）3Ｓｎ－ＯＨとＳｎ（－Ｓｉ－Ｏ－）4が存在することが明らかとなっており、このうちの（－Ｓｉ－Ｏ－）3Ｓｎ－ＯＨのほうが強いＬｅｗｉｓ酸を有しており、過酸化水素によるアダマンタン酸化反応に寄与していると報告されている（Ｊｏｕｒｎａｌ ｏｆ Ｃａｔａｌｙｓｉｓ， ｖｏｌ．２３４， ｐｐ．１１１（２００５））。また、Ｚｒを導入したゼオライト（ＺｒＢＥＡ）でも同様に、２種類の活性サイトのうち（－Ｓｉ－Ｏ－）3Ｚｒ－ＯＨのほうが強いＬｅｗｉｓ酸を有しており、エタノールからの１，３－ブタジエン合成反応速度と（－Ｓｉ－Ｏ－）3Ｚｒ－ＯＨ の数に相関が見られることが報告されている（ＡＣＳ Ｃａｔａｌｙｓｉｓ， ｖｏｌ．５， ｐｐ．４８３３（２０１５）， Ｊｏｕｒｎａｌ ｏｆ Ｐｈｙｓｉｃａｌ Ｃｈｅｍｉｓｔｒｙ， ｖｏｌ．１１９， ｐｐ．１７６３３（２０１５））。 In recent years, it has become clear that the coordination state of metals in zeolite affects Lewis acidity and reactivity. It has been clarified that Sn-introduced zeolite (SnBEA) has two types of active sites, (--Si--O--) 3 Sn--OH and Sn(--Si--O--) 4 . (--Si--O--) 3 Sn--OH has a stronger Lewis acid and is reported to contribute to the adamantane oxidation reaction by hydrogen peroxide (Journal of Catalysis, vol.234, pp. 111 (2005)). Similarly, in zeolite into which Zr is introduced (ZrBEA), among the two types of active sites, (—Si—O—) 3 Zr—OH has a stronger Lewis acid, and 1,3- It has been reported that there is a correlation between the butadiene synthesis reaction rate and the number of (—Si—O—) 3 Zr—OH (ACS Catalysis, vol.5, pp.4833 (2015), Journal of Physical Chemistry, vol. .119, pp. 17633 (2015)).
当該特許で記述する触媒は、ゼオライト構造を有していないが、二酸化ケイ素中に活性金属が存在しているという状態は先の報告と同様であり、活性金属周辺の配位状態（－ＯＨ基、－ＯＳｉ基のどちらを有するか）が、触媒のＬｅｗｉｓ酸性や反応性に大きく寄与していると予想される。そのため、元素（Ａ）上、または近辺に－Ｏ－Ｓｉ結合を生成することによって触媒の活性・選択性が変化していると考えられる。 The catalyst described in the patent does not have a zeolite structure, but the state in which the active metal is present in silicon dioxide is the same as in the previous report, and the coordination state around the active metal (-OH group , —OSi group) is expected to greatly contribute to the Lewis acidity and reactivity of the catalyst. Therefore, it is considered that the activity and selectivity of the catalyst are changed by forming a --O--Si bond on or near the element (A).
本発明では、触媒の29Ｓｉ－ＮＭＲのケミカルシフト値：－１１１ｐｐｍ付近の極大値のシグナル強度を１とした場合の、ケミカルシフト値：－１０５ｐｐｍでのシグナル強度が０．５５以上であることが好ましい。このようなケミカルシフト値のシグナル強度を有する触媒は、触媒活性が高い。 In the present invention, the signal intensity at the chemical shift value of -105 ppm is 0.55 or more when the signal intensity at the maximum value near -111 ppm of the chemical shift value of the catalyst is 1 . preferable. A catalyst having a signal intensity of such a chemical shift value has high catalytic activity.
加水分解性基を有するケイ素化合物中のケイ素と元素（Ａ）のモル比（加水分解性基を有するケイ素化合物中のケイ素［ｍｏｌ］／元素（Ａ）［ｍｏｌ］）は、特に限定されないが、０．１から１００の範囲が好ましい。加水分解性基を有するケイ素化合物中のケイ素と元素（Ａ）のモル比が低すぎるとケイ素化合物処理による効果が十分得られない。加水分解性基を有するケイ素化合物中のケイ素と元素（Ａ）のモル比が高すぎると、ケイ素が元素（Ａ）を完全に覆ってしまい、触媒活性が低下することがあると考えられる。 The molar ratio of silicon in the silicon compound having a hydrolyzable group and the element (A) (silicon [mol] in the silicon compound having a hydrolyzable group/element (A) [mol]) is not particularly limited, A range of 0.1 to 100 is preferred. If the molar ratio of silicon to element (A) in the silicon compound having a hydrolyzable group is too low, the effect of silicon compound treatment cannot be obtained sufficiently. If the molar ratio of silicon to element (A) in the silicon compound having a hydrolyzable group is too high, silicon may completely cover element (A), resulting in a decrease in catalytic activity.
