JP2020040065A - Catalyst for 1,3-butadiene synthesis, apparatus for producing 1,3-butadiene, and method for producing 1,3-butadiene - Google Patents
Catalyst for 1,3-butadiene synthesis, apparatus for producing 1,3-butadiene, and method for producing 1,3-butadiene Download PDFInfo
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 65
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 62
- 238000000034 method Methods 0.000 description 23
- 239000006227 byproduct Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- -1 cyclopentadienyl compound Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- IENXJNLJEDMNTE-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.NCCN IENXJNLJEDMNTE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical class O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical group [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、１，３−ブタジエン合成用触媒、１，３−ブタジエンの製造装置及び１，３−ブタジエンの製造方法に関する。 The present invention relates to a catalyst for synthesizing 1,3-butadiene, an apparatus for producing 1,3-butadiene, and a method for producing 1,3-butadiene.
１，３−ブタジエン等のブタジエンは、スチレン−ブタジエンゴム（ＳＢＲ）等の原料として用いられている。従来、ブタジエンは石油からエチレンを合成するナフサクラッキングの際に副生するＣ４留分から精製されたものが使用されていた。しかし、シェールガスの利用量の増加に伴って石油の利用量が減少し、その結果、石油のナフサクラッキングで得られるブタジエンの生産量も減少している。そのため、１，３−ブタジエンを製造するための代替方法が求められている。 Butadiene such as 1,3-butadiene is used as a raw material for styrene-butadiene rubber (SBR) and the like. Conventionally, butadiene used has been purified from a C4 fraction produced as a by-product during naphtha cracking for synthesizing ethylene from petroleum. However, as the use of shale gas increases, the use of petroleum decreases, and as a result, the production of butadiene obtained from naphtha cracking of petroleum also decreases. Therefore, there is a need for an alternative method for producing 1,3-butadiene.
１，３−ブタジエンの製造方法としては、例えば、１−ブテンを原料とした酸化的脱水素反応により１，３−ブタジエンを得る方法が知られている。しかし、該方法では、生成物中に１，３−ブタジエンと分離が困難な１−ブテンが残存するため、精製過程が煩雑になり経済性が劣る。 As a method for producing 1,3-butadiene, for example, a method for obtaining 1,3-butadiene by an oxidative dehydrogenation reaction using 1-butene as a raw material is known. However, according to this method, 1-butene, which is difficult to separate from 1,3-butadiene, remains in the product, so that the purification process is complicated and economical efficiency is poor.
ところで、近年では、石油から得られる化学工業原料に代えてバイオマス由来原料から誘導された化学工業原料が注目されており、１，３−ブタジエンについてもサトウキビやトウモロコシ等のバイオマス由来のバイオエタノールから製造することの重要度が増している。エタノールの二量化反応により１，３−ブタジエンを製造する方法としては、例えば、以下の方法（ｉ）、（ｉｉ）が提案されている。 By the way, in recent years, chemical industrial raw materials derived from biomass-derived raw materials have attracted attention instead of chemical industrial raw materials obtained from petroleum, and 1,3-butadiene is also produced from bioethanol derived from biomass such as sugarcane and corn. The importance of doing it is increasing. As a method for producing 1,3-butadiene by a dimerization reaction of ethanol, for example, the following methods (i) and (ii) have been proposed.
（ｉ）Ｈｆ、Ｃｕ、Ｚｎを中心とした１元系又は多元系の担持触媒を用いてエタノールから１，３−ブタジエンを製造する方法（非特許文献１）。
（ｉｉ）マグネシウムシリケート構造を有する触媒にエタノールを接触させて１，３−ブタジエンを得る方法（特許文献１）。
しかし、方法（ｉ）、（ｉｉ）でも、エタノールからエチレンを介して１−ブテンが副生するため、１−ブテンを除去するには精製過程が煩雑になり経済性が劣る問題がある。
(I) A method for producing 1,3-butadiene from ethanol using a one- or multi-component supported catalyst centering on Hf, Cu, and Zn (Non-Patent Document 1).
(Ii) A method of obtaining 1,3-butadiene by bringing ethanol into contact with a catalyst having a magnesium silicate structure (Patent Document 1).
However, even in the methods (i) and (ii), since 1-butene is by-produced from ethanol via ethylene, there is a problem that removing 1-butene complicates a purification process and lowers economic efficiency.
本発明は、１−ブテンの副生を充分に抑制しつつエタノールから１，３−ブタジエンを合成できる１，３−ブタジエン合成用触媒、並びに該１，３−ブタジエン合成用触媒を用いた１，３−ブタジエンの製造装置及び製造方法を提供することを目的とする。 The present invention provides a 1,3-butadiene synthesis catalyst capable of synthesizing 1,3-butadiene from ethanol while sufficiently suppressing 1-butene by-product, and a 1,3-butadiene synthesis catalyst using the 1,3-butadiene synthesis catalyst. An object of the present invention is to provide an apparatus and a method for producing 3-butadiene.
本発明の１，３−ブタジエン合成用触媒は、エタノールから１，３−ブタジエンを合成するための１，３−ブタジエン合成用触媒であって、成分（Ａ）：Ｃｕと、成分（Ｂ）：Ｚｎと、成分（Ｃ）：Ｂ、Ｂａ、Ｃａ、Ｇｅ、Ｋ、Ｌｉ、Ｍｇ、Ｎａ、Ｔａ及びＷからなる群から選ばれる１種以上と、のいずれかから選ばれる成分が多孔質担体に担持され、前記成分（Ａ）〜（Ｃ）の合計の担持量は、前記多孔質担体の質量に対して、１．０〜５．０質量％であり、前記多孔質担体における細孔容積の合計が０．２５〜１．５０ｍＬ／ｇである。
前記成分（Ｃ）は、Ｂａ、Ｃａ、Ｋ、Ｌｉ及びＮａからなる群から選ばれる１種以上であることが好ましい。
前記多孔質担体の平均細孔直径は０．１〜１００ｎｍであることが好ましい。
前記多孔質担体の比表面積は５０〜１０００ｍ２／ｇであることが好ましい。
The 1,3-butadiene synthesis catalyst of the present invention is a 1,3-butadiene synthesis catalyst for synthesizing 1,3-butadiene from ethanol, and comprises a component (A): Cu, and a component (B): Zn and one or more components selected from the group consisting of component (C): B, Ba, Ca, Ge, K, Li, Mg, Na, Ta and W are contained in the porous carrier. The total amount of the components (A) to (C) supported is 1.0 to 5.0% by mass with respect to the mass of the porous carrier, and the pore volume of the porous carrier is The sum is 0.25 to 1.50 mL / g.
