JP2017144421A - Catalyst for acetaldehyde synthesis, apparatus for manufacturing acetaldehyde, and method for manufacturing acetaldehyde - Google Patents
Catalyst for acetaldehyde synthesis, apparatus for manufacturing acetaldehyde, and method for manufacturing acetaldehyde Download PDFInfo
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 73
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 title claims 2
- 238000000034 method Methods 0.000 title abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910052732 germanium Inorganic materials 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 abstract description 3
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- 238000005259 measurement Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- UJAUQTYCLNYMPY-UHFFFAOYSA-N OB(O)O.N.N.N.O.O.O.O.O.O.O.O Chemical compound OB(O)O.N.N.N.O.O.O.O.O.O.O.O UJAUQTYCLNYMPY-UHFFFAOYSA-N 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 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
- 125000000217 alkyl group Chemical group 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 150000001880 copper compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
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- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical class O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940097042 glucuronate Drugs 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
- 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
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Abstract
Description
本発明は、アセトアルデヒド合成用触媒、アセトアルデヒドの製造装置及びアセトアルデヒドの製造方法に関する。 The present invention relates to an acetaldehyde synthesis catalyst, an acetaldehyde production apparatus, and an acetaldehyde production method.
アセトアルデヒドは工業的に重要な中間体であり、酢酸エチル、過酢酸、ピリジン誘導体、クロトンアルデヒド、パラアルデヒド等の原料として大量に使用されている。アセトアルデヒドの製造方法としては、エチレンのＷａｃｋｅｒ酸化によりアセトアルデヒドを得る方法が挙げられる。しかし、近年はバイオ素材への需要の高まりから、原料としてバイオエタノールを用いたアセトアルデヒドに注目が高まっている。 Acetaldehyde is an industrially important intermediate and is used in large quantities as a raw material for ethyl acetate, peracetic acid, pyridine derivatives, crotonaldehyde, paraaldehyde and the like. Examples of the method for producing acetaldehyde include a method for obtaining acetaldehyde by Wacker oxidation of ethylene. However, in recent years, due to the increasing demand for biomaterials, attention has been focused on acetaldehyde using bioethanol as a raw material.
エタノールからアセトアルデヒドを製造する方法としては、例えば、下記の方法（ｉ）〜（ｉｖ）が知られている。
（ｉ）硝酸銅等の銅化合物が多孔体に担持された触媒にエタノールを接触させてアセトアルデヒドを得る方法（特許文献１）。
（ｉｉ）酸素分子の存在下、Ｌａ２Ｏ３等の卑金属酸化物に金微粒子が分散、固定された触媒にエタノールを接触させてアセトアルデヒドを得る方法（特許文献２）。
（ｉｉｉ）Ｃｏと、Ｆｅ、Ｍｏ及びＡｌからなる群から選ばれる１種以上とが触媒担体に担持された触媒にエタノールを接触させてアセトアルデヒドを得る方法（特許文献３）。
（ｉｖ）Ｐｄ１．２Ｒｈ０．６Ｂｉ１．２等の活性成分を含む触媒活性組成物にエタノールを接触させてアセトアルデヒドを得る方法（特許文献４）。
As a method for producing acetaldehyde from ethanol, for example, the following methods (i) to (iv) are known.
(I) A method of obtaining acetaldehyde by bringing ethanol into contact with a catalyst in which a copper compound such as copper nitrate is supported on a porous body (Patent Document 1).
(Ii) A method of obtaining acetaldehyde by bringing ethanol into contact with a catalyst in which gold fine particles are dispersed and fixed in a base metal oxide such as La 2 O 3 in the presence of oxygen molecules (Patent Document 2).
(Iii) A method of obtaining acetaldehyde by bringing ethanol into contact with a catalyst in which Co and one or more selected from the group consisting of Fe, Mo and Al are supported on a catalyst carrier (Patent Document 3).
(Iv) A method of obtaining acetaldehyde by bringing ethanol into contact with a catalytically active composition containing an active component such as Pd 1.2 Rh 0.6 Bi 1.2 (Patent Document 4).