二酸化ケイ素上の元素（Ａ）の密度は、特に限定されないが、１～５０個／ｎｍ2の範囲が好ましい。元素（Ａ）の密度が低すぎると触媒単位体積あたりの１，３－ブタジエン生成速度が遅くなる。元素（Ａ）の密度が高すぎると、副反応が進行することにより１，３－ブタジエン選択率が低下する。 The density of element (A) on silicon dioxide is not particularly limited, but is preferably in the range of 1 to 50/nm 2 . If the density of element (A) is too low, the rate of 1,3-butadiene production per unit volume of catalyst will be low. If the density of element (A) is too high, the 1,3-butadiene selectivity will decrease due to the progress of side reactions.
触媒は、元素（Ａ）および二酸化ケイ素のほかに、亜鉛、銀、銅、金などの金属や、アルカリ金属、アルカリ土類金属、ランタノイド等を含んでいても構わない。
触媒の形状としては特に制限されるものではなく、粒状、円柱状、円筒状、ハニカム状など公知の形状であっても使用できる。
In addition to the element (A) and silicon dioxide, the catalyst may contain metals such as zinc, silver, copper and gold, alkali metals, alkaline earth metals, lanthanoids and the like.
The shape of the catalyst is not particularly limited, and known shapes such as granular, columnar, cylindrical and honeycomb shapes can be used.
[１，３－ブタジエンの製造方法]
本発明の１，３－ブタジエンの製造方法は、加熱下で、少なくともエタノールを含む原料を前記触媒に接触させることを特徴とする。エタノールとしては、特に限定されることが無く、例えば、サトウキビやトウモロコシなどのバイオマス由来のエタノールや、石油、石炭若しくは天然ガス由来のエタノールなどを挙げることができる。なお、バイオマス由来のエタノールを使用すれば、温室効果ガス削減に貢献することができる。
[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene of the present invention is characterized by bringing a raw material containing at least ethanol into contact with the catalyst under heating. Ethanol is not particularly limited, and examples thereof include ethanol derived from biomass such as sugarcane and corn, and ethanol derived from petroleum, coal, or natural gas. The use of biomass-derived ethanol can contribute to the reduction of greenhouse gases.
本発明の原料は、エタノール単独でもよいが、エタノールと共にアセトアルデヒドを含有していてもよい。
アセトアルデヒドを含有する場合、エタノールとアセトアルデヒドのモル比（ＥｔＯＨ：ＡｃＨ）は、９５：５～４０：６０、好ましくは９０：１０～５０：５０、さらに好ましくは８５：１５～５０：５０の範囲にある。
The raw material of the present invention may be ethanol alone, or may contain acetaldehyde together with ethanol.
When acetaldehyde is contained, the molar ratio of ethanol to acetaldehyde (EtOH:AcH) is in the range of 95:5 to 40:60, preferably 90:10 to 50:50, more preferably 85:15 to 50:50. be.
アセトアルデヒドはエタノールの脱水素反応により製造したものを使用することができる。エタノールの脱水素反応では、例えば、特開２００５－３４２６７５号公報、特開２０１１－０００５３２号公報公報などに開示された公知の銅触媒や銀触媒が使用される。具体的には、Ｃｕ系や、Ｎｉ、Ｐｄ、Ｐｔ等の元素周期表８族の金属等を好適に用いることができ、中でもＣｕを含有するものが更に好ましい。例えばＣｕ単独あるいはこれにＣｒ、Ｃｏ、Ｎｉ、Ｆｅ、Ｍｎ等の遷移金属元素を加えた２成分の金属を含むものが挙げられ、ＣｕとＮｉを含有するものが好ましく用いられる。更に３成分以上の金属を含むものも好ましく用いられる。またこれらをさらに二酸化ケイ素、酸化アルミニウム、酸化チタン、ゼオライト等に担持させたもの等も用いられる。 As acetaldehyde, one produced by a dehydrogenation reaction of ethanol can be used. In the dehydrogenation reaction of ethanol, for example, known copper catalysts and silver catalysts disclosed in JP-A-2005-342675 and JP-A-2011-000532 are used. Specifically, Cu-based materials and metals of group 8 of the periodic table such as Ni, Pd, and Pt can be preferably used, and among them, those containing Cu are more preferable. For example, Cu alone or containing a two-component metal in which a transition metal element such as Cr, Co, Ni, Fe, and Mn is added to Cu can be used, and those containing Cu and Ni are preferably used. Furthermore, those containing three or more metal components are also preferably used. In addition, those further supported by silicon dioxide, aluminum oxide, titanium oxide, zeolite and the like are also used.