The component (C) is preferably at least one selected from the group consisting of Ba, Ca, K, Li and Na.
The average pore diameter of the porous carrier is preferably 0.1 to 100 nm.
The specific surface area of the porous carrier is preferably 50 to 1000 m 2 / g.
本発明の１，３−ブタジエンの製造装置は、本発明の１，３−ブタジエン合成用触媒が充填された反応管と、エタノールを前記反応管内に供給する供給手段と、前記反応管から生成物を排出する排出手段と、を備える。 The apparatus for producing 1,3-butadiene of the present invention comprises a reaction tube filled with the catalyst for synthesizing 1,3-butadiene of the present invention, a supply unit for supplying ethanol into the reaction tube, and a product from the reaction tube. Discharging means for discharging water.
本発明の１，３−ブタジエンの製造方法は、本発明の１，３−ブタジエン合成用触媒にエタノールを接触させて１，３−ブタジエンを得る方法である。
前記エタノールは、ガス化されたエタノールであるであることが好ましい。
The method for producing 1,3-butadiene of the present invention is a method for obtaining 1,3-butadiene by bringing ethanol into contact with the catalyst for synthesizing 1,3-butadiene of the present invention.
Preferably, the ethanol is gasified ethanol.
本発明の１，３−ブタジエン合成用触媒を用いれば、１−ブテンの副生を充分に抑制しつつエタノールから１，３−ブタジエンを合成できる。
本発明の１，３−ブタジエンの製造装置を用いれば、１−ブテンの副生を充分に抑制しつつエタノールから１，３−ブタジエンを製造することができる。
本発明の１，３−ブタジエンの製造方法によれば、１−ブテンの副生を充分に抑制しつつエタノールから１，３−ブタジエンを製造することができる。
When the catalyst for synthesizing 1,3-butadiene of the present invention is used, 1,3-butadiene can be synthesized from ethanol while sufficiently suppressing 1-butene by-product.
By using the apparatus for producing 1,3-butadiene of the present invention, 1,3-butadiene can be produced from ethanol while sufficiently suppressing 1-butene by-product.
According to the method for producing 1,3-butadiene of the present invention, 1,3-butadiene can be produced from ethanol while sufficiently suppressing 1-butene by-product.
以下の用語の定義は、本明細書及び特許請求の範囲にわたって適用される。
「１，３−ブタジエンの選択率」とは、合成用触媒を用いた反応で消費されたエタノールのモル数のうち、１，３−ブタジエンへ変換されたエタノールのモル数が占める百分率を意味する。
「１−ブテンの選択率」とは、合成用触媒を用いた反応で消費されたエタノールのモル数のうち、１−ブテンへ変換されたエタノールのモル数が占める百分率を意味する。
The following term definitions apply throughout the present description and claims.
The “selectivity of 1,3-butadiene” means the percentage of the moles of ethanol converted to 1,3-butadiene out of the moles of ethanol consumed in the reaction using the synthesis catalyst. .
The “selectivity of 1-butene” means the percentage of the number of moles of ethanol converted to 1-butene in the number of moles of ethanol consumed in the reaction using the synthesis catalyst.
［１，３−ブタジエン合成用触媒］
本発明の１，３−ブタジエン合成用触媒（以下、単に「合成用触媒」という。）は、エタノールから１，３−ブタジエンを合成するための触媒である。本発明の合成用触媒は、成分（Ａ）：Ｃｕと、成分（Ｂ）：Ｚｎと、成分（Ｃ）：Ｂ、Ｂａ、Ｃａ、Ｇｅ、Ｋ、Ｌｉ、Ｍｇ、Ｎａ、Ｔａ及びＷからなる群から選ばれる１種以上と、を含む。本発明の合成用触媒が成分（Ａ）〜（Ｃ）を含むことで、１−ブテンの副生を充分に抑制しつつエタノールから１，３−ブタジエンを合成することができる。
[Catalyst for 1,3-butadiene synthesis]
The 1,3-butadiene synthesis catalyst of the present invention (hereinafter, simply referred to as “synthesis catalyst”) is a catalyst for synthesizing 1,3-butadiene from ethanol. The synthesis catalyst of the present invention comprises component (A): Cu, component (B): Zn, and component (C): B, Ba, Ca, Ge, K, Li, Mg, Na, Ta and W. And one or more selected from the group. When the synthesis catalyst of the present invention contains the components (A) to (C), 1,3-butadiene can be synthesized from ethanol while sufficiently suppressing 1-butene by-product.
成分（Ｃ）としては、１−ブテンの副生を抑制する効果がより高い点から、Ｂ、Ｂａ、Ｃａ、Ｇｅ、Ｋ、Ｌｉ、Ｎａ及びＷからなる群から選ばれる１種以上であることが好ましい。また、成分（Ｃ）としては、１−ブテンの副生に加えてエチレンの副生も抑制できる点から、Ｂ、Ｂａ、Ｃａ及びＧｅからなる群から選ばれる１種以上であることがより好ましい。 The component (C) is at least one selected from the group consisting of B, Ba, Ca, Ge, K, Li, Na, and W, since the effect of suppressing the by-product of 1-butene is higher. Is preferred. In addition, the component (C) is more preferably at least one selected from the group consisting of B, Ba, Ca, and Ge from the viewpoint that by-product of ethylene can be suppressed in addition to 1-butene. .