しかし、方法（ｉ）〜（ｉｖ）では、エタノール酸化によるアセトアルデヒドの選択率が低いため、工業的なアセトアルデヒドの製造方法としては経済性が悪い。 However, in the methods (i) to (iv), the selectivity of acetaldehyde by ethanol oxidation is low, so that it is not economical as an industrial method for producing acetaldehyde.
本発明は、エタノールから高い選択率でアセトアルデヒドを合成できる経済性に優れたアセトアルデヒド合成用触媒、並びに該アセトアルデヒド合成用触媒を用いたアセトアルデヒドの製造装置及び製造方法を提供することを目的とする。 An object of the present invention is to provide an economical acetaldehyde synthesis catalyst capable of synthesizing acetaldehyde from ethanol with high selectivity, and an acetaldehyde production apparatus and production method using the acetaldehyde synthesis catalyst.
本発明のアセトアルデヒド合成用触媒は、エタノールからアセトアルデヒドを合成するためのアセトアルデヒド合成用触媒であって、成分（Ａ）：Ｃｕと、成分（Ｂ）：Ｚｎと、成分（Ｃ）：Ｂ、Ｇｅ、Ｈｆ及びＷからなる群から選ばれる１種以上と、を含む。
前記成分（Ｃ）は、Ｂ、Ｇｅ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。
前記成分（Ｃ）は、Ｈｆと、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種以上との組み合わせであることが好ましい。
The acetaldehyde synthesis catalyst of the present invention is an acetaldehyde synthesis catalyst for synthesizing acetaldehyde from ethanol, and the component (A): Cu, the component (B): Zn, and the component (C): B, Ge, One or more selected from the group consisting of Hf and W.
The component (C) is preferably at least one selected from the group consisting of B, Ge and W.
The component (C) is preferably a combination of Hf and one or more selected from the group consisting of B, Ge and W.
本発明のアセトアルデヒドの製造装置は、本発明のアセトアルデヒド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 acetaldehyde production apparatus of the present invention comprises a reaction tube filled with the acetaldehyde synthesis catalyst of the present invention, a supply means for supplying ethanol into the reaction tube, and a discharge means for discharging a product from the reaction tube. Prepare.
本発明のアセトアルデヒドの製造方法は、エタノールを本発明のアセトアルデヒド合成用触媒に接触させてアセトアルデヒドを得る方法である。 The method for producing acetaldehyde of the present invention is a method for obtaining acetaldehyde by contacting ethanol with the catalyst for synthesizing acetaldehyde of the present invention.
本発明のアセトアルデヒド合成用触媒を用いれば、エタノールから高い選択率でアセトアルデヒドを合成でき、経済性に優れている。
本発明のアセトアルデヒドの製造装置を用いれば、エタノールから高い選択率でアセトアルデヒドを製造することができ、経済性に優れている。
本発明のアセトアルデヒドの製造方法によれば、エタノールから高い選択率でアセトアルデヒドを製造することができ、経済性に優れている。
By using the catalyst for synthesizing acetaldehyde of the present invention, acetaldehyde can be synthesized from ethanol with high selectivity, and it is excellent in economic efficiency.
If the apparatus for producing acetaldehyde of the present invention is used, acetaldehyde can be produced from ethanol with high selectivity, which is excellent in economic efficiency.
According to the method for producing acetaldehyde of the present invention, acetaldehyde can be produced from ethanol with high selectivity, which is excellent in economic efficiency.
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。
「アセトアルデヒドの選択率」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、アセトアルデヒド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 definitions of terms apply throughout this specification and the claims.
“Selectivity of acetaldehyde” means the percentage of the number of moles of ethanol converted to acetaldehyde in the number of moles of ethanol consumed in the reaction using the synthesis catalyst.