反応条件としては特に制限されるものではなく、通常２００～３００℃程度の範囲で、所定のアセトアルデヒド生成量となるような条件で反応を行う。
かかる製造方法は、回分式、半回分式、連続式等の周知の方式を採用できる。連続式を採用すると、大量合成が可能であり、運転作業負荷が軽い上に、未反応原料を反応系に再利用することにより原料のエタノールの使用率を極めて高いレベルに向上させることができる。そのため、簡便且つ効率的に１，３－ブタジエンを分離、回収することができる連続式を採用することが好ましい。
The reaction conditions are not particularly limited, and the reaction is usually carried out at a temperature in the range of about 200 to 300° C. under such conditions that a predetermined amount of acetaldehyde is produced.
Known methods such as a batch method, a semi-batch method, and a continuous method can be adopted for such a production method. When the continuous system is adopted, large-scale synthesis is possible, the operation workload is light, and unreacted raw materials are reused in the reaction system, so that the usage rate of raw material ethanol can be improved to an extremely high level. Therefore, it is preferable to employ a continuous system capable of separating and recovering 1,3-butadiene simply and efficiently.
原料を上記触媒に接触させる方法としては、例えば、懸濁床方式、流動床方式、固定床方式等を挙げることができる。また、本発明は、気相法、液相法のいずれであってもよい
が、気相法を用いることが好ましい。
Examples of methods for bringing the raw material into contact with the catalyst include a suspended bed method, a fluidized bed method, and a fixed bed method. Further, the present invention may be carried out by either a vapor phase method or a liquid phase method, but the vapor phase method is preferably used.
気相で反応を行う場合、原料ガス(例えば、エタノールガス、好ましくはエタノールガスとアセトアルデヒドガスの混合物)は、希釈することなく反応器に供給してもよく、窒素、ヘリウム、アルゴン、水蒸気、などの不活性ガスにより適宜希釈して反応器に供給してもよい。 When the reaction is carried out in the gas phase, the raw material gas (e.g., ethanol gas, preferably a mixture of ethanol gas and acetaldehyde gas) may be supplied to the reactor without dilution, and nitrogen, helium, argon, water vapor, etc. may be appropriately diluted with an inert gas and supplied to the reactor.
反応時に、エタノールを含む原料にアセトアルデヒドを添加してもよく、エタノールとアセトアルデヒド（添加後の総量）のモル比(ＥｔＯＨ：ＡｃＨ)が前記の比率となるようにすればよい。 During the reaction, acetaldehyde may be added to the raw material containing ethanol, and the molar ratio (EtOH:AcH) of ethanol and acetaldehyde (total amount after addition) should be the above ratio.
反応温度としては、例えば３００℃以上４５０以下℃程度、好ましくは３２０～３８０℃の範囲にある。温度が高すぎると、１，３－ブタジエン選択率が低下する。一方、温度が低すぎるとブタジエン生成速度が十分でない。 The reaction temperature is, for example, about 300°C to 450°C, preferably 320 to 380°C. If the temperature is too high, the 1,3-butadiene selectivity will decrease. On the other hand, if the temperature is too low, the rate of production of butadiene is not sufficient.
反応圧力は、常圧から高圧までの広い範囲で適宜設定できるが、製造効率や装置構成などの観点から、エタノールおよびアセトアルデヒドの分圧が０．１～１．０ＭＰａＡに設定することが好ましい。 Although the reaction pressure can be appropriately set in a wide range from normal pressure to high pressure, it is preferable to set the partial pressure of ethanol and acetaldehyde to 0.1 to 1.0 MPaA from the viewpoint of production efficiency, apparatus configuration, and the like.
原料と触媒との接触時間は、原料の供給速度を調整することによりコントロールすることができ、単位触媒あたりの重量空間速度（ＷＨＳＶ）は０．１～３０ｇ-(EtOH+AcH)・ｇ-cat -1・ｈ-1、好ましくは０．５～２０ｇ-(EtOH+AcH)・ｇ-cat -1・ｈ-1の範囲が好ましい。ＷＨＳＶが低すぎると反応器サイズが大きくなり設備費の点から好ましくない。一方、ＷＨＳＶが高すぎるとブタジエン収率が低下する。 The contact time between the raw material and the catalyst can be controlled by adjusting the feed rate of the raw material . −1 ·h −1 , preferably in the range of 0.5 to 20 g −(EtOH+AcH) ·g −cat −1 ·h −1 . If the WHSV is too low, the size of the reactor becomes large, which is not preferable in terms of equipment costs. On the other hand, if the WHSV is too high, the butadiene yield will decrease.