本発明の合成用触媒は、下記（１）式で表される組成の触媒であることが好ましい。
ａＣｕ・ｂＺｎ・ｃＭ１ ・・・・（１）
ただし、（１）式中、Ｍ１は、Ｂ、Ｂａ、Ｃａ、Ｇｅ、Ｋ、Ｌｉ、Ｍｇ、Ｎａ、Ｔａ及びＷからなる群から選ばれる１種以上を表し、ａ、ｂ及びｃは多孔質担体に対する質量百分率を表す。
The synthesis catalyst of the present invention is preferably a catalyst having a composition represented by the following formula (1).
aCu.bZn.cM 1 ... (1)
Here, in the formula (1), M 1 represents at least one selected from the group consisting of B, Ba, Ca, Ge, K, Li, Mg, Na, Ta and W, and a, b and c are porous. Represents the mass percentage based on the weight of the carrier.
（１）式中のａは、１０〜０．０１が好ましく、５〜０．１がより好ましく、２．５〜０．５がさらに好ましい。ａが前記下限値未満であれば、反応中間体であるアセトアルデヒドの生成量が増加する（１，３−ブタジエンの選択率が減少する）。ａが前記上限値超であれば、副生物であるエチレンの生成量が増加する（１，３−ブタジエンの選択率が減少する）。
（１）式中のｂは、１０〜０．０１が好ましく、５〜０．０５がより好ましく、１〜０．１がさらに好ましい。ｂが前記下限値未満であれば、副生物であるエチレンの生成量が増加する（１，３−ブタジエンの選択率が減少する）。ｂが前記上限値超であれば、副生物であるプロピレンの生成量が増加する（１，３−ブタジエンの選択率が減少する）。
（１）式中のｃは、１０〜０．０１が好ましく、５〜０．１がより好ましい。ｃが前記下限値未満であれば、原料転化率（エタノールが反応物へ変化する割合）が減少する。ｃが前記上限値超であれば、Ｃ４以上の副生物質が増加する（１，３−ブタジエンの選択率が減少する）。
A in the formula (1) is preferably from 10 to 0.01, more preferably from 5 to 0.1, and even more preferably from 2.5 to 0.5. If a is less than the lower limit, the production amount of acetaldehyde as a reaction intermediate increases (selectivity of 1,3-butadiene decreases). If a exceeds the upper limit, the amount of ethylene produced as a by-product increases (the selectivity for 1,3-butadiene decreases).
B in the formula (1) is preferably from 10 to 0.01, more preferably from 5 to 0.05, even more preferably from 1 to 0.1. If b is less than the lower limit, the amount of ethylene as a by-product increases (the selectivity for 1,3-butadiene decreases). If b exceeds the upper limit, the amount of propylene produced as a by-product increases (the selectivity for 1,3-butadiene decreases).
(1) c in the formula is preferably from 10 to 0.01, more preferably from 5 to 0.1. If c is less than the lower limit, the raw material conversion (the rate at which ethanol changes to a reactant) decreases. If c exceeds the upper limit, by-products of C4 or more increase (selectivity of 1,3-butadiene decreases).
本発明の合成用触媒における成分（Ａ）と成分（Ｂ）との質量比（Ａ／Ｂ）は、１００〜０．１が好ましく、１０〜０．５がより好ましい。質量比（Ａ／Ｂ）が前記範囲内であれば、１−ブテンの副生を抑制する効果がより高くなる。 The mass ratio (A / B) of the component (A) to the component (B) in the synthesis catalyst of the present invention is preferably from 100 to 0.1, and more preferably from 10 to 0.5. When the mass ratio (A / B) is within the above range, the effect of suppressing 1-butene by-product becomes higher.
本発明の合成用触媒における成分（Ａ）と成分（Ｃ）との質量比（Ａ／Ｃ）は、１００〜０．１が好ましく、１０〜０．５がより好ましい。質量比（Ａ／Ｃ）が前記範囲内であれば、１−ブテンの副生を抑制する効果がより高くなる。 The mass ratio (A / C) of the component (A) to the component (C) in the synthesis catalyst of the present invention is preferably 100 to 0.1, and more preferably 10 to 0.5. When the mass ratio (A / C) is within the above range, the effect of suppressing 1-butene by-product becomes higher.
本発明の合成用触媒としては、１，３−ブタジエンの選択率がより高くなる点から、成分（Ａ）〜（Ｃ）が多孔質担体に担持された担持触媒が好ましい。多孔質担体の材質は、特に限定されず、例えば、シリカ、ジルコニア、チタニア、マグネシア等が挙げられる。なかでも、比表面積や細孔直径が異なる種々の製品が市場で調達できることから、シリカが好ましい。 As the synthesis catalyst of the present invention, a supported catalyst in which the components (A) to (C) are supported on a porous carrier is preferable because the selectivity for 1,3-butadiene is higher. The material of the porous carrier is not particularly limited, and examples thereof include silica, zirconia, titania, and magnesia. Among them, silica is preferable because various products having different specific surface areas and pore diameters can be procured on the market.
多孔質担体の大きさは特に限定されず、例えば、シリカの多孔質担体であれば、粒子径１５０〜２３６０μｍのものが好ましい。多孔質担体の粒子径は、篩分けにより調節される。多孔質担体は、粒子径分布ができるだけ狭いものが好ましい。 The size of the porous carrier is not particularly limited. For example, a porous carrier made of silica preferably has a particle size of 150 to 2360 μm. The particle size of the porous carrier is adjusted by sieving. The porous carrier preferably has a particle size distribution as narrow as possible.