［アセトアルデヒド合成用触媒］
本発明のアセトアルデヒド合成用触媒（以下、単に「合成用触媒」という。）は、エタノールからアセトアルデヒド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、Ｇｅ、Ｈｆ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、高い選択率でアセトアルデヒドを合成することができる。
[Acetaldehyde synthesis catalyst]
The acetaldehyde synthesis catalyst of the present invention (hereinafter simply referred to as “synthesis catalyst”) is a catalyst for synthesizing acetaldehyde from ethanol. The synthesis catalyst of the present invention contains component (A): Cu, component (B): Zn, and component (C): one or more selected from the group consisting of B, Ge, Hf and W. When the synthesis catalyst of the present invention contains components (A) to (C), acetaldehyde can be synthesized with high selectivity.
成分（Ｃ）としては、アセトアルデヒドの選択率がより高くなる点から、Ｂ、Ｇｅ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。さらに、成分（Ｃ）としては、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種がより好ましい。すなわち、本発明の合成用触媒としては、Ｃｕと、Ｚｎと、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種との三元系触媒がより好ましい。 The component (C) is preferably at least one selected from the group consisting of B, Ge and W from the point that the selectivity of acetaldehyde becomes higher. Furthermore, as the component (C), one selected from the group consisting of B, Ge and W is more preferable. That is, the synthesis catalyst of the present invention is more preferably a ternary catalyst of Cu, Zn, and one selected from the group consisting of B, Ge, and W.
また、成分（Ｃ）としては、アセトアルデヒドの選択率がより高くなる点から、Ｈｆと、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種以上との組み合わせも好ましい。さらに、成分（Ｃ）としては、Ｈｆと、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種との組み合わせがより好ましい。すなわち、本発明の合成用触媒としては、Ｃｕと、Ｚｎと、Ｈｆと、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種との四元系触媒がより好ましい。 Moreover, as a component (C), the combination of Hf and 1 or more types chosen from the group which consists of B, Ge, and W from the point from which the selectivity of acetaldehyde becomes higher is also preferable. Furthermore, as the component (C), a combination of Hf and one selected from the group consisting of B, Ge, and W is more preferable. That is, the catalyst for synthesis of the present invention is more preferably a quaternary catalyst of Cu, Zn, Hf, and one selected from the group consisting of B, Ge, and W.
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、Ｇｅ、Ｈｆ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)
However, in (1), M 1 is, it represents B, Ge, at least one member selected from the group consisting of Hf and W, a, b and c represents the mass percentage of the porous 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、副生物であるエチレンの割合が増加する。ａが前記上限値超であれば、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。
（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（アセトアルデヒド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（アセトアルデヒド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が前記下限値以上であれば、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が前記上限値以下であれば、Ｃ４以上の副生物質が増加する（アセトアルデヒドの選択率が減少する）。
(1) As for a in a formula, 10-0.01 are preferred, 5-0.1 are more preferred, and 2.5-0.5 are still more preferred. If a is less than the lower limit, the proportion of ethylene as a by-product increases. If a exceeds the upper limit, the raw material conversion rate (ratio in which ethanol changes into a reaction product) decreases.
(1) As for b in a formula, 10-0.01 are preferred, 5-0.05 are more preferred, and 1-0.1 are still more preferred. If b is less than the lower limit, the production amount of ethylene as a by-product increases (selectivity of acetaldehyde decreases). If b exceeds the upper limit, the amount of propylene produced as a by-product increases (selectivity of acetaldehyde decreases).
(1) c in the formula is preferably 10 to 0.01, and more preferably 5 to 0.1. If c is more than the said lower limit, a raw material conversion rate (ratio which ethanol changes into a reaction material) will reduce. If c is less than or equal to the above upper limit value, C4 or higher by-product substances increase (selectivity of acetaldehyde decreases).
本発明の合成用触媒は、下記（２）式で表される組成の触媒であることがより好ましい。
ａＣｕ・ｂＺｎ・ｄＨｆ・ｅＭ１１ ・・・・（２）
ただし、（２）式中、Ｍ１１は、Ｂ、Ｇｅ及びＷからなる群から選ばれる１種以上を表し、ａ、ｂ、ｄ及びｅ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 more preferably a catalyst having a composition represented by the following formula (2).
aCu · bZn · dHf · eM 11 (2)
However, (2) where, M 11 is, B, represents one or more selected from the group consisting of Ge and W, a, b, d and e represent the mass percentage of the porous carrier.