反応終了後、反応生成物は、例えば、蒸留、抽出等の分離手段や、これらを組み合わせた分離手段により、軽質ガス、Ｃ４留分、重質分、水、エタノール、アセトアルデヒド等に分離精製することができる。
本発明では、上述した触媒を用いて１，３－ブタジエンをより効率的に製造することができるため、産業上の利用可能性は高い。
After completion of the reaction, the reaction product is separated and purified into light gas, C4 fraction, heavy fraction, water, ethanol, acetaldehyde, etc. by separation means such as distillation, extraction, etc., or a separation means combining these. can be done.
INDUSTRIAL APPLICABILITY In the present invention, 1,3-butadiene can be produced more efficiently using the above-described catalyst, and thus the industrial applicability is high.
［実施例］
以下、本発明を実施例によりさらに詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。
＜触媒調製＞
調製例１
タンタルエトキシド（９９．９８％、Ｓｉｇｍａ－Ａｌｄｒｉｃｈ製）０．３ｇをエタノール（和光純薬工業（株）製）１００ｍｌに溶解させ、ＮＩＰＧＥＬ ＣＸ－２００（東ソー・シリカ（株）製、比表面積３９２ｍ2／ｇ）１０．０ｇを加えて２時間撹拌したのち、エバポレーターを用いてエタノールを蒸発させた。１２０℃乾燥後、空気流通下５００℃で焼成し、Ｔａ2Ｏ5／ＳｉＯ2 （Ｔａ2Ｏ5担持量：１．６重量％）触媒を得た。この触媒をＴａ2Ｏ5（１．６）／ＳｉＯ2と表記する。この触媒の比表面積は３３５ｍ2／ｇであり、担体ＳｉＯ2上のＴａ原子密度は１４．９個／ｎｍ2であった。
[Example]
EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
<Catalyst preparation>
Preparation example 1
0.3 g of tantalum ethoxide (99.98%, manufactured by Sigma-Aldrich) is dissolved in 100 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and NIPGEL CX-200 (manufactured by Tosoh Silica Co., Ltd., specific surface area 392 m 2 /g) was added and stirred for 2 hours, and then ethanol was evaporated using an evaporator. After drying at 120° C., it was calcined at 500° C. under air circulation to obtain a Ta 2 O 5 /SiO 2 (Ta 2 O 5 loading: 1.6% by weight) catalyst. This catalyst is denoted as Ta 2 O 5 (1.6)/SiO 2 . The specific surface area of this catalyst was 335 m 2 /g, and the Ta atom density on the support SiO 2 was 14.9/nm 2 .
調製例２
タンタルエトキシド０．０６ｇをエタノール１００ｍｌに溶解させ、ＮＩＰＧＥＬ ＣＸ－２００ １０．０ｇを加えて２時間撹拌したのち、エバポレーターを用いてエタノールを蒸発させた。１２０℃乾燥後、空気流通下５００℃で焼成し、Ｔａ2Ｏ5／ＳｉＯ2 （Ｔａ2Ｏ5担持量：０．１６重量％）触媒を得た。この触媒をＴａ2Ｏ5（０．１６）／ＳｉＯ2と表記する。この触媒の比表面積は３５７ｍ2／ｇであり、担体ＳｉＯ2上のＴａ原子密度は２．８個／ｎｍ2であった。
Preparation example 2
0.06 g of tantalum ethoxide was dissolved in 100 ml of ethanol, 10.0 g of NIPGEL CX-200 was added, and after stirring for 2 hours, ethanol was evaporated using an evaporator. After drying at 120° C., it was calcined at 500° C. under air circulation to obtain a Ta 2 O 5 /SiO 2 (Ta 2 O 5 loading: 0.16% by weight) catalyst. This catalyst is represented as Ta 2 O 5 (0.16)/SiO 2 . The specific surface area of this catalyst was 357 m 2 /g, and the Ta atom density on the support SiO 2 was 2.8/nm 2 .
調製例３
オキシ硝酸ジルコニウム二水和物０．２２ｇを蒸留水５０．０ｍｌに溶解させ、ＮＩＰＧＥＬ ＣＸ－２００ １０．０ｇを加えて３０分撹拌したのち、エバポレーターを用いて水を蒸発させた。１２０℃乾燥後、空気流通下５００℃で焼成し、ＺｒＯ2／ＳｉＯ2 （ＺｒＯ2担持量：１．０重量％）触媒を得た。この触媒をＺｒＯ2（１．０）／ＳｉＯ2と表記する。この触媒の比表面積は３４１ｍ2／ｇであり、担体ＳｉＯ2上のＺｒ原子密度は１４．７個／ｎｍ2であった。
Preparation example 3
0.22 g of zirconium oxynitrate dihydrate was dissolved in 50.0 ml of distilled water, 10.0 g of NIPGEL CX-200 was added, and after stirring for 30 minutes, the water was evaporated using an evaporator. After drying at 120° C., it was calcined at 500° C. under air circulation to obtain a ZrO 2 /SiO 2 (ZrO 2 loading: 1.0% by weight) catalyst. This catalyst is denoted as ZrO 2 (1.0)/SiO 2 . The specific surface area of this catalyst was 341 m 2 /g, and the Zr atom density on the support SiO 2 was 14.7/nm 2 .