多孔質担体における細孔容積の合計（全細孔容積）は、０．１０〜２．５０ｍＬ／ｇが好ましく、０．２５〜１．５０ｍＬ／ｇがより好ましい。全細孔容積が前記下限値以上であれば、充分な量の成分（Ａ）〜（Ｃ）を担持しやすく、１，３−ブタジエンの選択率がより高くなる。全細孔容積が前記上限値以下であれば、エタノールと合成用触媒との接触時間が充分となりやすく、１，３−ブタジエンの選択率が高くなりやすい。
なお、多孔質担体の全細孔容積は、水滴定法により測定される値である。水滴定法とは、多孔質担体の表面に水分子を吸着させ、分子の凝縮から細孔分布を測定する方法である。
The total pore volume (total pore volume) of the porous carrier is preferably from 0.10 to 2.50 mL / g, more preferably from 0.25 to 1.50 mL / g. When the total pore volume is equal to or larger than the lower limit, a sufficient amount of the components (A) to (C) can be easily supported, and the selectivity of 1,3-butadiene becomes higher. When the total pore volume is equal to or less than the upper limit, the contact time between ethanol and the synthesis catalyst tends to be sufficient, and the selectivity for 1,3-butadiene tends to increase.
The total pore volume of the porous carrier is a value measured by a water titration method. The water titration method is a method in which water molecules are adsorbed on the surface of a porous carrier, and the pore distribution is measured from the condensation of the molecules.
多孔質担体の平均細孔直径は、０．１〜１００ｎｍが好ましく、１．０〜５０ｎｍがより好ましい。平均細孔直径が前記下限値以上であれば、充分な量の成分（Ａ）〜（Ｃ）を担持しやすく、１，３−ブタジエンの選択率がより高くなる。平均細孔直径が前記上限値以下であれば、エタノールと合成用触媒との接触時間が充分となりやすく、１，３−ブタジエンの選択率が高くなりやすい。 The average pore diameter of the porous carrier is preferably from 0.1 to 100 nm, more preferably from 1.0 to 50 nm. When the average pore diameter is equal to or larger than the lower limit, a sufficient amount of the components (A) to (C) can be easily supported, and the selectivity for 1,3-butadiene can be further increased. When the average pore diameter is equal to or less than the upper limit, the contact time between ethanol and the synthesis catalyst tends to be sufficient, and the selectivity for 1,3-butadiene tends to increase.
なお、平均細孔直径は、以下の手法で測定される値である。平均細孔直径が０．１ｎｍ以上１０ｎｍ未満の場合、平均細孔直径は、全細孔容積とＢＥＴ比表面積とから算出される。平均細孔直径が１０ｎｍ以上の場合、平均細孔直径は、水銀圧入法ポロシメーターにより測定される。ＢＥＴ比表面積は、窒素を吸着ガスとし、その吸着量とその時の圧力から算出される値である。水銀圧入法は、水銀を加圧して多孔質担体の細孔に圧入させ、その圧力と圧入された水銀量から平均細孔直径を算出するものである。 The average pore diameter is a value measured by the following method. When the average pore diameter is 0.1 nm or more and less than 10 nm, the average pore diameter is calculated from the total pore volume and the BET specific surface area. When the average pore diameter is 10 nm or more, the average pore diameter is measured by a mercury intrusion porosimeter. The BET specific surface area is a value calculated from the amount of adsorption and the pressure at that time using nitrogen as the adsorption gas. In the mercury intrusion method, mercury is pressurized and injected into the pores of a porous carrier, and the average pore diameter is calculated from the pressure and the amount of the injected mercury.
多孔質担体の比表面積は、５０〜１０００ｍ２／ｇが好ましく、１００〜７５０ｍ２／ｇがより好ましい。比表面積が前記下限値以上であれば、成分（Ａ）〜（Ｃ）の担持量が充分となりやすく、１，３−ブタジエンの選択率がより高くなる。比表面積が前記上限値以下であれば、エタノールと合成用触媒との接触時間が充分となりやすく、１，３−ブタジエンの選択率が高くなりやすい。
なお、前記比表面積は、窒素を吸着ガスとし、ＢＥＴ式ガス吸着法により測定されるＢＥＴ比表面積である。
The specific surface area of the porous support preferably has 50~1000m 2 / g, 100~750m 2 / g is more preferable. When the specific surface area is equal to or more than the lower limit, the amounts of the components (A) to (C) supported are likely to be sufficient, and the selectivity for 1,3-butadiene is further increased. When the specific surface area is equal to or less than the upper limit, the contact time between ethanol and the synthesis catalyst tends to be sufficient, and the selectivity for 1,3-butadiene tends to increase.
The specific surface area is a BET specific surface area measured by a BET gas adsorption method using nitrogen as an adsorption gas.
多孔質担体における全細孔容積と比表面積との積は、５〜７５００ｍＬ・ｍ２／ｇ２が好ましく、５００〜５０００ｍＬ・ｍ２／ｇ２がより好ましい。前記積が前記下限値以上であれば、成分（Ａ）〜（Ｃ）の担持量が充分となりやすく、１，３−ブタジエンの選択率がより高くなる。前記積が前記上限値以下であれば、エタノールと合成用触媒との接触時間が充分となりやすく、１，３−ブタジエンの選択率が高くなりやすい。 The product of the total pore volume and the specific surface area of the porous support preferably has 5~7500mL · m 2 / g 2, and more preferably 500~5000mL · m 2 / g 2. When the product is equal to or larger than the lower limit, the amounts of the components (A) to (C) supported are likely to be sufficient, and the selectivity for 1,3-butadiene is further increased. When the product is equal to or less than the upper limit, the contact time between ethanol and the catalyst for synthesis tends to be sufficient, and the selectivity for 1,3-butadiene tends to increase.