（２）式中のａ及びｂの好ましい範囲は、（１）式中のａ及びｂの好ましい範囲と同じである。
（２）式中のｄ＋ｅの好ましい範囲は、（１）式中のｃの好ましい範囲と同じである。
The preferable range of a and b in the formula (2) is the same as the preferable range of a and b in the formula (1).
The preferable range of d + e in the formula (2) is the same as the preferable range of c in the formula (1).
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、アセトアルデヒドの選択率がより高くなる。 The mass ratio (A / B) of the component (A) to the component (B) in the synthesis catalyst of the present invention is preferably 100 to 0.1, and more preferably 10 to 0.5. If mass ratio (A / B) is in the said range, the selectivity of acetaldehyde will become 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、アセトアルデヒドの選択率がより高くなる。 The mass ratio (A / C) between the component (A) and the component (C) in the synthesis catalyst of the present invention is preferably 100 to 0.1, and more preferably 10 to 0.5. If a mass ratio (A / C) is in the said range, the selectivity of acetaldehyde will become higher.
本発明の合成用触媒が成分（Ｃ）としてＨｆと、Ｂ、Ｇｅ、Ｈｆ及びＷからなる群から選ばれる１種以上とを含む場合、Ｈｆに対する成分（Ｃ）のＨｆ以外の金属の質量比は、１以下が好ましい。前記質量比が１以下であれば、Ｈｆが寄与する反応を阻害しにくい。 When the synthesis catalyst of the present invention contains Hf as component (C) and one or more selected from the group consisting of B, Ge, Hf and W, the mass ratio of the metal other than Hf of component (C) to Hf Is preferably 1 or less. If the mass ratio is 1 or less, it is difficult to inhibit the reaction contributed by Hf.
本発明の合成用触媒としては、アセトアルデヒド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 from the viewpoint that the selectivity of acetaldehyde becomes higher. The material of the porous carrier is not particularly limited, and examples thereof include silica, zirconia, titania, magnesia and the like. Among these, 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 diameter 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、アセトアルデヒド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、アセトアルデヒド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) in the porous carrier is preferably 0.10 to 2.50 mL / g, and more preferably 0.25 to 1.50 mL / g. If the total pore volume is equal to or greater than the lower limit, a sufficient amount of components (A) to (C) can be easily carried, and the selectivity of acetaldehyde becomes higher. If the total pore volume is less than or equal to the above upper limit value, the contact time between ethanol and the catalyst for synthesis tends to be sufficient, and the selectivity for acetaldehyde 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、アセトアルデヒド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、アセトアルデヒド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 greater than the lower limit, a sufficient amount of components (A) to (C) can be easily carried, and the selectivity for acetaldehyde becomes higher. When the average pore diameter is not more than the above upper limit, the contact time between ethanol and the catalyst for synthesis tends to be sufficient, and the selectivity for acetaldehyde 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 porosimetry 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 pressed into the pores of the porous carrier, and the average pore diameter is calculated from the pressure and the amount of mercury inserted.
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、アセトアルデヒド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、アセトアルデヒド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. If the specific surface area is equal to or greater than the lower limit, the amount of the components (A) to (C) supported is likely to be sufficient, and the selectivity for acetaldehyde is further increased. If the specific surface area is not more than the above upper limit value, the contact time between ethanol and the catalyst for synthesis tends to be sufficient, and the selectivity for acetaldehyde 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、アセトアルデヒド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、アセトアルデヒド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. If the said product is more than the said lower limit, the load of component (A)-(C) will become easy enough, and the selectivity of acetaldehyde will become higher. If the product is less than or equal to the upper limit, the contact time between ethanol and the catalyst for synthesis tends to be sufficient, and the selectivity for acetaldehyde 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アセトアルデヒド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、アセトアルデヒドの選択率を高めやすい。 The total supported amount of the components (A) to (C) on the porous carrier is preferably 1.0 to 10.0% by mass, and 2.5 to 5.0% by mass with respect to the mass of the porous carrier. Is more preferable. If the loading amount is equal to or more than the lower limit value, a sufficient amount of components (A) to (C) is loaded, so that the selectivity of acetaldehyde tends to increase. If the loading amount is less than or equal to the above upper limit value, the components (A) to (C) are likely to be in a uniform and highly dispersed state, so that the selectivity of acetaldehyde can be easily increased.