調製例４
塩化ハフニウム０．２７ｇを蒸留水５０．０ｍｌに溶解させ、ＮＩＰＧＥＬ ＣＸ－２００ １０．０ｇを加えて３０分撹拌したのち、エバポレーターを用いて水を蒸発させた。１２０℃乾燥後、空気流通下５００℃で焼成し、ＨｆＯ2／ＳｉＯ2 （ＨｆＯ2担持量１．７重量％）触媒を得た。この触媒をＨｆＯ2（１．７）／ＳｉＯ2と表記する。この触媒の比表面積は３５０ｍ2／ｇであり、担体ＳｉＯ2上のＺｒ原子密度は１４．３個／ｎｍ2であった。
Preparation example 4
0.27 g of hafnium chloride was dissolved in 50.0 ml of distilled water, 10.0 g of NIPGEL CX-200 was added, and after stirring for 30 minutes, the water was evaporated using an evaporator. After drying at 120° C., it was calcined at 500° C. under air flow to obtain a HfO 2 /SiO 2 (HfO 2 loading amount: 1.7% by weight) catalyst. This catalyst is denoted as HfO 2 (1.7)/SiO 2 . The specific surface area of this catalyst was 350 m 2 /g, and the Zr atom density on the support SiO 2 was 14.3/nm 2 .
調製例５
調製例１で得られたＴａ2Ｏ5（１．６）／ＳｉＯ2 ３．０ｇにＮＨ3水（ｐＨ＝１０．０） １５ｍｌを加えて、そこに３－アミノプロピルトリエトキシシラン（信越化学工業（株）製） ０．０７０ｇを滴下し、撹拌しながら６０℃まで昇温して４時間保持した。その後、遠心分離で触媒を回収し、１２０℃乾燥後、空気流通下５００℃で焼成した。このように得られた触媒をＳｉ－Ｔａ2Ｏ5（１．６）／ＳｉＯ2と表記する。この触媒の比表面積は２８９ｍ2／ｇであった。
Preparation example 5
15 ml of NH 3 water (pH=10.0) was added to 3.0 g of Ta 2 O 5 (1.6)/SiO 2 obtained in Preparation Example 1, and 3-aminopropyltriethoxysilane (Shin-Etsu Chemical (manufactured by Kogyo Co., Ltd.) was added dropwise, and the temperature was raised to 60°C with stirring and maintained for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120°C, and calcined at 500°C under air flow. The catalyst thus obtained is denoted as Si--Ta 2 O 5 (1.6)/SiO 2 . The specific surface area of this catalyst was 289 m 2 /g.
調製例６
ケイ酸エチル（和光純薬工業（株）製）１２．５ｇ、エタノール１２．５ｍｌ、蒸留水１．１ｇ、硝酸０．５５ｇ（和光純薬工業（株）製）を混合し、撹拌しながら７６℃で３時間還流した。一方で、タンタルエトキシド０．３ｇをエタノール１００ｍｌに溶解させ、ＮＩＰＧＥＬ ＣＸ－２００ １０．０ｇを加えて室温で２時間撹拌した。これら２つの溶液を混合し、７６℃で５時間還流した。その後、遠心分離で触媒を回収し、１２０℃乾燥後、空気流通下５００℃で焼成した。このように得られた触媒をＳｉ（ＴＥＯＳ）－Ｔａ2Ｏ5（１．６）／ＳｉＯ2と表記する。この触媒の比表面積は３６１ｍ2／ｇであった。
Preparation example 6
12.5 g of ethyl silicate (manufactured by Wako Pure Chemical Industries, Ltd.), 12.5 ml of ethanol, 1.1 g of distilled water, and 0.55 g of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and stirred for 76 It was refluxed at 0 C for 3 hours. On the other hand, 0.3 g of tantalum ethoxide was dissolved in 100 ml of ethanol, 10.0 g of NIPGEL CX-200 was added, and the mixture was stirred at room temperature for 2 hours. These two solutions were mixed and refluxed at 76° C. for 5 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120°C, and calcined at 500°C under air flow. The catalyst thus obtained is denoted as Si(TEOS)--Ta 2 O 5 (1.6)/SiO 2 . The specific surface area of this catalyst was 361 m 2 /g.