多孔質担体への成分（Ａ）〜（Ｃ）の合計の担持量は、多孔質担体の質量に対して、１．０〜１０．０質量％が好ましく、２．５〜５．０質量％がより好ましい。担持量が前記下限値以上であれば、充分な量の成分（Ａ）〜（Ｃ）が担持されることで１，３−ブタジエンの選択率が高くなりやすい。担持量が前記上限値以下であれば、成分（Ａ）〜（Ｃ）を均一かつ高分散状態にしやすいため、１，３−ブタジエンの選択率を高めやすい。 The total amount of the components (A) to (C) carried on the porous carrier is preferably 1.0 to 10.0% by mass, more preferably 2.5 to 5.0% by mass, based on the mass of the porous carrier. Is more preferred. When the supported amount is equal to or more than the lower limit, the selectivity of 1,3-butadiene tends to be increased by supporting a sufficient amount of the components (A) to (C). When the supported amount is equal to or less than the upper limit, the components (A) to (C) are easily made to be in a uniform and highly dispersed state.
本発明の合成用触媒は、触媒金属として成分（Ａ）〜（Ｃ）を用いる以外は、従来公知の触媒の製造方法に準じて製造できる。本発明の合成用触媒を担持触媒とする場合、例えば、含浸法、イオン交換法等が挙げられ、含浸法が好ましい。含浸法を用いて得た担持触媒は、成分（Ａ）〜（Ｃ）がより均一に分散され、エタノールとの接触効率がより高められるため、１，３−ブタジエンの選択率をより高めることができる。 The synthesis catalyst of the present invention can be produced according to a conventionally known method for producing a catalyst, except that the components (A) to (C) are used as the catalyst metal. When the synthesis catalyst of the present invention is used as a supported catalyst, for example, an impregnation method, an ion exchange method and the like are mentioned, and the impregnation method is preferable. In the supported catalyst obtained by using the impregnation method, the components (A) to (C) are more uniformly dispersed and the contact efficiency with ethanol is further increased, so that the selectivity of 1,3-butadiene can be further increased. it can.
含浸法では、例えば、成分（Ａ）〜（Ｃ）の原料化合物を溶媒に溶解した溶液（含浸液）に多孔質担体を浸漬する等して、含浸液を多孔質担体に含浸させた後、乾燥し、焼成して、還元処理を施して合成用触媒とする。 In the impregnation method, for example, the porous carrier is immersed in the porous carrier by, for example, immersing the porous carrier in a solution (impregnating solution) in which the raw material compounds of the components (A) to (C) are dissolved in a solvent. It is dried, calcined and subjected to a reduction treatment to obtain a synthesis catalyst.
成分（Ａ）〜（Ｃ）の原料化合物としては、特に限定されず、金属触媒を調製する際に通常用いられるものを用いることができる。具体的には、例えば、酸化物、塩化物、硫化物、硝酸塩、炭酸塩等の無機塩、シュウ酸塩、アセチルアセトナート塩、ジメチルグリオキシム塩、エチレンジアミン酢酸塩等の有機塩又はキレート化合物、カルボニル化合物、シクロペンタジエニル化合物、アンミン錯体、アルコキシド化合物、アルキル化合物等が挙げられる。なかでも、塩化物又は硫化物が好ましい。
溶媒としては、水、メタノール、エタノール、テトラヒドロフラン、ジオキサン、ヘキサン、ベンゼン、トルエン等が挙げられる。
The raw material compounds of the components (A) to (C) are not particularly limited, and those usually used when preparing a metal catalyst can be used. Specifically, for example, oxides, chlorides, sulfides, nitrates, inorganic salts such as carbonates, oxalates, acetylacetonate salts, dimethylglyoxime salts, organic salts or chelate compounds such as ethylenediamine acetate, Examples include a carbonyl compound, a cyclopentadienyl compound, an ammine complex, an alkoxide compound, and an alkyl compound. Among them, chloride or sulfide is preferable.
Examples of the solvent include water, methanol, ethanol, tetrahydrofuran, dioxane, hexane, benzene, toluene and the like.
含浸液を多孔質担体に含浸させる方法としては、全ての原料化合物を溶解した溶液を担体に含浸させる方法（同時法）、各原料化合物を別個に溶解した溶液を調製し、逐次的に担体に各溶液を含浸させる方法（逐次法）等が挙げられる。 As a method of impregnating the porous carrier with the impregnating liquid, a method in which a solution in which all the raw material compounds are dissolved is impregnated into the carrier (simultaneous method), a solution in which each raw material compound is separately dissolved is prepared, and the carrier is sequentially loaded on the carrier. A method of impregnating each solution (sequential method) and the like can be mentioned.
乾燥温度及び焼成温度は、溶媒の種類等に応じて適宜決定できる。例えば、溶媒が水の場合、乾燥温度を８０〜１２０℃、焼成温度を３００〜６００℃とすることができる。 The drying temperature and the calcination temperature can be appropriately determined according to the type of the solvent and the like. For example, when the solvent is water, the drying temperature can be set to 80 to 120 ° C and the firing temperature can be set to 300 to 600 ° C.
以上説明した本発明の合成用触媒は、成分（Ａ）〜（Ｃ）を含むため、１−ブテンの副生を抑制しつつ１，３−ブタジエンを合成できる。そのため、１−ブテンを除去するための煩雑な精製工程を必要とせず、経済性に優れている。また、本発明の合成用触媒を用いれば、バイオエタノールから１，３−ブタジエンを合成できるため、環境負荷も低減できる。 Since the synthesis catalyst of the present invention described above contains the components (A) to (C), 1,3-butadiene can be synthesized while suppressing the by-product of 1-butene. Therefore, a complicated purification step for removing 1-butene is not required, and the process is excellent in economy. Further, when the synthesis catalyst of the present invention is used, 1,3-butadiene can be synthesized from bioethanol, so that the environmental load can be reduced.