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、アセトアルデヒド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 catalyst production method 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 can be mentioned, and an 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 acetaldehyde can be further increased.
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 impregnated with the porous carrier by 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。 It does not specifically limit as a raw material compound of component (A)-(C), What is normally used when preparing a metal catalyst can be used. Specifically, for example, inorganic salts such as oxides, chlorides, sulfides, nitrates, carbonates, oxalates, acetylacetonate salts, dimethylglyoxime salts, organic salts such as ethylenediamine acetate, or chelate compounds, Examples include carbonyl compounds, cyclopentadienyl compounds, ammine complexes, alkoxide compounds, and alkyl compounds. Of these, chloride or sulfide is preferred.
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 impregnating liquid into the porous carrier, a method of impregnating the carrier with a solution in which all raw material compounds are dissolved (simultaneous method), a solution in which each raw material compound is separately dissolved is prepared, and sequentially applied to the carrier. Examples include a method of impregnating each solution (sequential method).
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 firing temperature can be appropriately determined according to the type of the solvent. For example, when the solvent is water, the drying temperature can be 80 to 120 ° C., and the firing temperature can be 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、エタノール酸化によって高い選択率でアセトアルデヒドを合成できるため、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アセトアルデヒドを製造することもできるため、環境負荷の低減にも寄与できる。 Since the catalyst for synthesis of the present invention described above contains components (A) to (C), acetaldehyde can be synthesized with high selectivity by ethanol oxidation, and thus is excellent in economic efficiency. Moreover, if the synthesis catalyst of the present invention is used, acetaldehyde can also be produced from bioethanol, which can contribute to a reduction in environmental burden.
［アセトアルデヒドの製造装置］
本発明のアセトアルデヒドの製造装置は、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、本発明のアセトアルデヒドの製造装置の一例について、図１に基づいて説明する。
[Acetaldehyde production equipment]
The acetaldehyde production apparatus of the present invention includes a reaction tube filled with the synthesis catalyst of the present invention, a supply unit that supplies ethanol into the reaction tube, and a discharge unit that discharges a product from the reaction tube. . Hereinafter, an example of the acetaldehyde production apparatus of the present invention will be described with reference to FIG.
本実施形態のアセトアルデヒドの製造装置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、エタノールからアセトアルデヒド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 synthetic 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
The
以上説明した本発明のアセトアルデヒドの製造装置では、成分（Ａ）〜（Ｃ）を含む本発明の合成用触媒を用いるため、エタノール酸化によって高い選択率でアセトアルデヒドを製造することができ、経済性に優れている。また、バイオエタノールからアセトアルデヒド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 acetaldehyde production apparatus of the present invention described above, since the synthesis catalyst of the present invention containing components (A) to (C) is used, acetaldehyde can be produced with high selectivity by ethanol oxidation, which is economical. Are better. Moreover, since acetaldehyde can also be manufactured from bioethanol, an environmental load can also be reduced.
［アセトアルデヒドの製造方法］
本発明のアセトアルデヒドの製造方法は、前記した本発明の合成用触媒を用いてエタノールからアセトアルデヒドを製造する方法である。本発明のアセトアルデヒドの製造方法では、エタノールを本発明の合成用触媒に接触させる。これにより、エタノールが酸化させてアセトアルデヒドが得られる。
[Method for producing acetaldehyde]
The method for producing acetaldehyde of the present invention is a method for producing acetaldehyde from ethanol using the synthesis catalyst of the present invention described above. In the method for producing acetaldehyde of the present invention, ethanol is brought into contact with the synthesis catalyst of the present invention. Thereby, ethanol is oxidized and acetaldehyde is obtained.