調製例７
調製例２で得られたＴａ2Ｏ5（０．１６）／ＳｉＯ2 ３．０ｇにＮＨ3水（ｐＨ＝１０．０）１５ｍｌを加えて、そこに３－アミノプロピルトリエトキシシラン０．０２６ｇを滴下し、撹拌しながら６０℃まで昇温して４時間保持した。その後、遠心分離で触媒を回収し、１２０℃乾燥後、空気流通下５００℃で焼成した。このように得られた触媒をＳｉ－Ｔａ2Ｏ5（０．１６）／ＳｉＯ2と表記する。この触媒の比表面積は３１４ｍ2／ｇであった。
Preparation Example 7
15 ml of NH 3 water (pH=10.0) was added to 3.0 g of Ta 2 O 5 (0.16)/SiO 2 obtained in Preparation Example 2, and 0.026 g of 3-aminopropyltriethoxysilane was added. was added dropwise, and the temperature was raised to 60° C. with stirring and maintained for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120°C, and calcined at 500°C under air flow. The catalyst thus obtained is denoted as Si--Ta 2 O 5 (0.16)/SiO 2 . The specific surface area of this catalyst was 314 m 2 /g.
調製例８
調製例３で得られたＺｒＯ2（１．０）／ＳｉＯ2 ３．０ｇにＮＨ3水（ｐＨ＝１０．０） １５ｍｌを加えて、そこに３－アミノプロピルトリエトキシシラン０．０８３ｇを滴下し、撹拌しながら６０℃まで昇温して４時間保持した。その後、遠心分離で触媒を回収し、１２０℃乾燥後、空気流通下５００℃で焼成した。このように得られた触媒をＳｉ－ＺｒＯ2（１．０）／ＳｉＯ2と表記する。この触媒の比表面積は３０５ｍ2／ｇであった。
Preparation Example 8
15 ml of NH 3 water (pH=10.0) was added to 3.0 g of ZrO 2 (1.0)/SiO 2 obtained in Preparation Example 3, and 0.083 g of 3-aminopropyltriethoxysilane was added dropwise. The temperature was raised to 60° C. with stirring and maintained for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120°C, and calcined at 500°C under air flow. The catalyst thus obtained is denoted as Si--ZrO 2 (1.0)/SiO 2 . The specific surface area of this catalyst was 305 m 2 /g.
調製例９
調製例４で得られたＨｆＯ2（１．７）／ＳｉＯ2 ３．０ｇにＮＨ3水（ｐＨ＝１０．０）１５ｍｌを加えて、そこに３－アミノプロピルトリエトキシシラン０．０８３ｇを滴下し、撹拌しながら６０℃まで昇温して４時間保持した。その後、遠心分離で触媒を回収し、１２０℃乾燥後、空気流通下５００℃で焼成した。このように得られた触媒をＳｉ－ＨｆＯ2（１．７）／ＳｉＯ2と表記する。この触媒の比表面積は３０７ｍ2／ｇであった。
Preparation Example 9
15 ml of NH 3 water (pH=10.0) was added to 3.0 g of HfO 2 (1.7)/SiO 2 obtained in Preparation Example 4, and 0.083 g of 3-aminopropyltriethoxysilane was added dropwise. The temperature was raised to 60° C. with stirring and maintained for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120°C, and calcined at 500°C under air flow. The catalyst thus obtained is denoted as Si--HfO 2 (1.7)/SiO 2 . The specific surface area of this catalyst was 307 m@2 /g.
比較例１～４、実施例１～５
＜反応試験＞
表１に記載の触媒 ０．６３ｇ を固定床流通型反応器に充填し、以下の反応条件で実験を行った。
Comparative Examples 1-4, Examples 1-5
<Reaction test>
A fixed bed flow reactor was filled with 0.63 g of the catalyst shown in Table 1, and an experiment was conducted under the following reaction conditions.
反応器に窒素（６．８Ｎｍｌ／ｍｉｎ）を流しながら３５０℃まで昇温し０．２６ＭＰａＧまで昇圧した後、原料ガスとしてエタノール（１１．０Ｎｍｌ／ｍｉｎ）とアセトアルデヒド（４．４Ｎｍｌ／ｍｉｎ）および窒素（６．８Ｎｍｌ／ｍｉｎ）を混合して反応器に供給した（ＷＨＳＶ＝３．０ｇ-(EtOH+AcH)・ｇ-cat
-1・ｈ-1）。反応器出口ガス組成をガスクロマトグラフにより求めた。
転化率、選択率は以下の式により求めた。
While flowing nitrogen (6.8 Nml / min) in the reactor, the temperature was raised to 350 ° C. and the pressure was increased to 0.26 MPaG, and then ethanol (11.0 Nml / min) and acetaldehyde (4.4 Nml / min) and nitrogen (6.8 Nml/min) were mixed and fed to the reactor (WHSV=3.0 g -(EtOH+AcH) ·g -cat -1 ·h -1 ). The reactor outlet gas composition was determined by gas chromatography.
The conversion rate and selectivity were determined by the following equations.