［１，３−ブタジエンの製造装置］
本発明の１，３−ブタジエンの製造装置は、本発明の合成用触媒が充填された反応管と、エタノールを前記反応管内に供給する供給手段と、前記反応管から生成物を排出する排出手段と、を備える。以下、本発明の１，３−ブタジエンの製造装置の一例について、図１に基づいて説明する。
[1,3-Butadiene production equipment]
The apparatus for producing 1,3-butadiene of the present invention includes a reaction tube filled with the synthesis catalyst of the present invention, a supply unit for supplying ethanol into the reaction tube, and a discharge unit for discharging a product from the reaction tube. And. Hereinafter, an example of an apparatus for producing 1,3-butadiene of the present invention will be described with reference to FIG.
本実施形態の１，３−ブタジエンの製造装置１０（以下、単に「製造装置１０」という。）は、本発明の合成用触媒が充填されて反応床２が形成された反応管１と、反応管１に接続された供給管３と、反応管１に接続された排出管４と、反応管１に接続された温度制御部５と、排出管４に設けられた圧力制御部６と、を備える。
The
反応床２は、本発明の合成用触媒のみが充填されたものでもよく、本発明の合成用触媒と希釈材とが充填されたものでもよい。なお、エタノールから１，３−ブタジエンを合成する反応は吸熱反応であるため、本発明の合成用触媒が過度に発熱することを防止する目的で使用される希釈剤は通常不要である。
希釈材としては、例えば、合成触媒の担体と同様のものや、石英砂、アルミナボール、アルミボール、アルミショット等が挙げられる。
反応床２に希釈材を充填する場合、希釈材／合成用触媒で表される質量比は、それぞれの種類や比重等を勘案して決定され、例えば、０．５〜５が好ましい。
The
Examples of the diluent include those similar to the carrier of the synthesis catalyst, quartz sand, alumina balls, aluminum balls, aluminum shots, and the like.
When the
反応管１は、材料ガス及び合成された生成物に対して不活性な材料からなるものが好ましく、１００〜５００℃程度の加熱、又は１０ＭＰａ程度の加圧に耐え得る形状のものが好ましい。反応管１としては、例えば、ステンレス製の略円筒形の部材が挙げられる。
供給管３は、材料ガスを反応管１内に供給する供給手段であり、例えば、ステンレス製等の配管が挙げられる。
排出管４は、反応床２で合成された生成物を含むガスを排出する排出手段であり、例えば、ステンレス製等の配管が挙げられる。
The
The
The
温度制御部５は、反応管１内の反応床２を任意の温度にできるものであればよく、例えば、電気炉等が挙げられる。
圧力制御部６は、反応管１内の圧力を任意の圧力にできるものであればよく、例えば、公知の圧力弁等が挙げられる。
なお、製造装置１０は、マスフロー等、ガスの流量を調整するガス流量制御部等の周知の機器を備えていてもよい。
The
The pressure control section 6 may be any as long as the pressure in the
The
以上説明した本発明の１，３−ブタジエンの製造装置では、成分（Ａ）〜（Ｃ）を含む本発明の合成用触媒を用いるため、１−ブテンの副生を抑制しつつ１，３−ブタジエンを製造することができる。そのため、１−ブテンを除去するための煩雑な精製工程を必要とせず、経済性に優れている。また、バイオエタノールから１，３−ブタジエンを製造することもできるため、環境負荷も低減できる。 In the apparatus for producing 1,3-butadiene of the present invention described above, since the synthesis catalyst of the present invention containing the components (A) to (C) is used, 1,3-butene is prevented from being produced as a 1,3-butene. Butadiene can be produced. Therefore, a complicated purification step for removing 1-butene is not required, and the process is excellent in economy. Moreover, since 1,3-butadiene can be produced from bioethanol, the environmental load can be reduced.
［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、前記した本発明の合成用触媒を用いてエタノールから１，３−ブタジエンを製造する方法である。本発明の１，３−ブタジエンの製造方法では、本発明の合成用触媒にエタノールを接触させる。これにより、エタノールの二量化反応を経て１，３−ブタジエンが得られる。
[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene of the present invention is a method for producing 1,3-butadiene from ethanol using the above-described synthesis catalyst of the present invention. In the method for producing 1,3-butadiene of the present invention, ethanol is brought into contact with the synthesis catalyst of the present invention. Thereby, 1,3-butadiene is obtained through a dimerization reaction of ethanol.
エタノールと合成用触媒との接触させる態様は、特に限定されず、例えば、反応管内に合成用触媒を充填して反応床を形成し、該反応管にエタノールを供給して反応床の合成用触媒と接触させる態様が挙げられる。なお、反応床は、固定床、移動床、流動床等のいずれでもよい。 The mode of contacting the ethanol with the synthesis catalyst is not particularly limited. For example, the reaction tube is filled with the synthesis catalyst to form a reaction bed, and ethanol is supplied to the reaction tube to form the reaction bed synthesis catalyst. And a mode of contacting with the contact. The reaction bed may be a fixed bed, a moving bed, a fluidized bed, or the like.
合成用触媒に接触させるエタノールは、転化率を高くしやすい点から、ガス状であることが好ましい。なお、合成用触媒に接触させるエタノールは、液状であってもよい。合成用触媒にエタノールを接触させる際には、エタノールのみを接触させてもよく、本発明の目的を損なわない範囲であればエタノールとその他の成分の混合物を接触させてもよい。 The ethanol to be brought into contact with the synthesis catalyst is preferably in a gaseous state from the viewpoint of easily increasing the conversion. The ethanol to be brought into contact with the synthesis catalyst may be in a liquid state. When ethanol is brought into contact with the synthesis catalyst, only ethanol may be brought into contact, or a mixture of ethanol and other components may be brought into contact as long as the object of the present invention is not impaired.
ガス化したエタノールと不活性ガスを含む混合ガスとして合成用触媒に接触させてもよい。不活性ガスを含有していると、１，３−ブタジエンの合成効率のさらなる向上を図れる。混合ガス中の不活性ガスの含有量は、例えば、５〜５０体積％が好ましく、１０〜４０体積％がより好ましく、１５〜３０体積％がさらに好ましい。 The gas may be brought into contact with the synthesis catalyst as a mixed gas containing ethanol and an inert gas. When an inert gas is contained, the synthesis efficiency of 1,3-butadiene can be further improved. The content of the inert gas in the mixed gas is, for example, preferably 5 to 50% by volume, more preferably 10 to 40% by volume, and still more preferably 15 to 30% by volume.