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 bringing ethanol into contact with the synthesis catalyst is not particularly limited. For example, a reaction bed is formed by filling the reaction tube with the synthesis catalyst, and ethanol is supplied to the reaction tube to prepare the reaction bed synthesis catalyst. And an embodiment in which the contact is made. 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 brought into contact with the synthesis catalyst is preferably in the form of a gas from the viewpoint of easily increasing the conversion rate. Note that the ethanol to be brought into contact with the synthesis catalyst may be liquid. 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、アセトアルデヒド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。 You may make it contact with the catalyst for a synthesis | combination as mixed gas containing the gasified ethanol and inert gas. When the inert gas is contained, the synthesis efficiency of acetaldehyde can be further improved. For example, the content of the inert gas in the mixed gas is 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、アセトアルデヒド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) when ethanol is brought into contact with the catalyst for synthesis is preferably 300 to 500 ° C, more preferably 350 to 450 ° C. If reaction temperature is more than the said lower limit, the speed | rate of an oxidation reaction will fully increase and acetaldehyde can be manufactured more efficiently. If reaction temperature is below the said upper limit, it will be easy to suppress degradation of the catalyst for synthesis.
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) when ethanol is brought into contact with the synthesis catalyst, 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 brought into contact with the synthesis catalyst is preferably 0.1 to 10000 L / L-catalyst / hr, more preferably 10 to 5000 L / L-catalyst / hr, and 100 to 2500 L / L- in terms of standard state. More preferred is catalyst / hr. 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、アセトアルデヒドが生成する。アセトアルデヒドを含む生成ガス２２は、排出管４から排出される。生成ガス２２には、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アセトアルデヒド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 acetaldehyde obtained after the reaction by contact with the catalyst for synthesis is subjected to purification such as gas-liquid separation or distillation purification as necessary to remove unreacted ethanol and by-products.
以上説明した本発明のアセトアルデヒド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、エタノール酸化によって高い選択率でアセトアルデヒドを製造することができ、経済性に優れている。また、バイオエタノールからアセトアルデヒド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 acetaldehyde of the present invention described above, since the synthesis catalyst of the present invention containing components (A) to (C) is used, acetaldehyde can be produced with high selectivity by ethanol oxidation, and the economy Excellent in properties. Moreover, since acetaldehyde can also be manufactured from bioethanol, an environmental load can also be reduced.
以下、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。
［実施例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（Ｉ−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。
また、成分（Ａ）の原料化合物と成分（Ｃ）の原料化合物の使用量を変更し、多孔質担体の質量に対する成分（Ａ）と成分（Ｃ）の割合を表１に示すとおりに変更した以外は、上記と同様にして合成用触媒（Ｉ−１）〜（Ｉ−３）を得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
[Example 1]
0.0761 g of copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) which is a raw material compound of component (A), and zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0 which is a raw material compound of component (B) 0 And an aqueous solution containing 1.455 g (primary impregnation solution). Next, the aqueous solution was treated with 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 further 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.), which is a raw material of the component (C), was prepared. Using this aqueous solution, the primary support was treated in the same manner as in the primary impregnation step to obtain a synthesis catalyst (1-1).
The proportions of the components (A) to (C) in the resultant synthesis catalyst (I-1) were 1% by mass for the component (A) and 0.5% for the component (B) with respect to the mass of the porous carrier. The mass% and the component (C) were 3.0 mass%.
Moreover, the usage-amount of the raw material compound of a component (A) and the raw material compound of a component (C) was changed, and the ratio of the component (A) and the component (C) with respect to the mass of a porous support | carrier was changed as shown in Table 1. Except for the above, synthesis catalysts (I-1) to (I-3) were obtained in the same manner as above.