比較例１のＴａ2Ｏ5（１．６）／ＳｉＯ2では１，３－ブタジエン選択率６６．２Ｃ－ｍｏｌ％、１，３－ブタジエン収率３２．３Ｃ－ｍｏｌ％であるのに対し、実施例１のＳｉ－Ｔａ2Ｏ5（１．６）／ＳｉＯ2では１，３－ブタジエン選択率７９．９Ｃ－ｍｏｌ％、１，３－ブタジエン収率３９．５Ｃ－ｍｏｌ％、実施例２のＳｉ(ＴＥＯＳ)-Ｔａ2Ｏ5（１．６）／ＳｉＯ2では１，３－ブタジエン選択率７３．４Ｃ－ｍｏｌ％、１，３－ブタジエン収率３６．８Ｃ－ｍｏｌ％と、ケイ素を含む物質により処理されることによって１，３－ブタジエン選択率、１，３－ブタジエン収率が向上した。処理によって転化率はほとんど変わらなかった。 In Ta 2 O 5 (1.6)/SiO 2 of Comparative Example 1, the 1,3-butadiene selectivity was 66.2 C-mol% and the 1,3-butadiene yield was 32.3 C-mol%. In the case of Si—Ta 2 O 5 (1.6)/SiO 2 of Example 1, the 1,3-butadiene selectivity was 79.9 C-mol% and the 1,3-butadiene yield was 39.5 C-mol%. Si(TEOS)-Ta 2 O 5 (1.6)/SiO 2 has a 1,3-butadiene selectivity of 73.4 C-mol% and a 1,3-butadiene yield of 36.8 C-mol%. The 1,3-butadiene selectivity and 1,3-butadiene yield were improved by treatment with the containing substance. The conversion hardly changed with the treatment.
Ｔａ担持量の異なるＴａ2Ｏ5（０．１６）／ＳｉＯ2でも、比較例２と比べてケイ素を含む化合物による処理を行った実施例３では、１，３－ブタジエン収率は１６．２Ｃ－ｍｏｌ％から１６．７Ｃ－ｍｏｌ％とやや向上し、１，３－ブタジエン選択率が６６．３Ｃ－ｍｏｌ％から７１．７Ｃ－ｍｏｌ％に向上した（それぞれ比較例２、実施例３）。 Even with Ta 2 O 5 (0.16)/SiO 2 having a different Ta loading amount, in Example 3 in which the treatment with a silicon-containing compound was performed compared to Comparative Example 2, the yield of 1,3-butadiene was 16.2C. -mol% to 16.7C-mol%, and the 1,3-butadiene selectivity improved from 66.3C-mol% to 71.7C-mol% (Comparative Example 2 and Example 3, respectively).
同様に、ＺｒＯ2（１．０）／ＳｉＯ2でも、比較例３に比べてケイ素を含む化合物による処理によって実施例４では、１，３－ブタジエン収率は３２．３Ｃ－ｍｏｌ％から３７．４Ｃ－ｍｏｌ％に、１，３－ブタジエン選択率は６７．５Ｃ－ｍｏｌ％から７７．３Ｃ－ｍｏｌ％に向上した（それぞれ比較例３、実施例４）。 Similarly, even with ZrO 2 (1.0)/SiO 2 , the 1,3-butadiene yield increased from 32.3 C-mol % to 37.3 C-mol % in Example 4 by treatment with a silicon-containing compound compared to Comparative Example 3. 4 C-mol%, the 1,3-butadiene selectivity improved from 67.5 C-mol% to 77.3 C-mol% (Comparative Example 3 and Example 4, respectively).
ＨｆＯ2（１．７）／ＳｉＯ2でも比較例４と実施例５とを対比すると、１，３－ブタジエン収率が３７．０Ｃ－ｍｏｌ％から３９．１Ｃ－ｍｏｌ％に、１，３－ブタジエン選択率が６４．１Ｃ－ｍｏｌ％から６８．０Ｃ－ｍｏｌ％に向上した（比較例３、実施例５）。 Comparing Comparative Example 4 and Example 5 also with HfO 2 (1.7)/SiO 2 , the 1,3-butadiene yield increased from 37.0 C-mol% to 39.1 C-mol%. The butadiene selectivity improved from 64.1 C-mol% to 68.0 C-mol% (Comparative Example 3, Example 5).