エタノールと合成用触媒とを接触させる際の温度（反応温度）は、３００〜５００℃が好ましく、３５０〜４５０℃がより好ましい。反応温度が前記下限値以上であれば、酸化反応の速度が充分に高まり、１，３−ブタジエンをより効率的に製造できる。反応温度が前記上限値以下であれば、合成用触媒の劣化を抑制しやすい。 The temperature (reaction temperature) at which ethanol is brought into contact with the synthesis catalyst is preferably 300 to 500C, more preferably 350 to 450C. When the reaction temperature is equal to or higher than the lower limit, the rate of the oxidation reaction is sufficiently increased, and 1,3-butadiene can be produced more efficiently. When the reaction temperature is equal to or lower than the upper limit, deterioration of the synthesis catalyst is easily suppressed.
エタノールと合成用触媒とを接触させる際の圧力（反応圧力）、例えば、常圧〜１ＭＰａとされる。 The pressure (reaction pressure) at the time of bringing ethanol into contact with the synthesis catalyst is, for example, normal pressure to 1 MPa.
合成用触媒と接触させるエタノールの空間速度は、標準状態換算で、０．１〜１００００Ｌ／Ｌ−触媒／ｈｒが好ましく、１０〜５０００Ｌ／Ｌ−触媒／ｈｒがより好ましく、１００〜２５００Ｌ／Ｌ−触媒／ｈｒがさらに好ましい。空間速度は、反応圧力及び反応温度を勘案して、適宜調整される。 The space velocity of ethanol to be brought into contact with the synthesis catalyst is preferably from 0.1 to 10000 L / L-catalyst / hr, more preferably from 10 to 5000 L / L-catalyst / hr, and more preferably from 100 to 2500 L / L-, in terms of standard condition. Catalyst / hr is more preferred. The space velocity is appropriately adjusted in consideration of the reaction pressure and the reaction temperature.
例えば、製造装置１０を用いる場合は、温度制御部５及び圧力制御部６により反応管１内を任意の温度及び任意の圧力とし、ガス化されたエタノールを含むガス２０を供給管３から反応管１内に流入させる。反応管１内においてエタノールが合成用触媒に接触して反応し、１，３−ブタジエンが生成する。１，３−ブタジエンを含む生成ガス２２は、排出管４から排出される。生成ガス２２には、アセトアルデヒド、プロピレン、エタン等の化合物が含まれていてもよい。
For example, when the
合成用触媒との接触による反応後に得られた１，３−ブタジエンを含む生成物に対しては、必要に応じて気液分離や蒸留精製等の精製を行い、未反応のエタノールや副生物を除去する。 The product containing 1,3-butadiene obtained after the reaction by contact with the synthesis catalyst is subjected to purification such as gas-liquid separation or distillation purification as necessary, to remove unreacted ethanol and by-products. Remove.
以上説明した本発明の１，３−ブタジエンの製造方法によれば、成分（Ａ）〜（Ｃ）を含む本発明の合成用触媒を用いるため、１−ブテンの副生を抑制しつつ１，３−ブタジエンを製造することができる。そのため、１−ブテンを除去するための煩雑な精製工程を必要とせず、経済性に優れている。また、バイオエタノールから１，３−ブタジエンを製造することもできるため、環境負荷も低減できる。 According to the method for producing 1,3-butadiene of the present invention described above, the synthesis catalyst including the components (A) to (C) is used. 3-butadiene can be produced. Therefore, a complicated purification step for removing 1-butene is not required, and the process is excellent in economy. Moreover, since 1,3-butadiene can be produced from bioethanol, the environmental load can be reduced.
以下、比較例及び実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。 Hereinafter, the present invention will be described in detail with reference to Comparative Examples and Examples, but the present invention is not limited by the following description.
［比較例１］
成分（Ａ）の原料化合物である硝酸銅三水和物（和光純薬社製）０．０７６１ｇと、成分（Ｂ）の原料化合物である硝酸亜鉛六水和物（和光純薬社製）０．０４５５ｇと、を含む水溶液２．１０ｇを調製した（一次含浸溶液）。次いで、該水溶液を多孔質担体（シリカ、粒子径：１．１８〜２．３６ｍｍ、平均細孔直径：１４．７ｎｍ、全細孔容積：０．９９ｍＬ／ｇ、比表面積：１９５ｍ２／ｇ）２．０ｇに滴下して含浸させた（一次含浸工程）。次いで、該多孔体担体を１１０℃で３時間乾燥し、さらに４００℃で４．５時間焼成して一次担持体を得た（一次担持工程）。続いて、成分（Ｃ）の原料である塩化ハフニウム（和光純薬社製）０．１０７ｇを含む水溶液２．０９ｇを調製した。該水溶液を用いて、一次担持体に一次含浸工程と同様の処理を行い、合成用触媒（１−１）を得た。
得られた合成用触媒（１−１）における成分（Ａ）〜（Ｃ）の割合は、多孔質担体の質量に対して、成分（Ａ）が１質量％、成分（Ｂ）が０．５質量％、成分（Ｃ）が３．０質量％であった。
[Comparative Example 1]
0.0761 g of copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a raw material compound of component (A) and zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.), which is a raw material compound of component (B) 0 0.0455 g, and 2.10 g of an aqueous solution containing (primary impregnation solution). Next, the aqueous solution was added to a porous carrier (silica, particle diameter: 1.18 to 2.36 mm, average pore diameter: 14.7 nm, total pore volume: 0.99 mL / g, specific surface area: 195 m 2 / g). 2.0 g was dropped and impregnated (primary impregnation step). Next, the porous carrier was dried at 110 ° C. for 3 hours, and calcined at 400 ° C. for 4.5 hours to obtain a primary carrier (primary carrier step). Subsequently, 2.09 g of an aqueous solution containing 0.107 g of hafnium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) as a raw material of the component (C) was prepared. Using the aqueous solution, the same treatment as in the primary impregnation step was performed on the primary carrier to obtain a synthesis catalyst (1-1).