［実施例２〜７］
成分（Ｃ）の原料化合物を変更して多孔質担体の質量に対する成分（Ａ）〜（Ｃ）の割合を表１及び表２に示すとおりにし、また焼成温度を表１及び表２に示すとおりに変更した以外は、実施例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２、５〜７：ほう酸アンモニウム八水和物（米山薬品工業社製）。
実施例３、５〜７：グルクロン酸ゲルマニウム（和光純薬社製）。
実施例４：高純度メタタングステン酸アンモニウム（日本無機化学工業社製）。
[Examples 2 to 7]
The raw material compound of component (C) is changed so that the ratio of components (A) to (C) to the mass of the porous carrier is as shown in Table 1 and Table 2, and the firing temperature is as shown in Table 1 and Table 2. Each synthesis catalyst was obtained in the same manner as in Example 1 except that the synthesis catalyst was changed. As raw material compounds of component (C) in each Example, those shown below were used.
Examples 2, 5-7: Ammonium borate octahydrate (manufactured by Yoneyama Pharmaceutical Co., Ltd.).
Examples 3, 5-7: Germanium glucuronate (manufactured by Wako Pure Chemical Industries, Ltd.).
Example 4: High purity ammonium metatungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.).
［アセトアルデヒドの選択率の測定］
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、アセトアルデヒドの選択率を求めた。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回ずつアセトアルデヒドの選択率を測定した。
実施例１〜７の合成用触媒を用いたそれぞれの反応について、アセトアルデヒドの選択率の測定結果を図２〜８に示す。
[Measurement of acetaldehyde selectivity]
A reaction bed was formed by filling 0.0500 g of the synthesis catalyst of each example into a stainless steel cylindrical reaction tube having a diameter of 1/16 inch (0.159 cm) and a length of 11 inches (27.9 cm).
Next, the temperature of the reaction bed (reaction temperature) is set to 400 ° C., 425 ° C., or 450 ° C., and gaseous ethanol is supplied to the reaction tube at a space velocity of 500 L / L-catalyst / hr and normal pressure, and passes through the reaction bed. The product gas was obtained. The product gas collected during the reaction at each reaction temperature was analyzed by gas chromatography to determine the selectivity of acetaldehyde. In each example, the reaction temperature was changed in the order of 400 ° C., 425 ° C., and 450 ° C. over time, and the selectivity of acetaldehyde was measured twice at each reaction temperature.
The measurement results of the selectivity of acetaldehyde for each reaction using the synthesis catalysts of Examples 1 to 7 are shown in FIGS.
図２〜５に示すように、成分（Ａ）〜（Ｃ）の三元系触媒である実施例１〜４の合成用触媒では、高い選択率でアセトアルデヒドを製造することができた。また、成分（Ｃ）として、Ｂ、Ｇｅ又はＷを用いた実施例２〜４の合成用触媒では、より高い選択率でアセトアルデヒドを製造することが可能であった。
また、図６〜８に示すように、成分（Ｃ）としてＨｆを含む２種の金属を用いた実施例５〜７の四元系触媒は、三元系触媒に比べて、さらに高い選択率でアセトアルデヒドを製造することが可能であった。
As shown in FIGS. 2 to 5, acetaldehyde could be produced with high selectivity in the synthesis catalysts of Examples 1 to 4 which are ternary catalysts of components (A) to (C). Moreover, in the synthesis catalysts of Examples 2 to 4 using B, Ge, or W as the component (C), it was possible to produce acetaldehyde with higher selectivity.
Moreover, as shown to FIGS. 6-8, the quaternary catalyst of Examples 5-7 using two types of metals containing Hf as a component (C) has a still higher selectivity than a ternary catalyst. It was possible to produce acetaldehyde.
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 アセトアルデヒドの製造装置
DESCRIPTION OF
Claims (5)
成分（Ａ）：Ｃｕと、成分（Ｂ）：Ｚｎと、成分（Ｃ）：Ｂ、Ｇｅ、Ｈｆ及びＷからなる群から選ばれる１種以上と、を含む、アセトアルデヒド合成用触媒。 A catalyst for acetaldehyde synthesis for synthesizing acetaldehyde from ethanol,
A catalyst for synthesizing acetaldehyde, comprising: component (A): Cu; component (B): Zn; and component (C): one or more selected from the group consisting of B, Ge, Hf and W.
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