＜29Ｓｉ－ＭＡＳ－ＮＭＲ測定＞
29Ｓｉ－ＭＡＳ－ＮＭＲ測定は以下の条件で実施した。
装置：Ａｇｉｌｅｎｔ社製ＶＮＭＲＳ－６００
パルスプログラム：シングルパルス
サンプル回転数：６ ｋＨｚ
繰り返し時間：１００ ｓｅｃ
パルス幅：９０°
積算回数：５１２回
二次標準としてポリジメチルシロキサン（ＰＤＭＳ）を用いて－３４．４４ｐｐｍに調整
< 29 Si-MAS-NMR measurement>
29 Si-MAS-NMR measurements were carried out under the following conditions.
Apparatus: Agilent VNMRS-600
Pulse program: Single pulse Sample rotation speed: 6 kHz
Repeat time: 100 sec
Pulse width: 90°
Accumulation times: 512 times Adjusted to -34.44 ppm using polydimethylsiloxane (PDMS) as a secondary standard
比較例５
調製例１で得られたＴａ2Ｏ5（１．６）／ＳｉＯ2の29Ｓｉ－ＭＡＳ－ＮＭＲを測定した。Ｑ２（－９１ｐｐｍ付近）、Ｑ３（－１０１ｐｐｍ付近）、Ｑ４（－１１１ｐｐｍ付近）に帰属されるシグナルが検出された。ケミカルシフト値－１１１ｐｐｍ付近の極大値のシグナル強度を１とした場合の、ケミカルシフト値－１０５ｐｐｍでのシグナル強度は０．４８であった。
Comparative example 5
29 Si-MAS-NMR of Ta 2 O 5 (1.6)/SiO 2 obtained in Preparation Example 1 was measured. Signals assigned to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. The signal intensity at the chemical shift value of −105 ppm was 0.48 when the maximum signal intensity near the chemical shift value of −111 ppm was set to 1.
実施例６
調製例６で得られたＳｉ－Ｔａ2Ｏ5（１．６）／ＳｉＯ2の29Ｓｉ－ＭＡＳ－ＮＭＲを測定した。Ｑ２（－９１ｐｐｍ付近）、Ｑ３（－１０１ｐｐｍ付近）、Ｑ４（－１１１ｐｐｍ付近）に帰属されるシグナルが検出された。ケミカルシフト値－１１１ｐｐｍ付近の極大値のシグナル強度を１とした場合の、ケミカルシフト値－１０５ｐｐｍでのシグナル強度は０．６８であった。
Example 6
29 Si-MAS-NMR of Si--Ta 2 O 5 (1.6)/SiO 2 obtained in Preparation Example 6 was measured. Signals assigned to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. The signal intensity at the chemical shift value of −105 ppm was 0.68 when the maximum signal intensity near the chemical shift value of −111 ppm was set to 1.
実施例７
調製例７で得られたＳｉ（ＴＥＯＳ）－Ｔａ2Ｏ5（１．６）／ＳｉＯ2の29Ｓｉ－ＭＡＳ－ＮＭＲを測定した。Ｑ２（－９１ｐｐｍ付近）、Ｑ３（－１０１ｐｐｍ付近）、Ｑ４（－１１１ｐｐｍ付近）に帰属されるシグナルが検出された。ケミカルシフト値－１１１ｐｐｍ付近の極大値のシグナル強度を１とした場合の、ケミカルシフト値－１０５ｐｐｍでのシグナル強度は０．５８であった。
Example 7
29 Si-MAS-NMR of Si(TEOS)--Ta 2 O 5 (1.6)/SiO 2 obtained in Preparation Example 7 was measured. Signals assigned to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. The signal intensity at the chemical shift value of −105 ppm was 0.58 when the maximum signal intensity near the chemical shift value of −111 ppm was set to 1.
Claims (8)
混合物を、加熱、濃縮、水熱合成から選ばれる少なくとも１種の処理を施したのち、乾燥・焼成する工程と、 a step of subjecting the mixture to at least one treatment selected from heating, concentration, and hydrothermal synthesis, followed by drying and firing;
乾燥・焼成物の表面水酸基およびオキソ基の少なくとも一部を、加水分解性基を有するケイ素化合物と反応させ、前記表面水酸基および前記オキソ基の少なくとも一部を－Ｏ－Ｓｉ基で置換する工程、 A step of reacting at least part of the surface hydroxyl groups and oxo groups of the dried/baked product with a silicon compound having a hydrolyzable group to replace at least part of the surface hydroxyl groups and the oxo groups with —O—Si groups;
を含む、エタノールを含む原料から１，３－ブタジエンを製造する１，３－ブタジエン製造触媒の製造方法。A method for producing a 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol.
前記物質の表面水酸基およびオキソ基の少なくとも一部を、加水分解性基を有するケイ素化合物と反応させ、前記表面水酸基および前記オキソ基の少なくとも一部を－Ｏ－Ｓｉ基で置換する工程と、 a step of reacting at least a portion of the surface hydroxyl groups and oxo groups of the substance with a silicon compound having a hydrolyzable group to replace at least a portion of the surface hydroxyl groups and the oxo groups with —O—Si groups;
を備える、エタノールを含む原料から１，３－ブタジエンを製造する１，３－ブタジエン製造触媒の製造方法。 A method for producing a 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol.
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