The ratio of the components (A) to (C) in the obtained synthesis catalyst (1-1) was such that the component (A) was 1% by mass and the component (B) was 0.5% with respect to the mass of the porous carrier. % By mass, and component (C) was 3.0% by mass.
［実施例１〜５］
成分（Ｃ）の原料化合物を変更し、多孔質担体の質量に対する成分（Ａ）〜（Ｃ）の割合を表１に示すとおりにした以外は、比較例１と同様にして各合成用触媒を得た。各実施例の成分（Ｃ）の原料化合物としては、以下に示すものを使用した。
実施例１：酢酸バリウム（和光純薬社製）。
実施例２：硝酸カルシウム四水和物（和光純薬社製）。
実施例３：硝酸カリウム（和光純薬社製）。
実施例４：硝酸リチウム（和光純薬社製）。
実施例５：硝酸ナトリウム（和光純薬社製）。
[Examples 1 to 5]
Each synthesis catalyst was prepared in the same manner as in Comparative Example 1 except that the raw material compound of the component (C) was changed and the ratio of the components (A) to (C) to the mass of the porous carrier was changed as shown in Table 1. Obtained. The following compounds were used as the starting compounds of the component (C) in each example.
Example 1: Barium acetate (manufactured by Wako Pure Chemical Industries, Ltd.).
Example 2: Calcium nitrate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.).
Example 3: Potassium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.).
Example 4: Lithium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.).
Example 5: Sodium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.).
［１−ブテンの選択率の測定］
各例の合成用触媒０．０５００ｇを直径１／１６インチ（０．１５９ｃｍ）、長さ１１インチ（２７．９ｃｍ）のステンレス製の円筒型の反応管に充填して反応床を形成した。
次いで、反応床の温度（反応温度）を４００℃、４２５℃、又は４５０℃として、空間速度５００Ｌ／Ｌ−触媒／ｈｒ、常圧でガス状のエタノールを反応管に供給し、反応床を通過させて生成ガスを得た。それぞれの反応温度での反応中に回収した生成ガスをガスクロマトグラフィーにより分析し、１−ブテンの選択率を求めた。
各例においては、時間経過とともに反応温度を４００℃、４２５℃、４５０℃の順に変化させ、各反応温度において２回ずつ１−ブテンの選択率を測定した。
[Measurement of 1-butene selectivity]
0.0500 g of the synthesis catalyst of each example was charged into a stainless steel cylindrical reaction tube having a diameter of 1/16 inch (0.159 cm) and a length of 11 inch (27.9 cm) to form a reaction bed.
Then, the temperature (reaction temperature) of the reaction bed is set to 400 ° C., 425 ° C., or 450 ° C., and a gaseous ethanol is supplied to the reaction tube at a space velocity of 500 L / L-catalyst / hr at normal pressure, and passes through the reaction bed. Then, a product gas was obtained. The product gas collected during the reaction at each reaction temperature was analyzed by gas chromatography to determine the 1-butene selectivity.
In each example, the reaction temperature was changed in the order of 400 ° C., 425 ° C., and 450 ° C. with the passage of time, and the selectivity of 1-butene was measured twice at each reaction temperature.
実施例１〜５及び比較例１の合成用触媒を用いたそれぞれの反応について、各反応温度での１−ブテンの選択率を図２〜７に示す。 For each reaction using the synthesis catalysts of Examples 1 to 5 and Comparative Example 1, the selectivity of 1-butene at each reaction temperature is shown in FIGS.
図２〜７に示すように、成分（Ａ）〜（Ｃ）を含む三元系触媒である実施例１〜５の合成用触媒では、Ｃｕ、Ｚｎ及びＨｆの三元系触媒である比較例１の合成用触媒に比べて、１−ブテンの副生を抑制できた。 As shown in FIGS. 2 to 7, the synthesis catalysts of Examples 1 to 5 which are ternary catalysts containing components (A) to (C) are comparative examples which are ternary catalysts of Cu, Zn and Hf. Compared with the synthesis catalyst of No. 1, the by-product of 1-butene was able to be suppressed.
１ 反応管
２ 反応床
３ 供給管
４ 排出管
５ 温度制御部
６ 圧力制御部
１０ １，３−ブタジエンの製造装置
Claims (7)
成分（Ａ）：Ｃｕと、成分（Ｂ）：Ｚｎと、成分（Ｃ）：Ｂ、Ｂａ、Ｃａ、Ｇｅ、Ｋ、Ｌｉ、Ｍｇ、Ｎａ、Ｔａ及びＷからなる群から選ばれる１種以上と、のいずれかから選ばれる成分が多孔質担体に担持され、
前記成分（Ａ）〜（Ｃ）の合計の担持量は、前記多孔質担体の質量に対して、１．０〜５．０質量％であり、
前記多孔質担体における細孔容積の合計が０．２５〜１．５０ｍＬ／ｇである、１，３−ブタジエン合成用触媒。 A 1,3-butadiene synthesis catalyst for synthesizing 1,3-butadiene from ethanol, comprising:
Component (A): Cu, component (B): Zn, and component (C): at least one selected from the group consisting of B, Ba, Ca, Ge, K, Li, Mg, Na, Ta and W. A component selected from any of the above is supported on a porous carrier,
The total carrying amount of the components (A) to (C) is 1.0 to 5.0% by mass based on the mass of the porous carrier.
A catalyst for synthesizing 1,3-butadiene, wherein the total pore volume of the porous carrier is 0.25 to 1.50 mL / g.
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