JPH055820B2 - - Google Patents
Info
- Publication number
- JPH055820B2 JPH055820B2 JP60010227A JP1022785A JPH055820B2 JP H055820 B2 JPH055820 B2 JP H055820B2 JP 60010227 A JP60010227 A JP 60010227A JP 1022785 A JP1022785 A JP 1022785A JP H055820 B2 JPH055820 B2 JP H055820B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ethylhexenal
- butyraldehyde
- niobic acid
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 30
- PYLMCYQHBRSDND-UHFFFAOYSA-N 2-ethyl-2-hexenal Chemical compound CCCC=C(CC)C=O PYLMCYQHBRSDND-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003513 alkali Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】
本発明はブチルアルデヒドの縮合脱水反応によ
る２−エチルヘキセナールの製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-ethylhexenal by condensation and dehydration reaction of butyraldehyde.
ブチルアルデヒドを脱水縮合させて２−エチル
ヘキセナールを合成する方法は既に知られてお
り、工業的にはアルカリ水溶液を触媒としてブチ
ルアルデヒドから２−エチルヘキセナールが製造
されている。 A method for synthesizing 2-ethylhexenal by dehydration condensation of butyraldehyde is already known, and 2-ethylhexenal is industrially produced from butyraldehyde using an aqueous alkali solution as a catalyst.
通常ブチルアルデヒドとアルカリ水溶液とを液
相で接触させ反応を行なわしめた後、油水分離に
よつて油層（２−エチルヘキセナールを含有す
る。）と水層（不純物を含むアルカリ水溶液であ
る。）とを分離し、油層を精留することにより２
−エチルヘキセナールを精製するという方法で工
業的に実施されている。 Usually, butyraldehyde and an alkaline aqueous solution are brought into contact in a liquid phase to cause a reaction, and then oil and water are separated to form an oil layer (containing 2-ethylhexenal) and an aqueous layer (alkaline aqueous solution containing impurities). By separating and rectifying the oil layer, 2
- It is carried out industrially by the method of purifying ethylhexenal.
しかしながらこのようなアルカリ水溶液を触媒
として用いる方法においては、有機物を含むアル
カリ水溶液の排水処理、油層へのアルカリの混入
による運転トラブル、それにアルカリを用いるこ
とによる材質上の制約等種々の問題点があつた。 However, this method of using an alkaline aqueous solution as a catalyst has various problems such as wastewater treatment of the alkaline aqueous solution containing organic substances, operational troubles due to alkali mixing into the oil layer, and material limitations due to the use of alkali. Ta.
本発明者らは運転が容易でかつプロセスが簡単
な２−エチルヘキセナールの製造方法について鋭
意研究を行ない本発明に到達したものである。 The present inventors have conducted extensive research into a method for producing 2-ethylhexenal that is easy to operate and has a simple process, and have arrived at the present invention.
すなわち、本発明はブチルアルデヒドを脱水縮
合させて２−エチルヘキセナールを製造する方法
において触媒として固体酸触媒であるニオブ酸を
用いることを特徴とする２−エチルヘキセナール
の製造方法である。本発明においては収率よく２
−エチルヘキセナールが得られるだけでなく、プ
ロセス排水中にアルカリ分が含まれないためその
排水処理が容易であり、また油層へのアルカリ混
入による運転トルブル等からも開放され工業的に
安定した運転が可能となる。 That is, the present invention is a method for producing 2-ethylhexenal, which is characterized in that niobic acid, which is a solid acid catalyst, is used as a catalyst in the method for producing 2-ethylhexenal by dehydration condensation of butyraldehyde. In the present invention, 2
- Not only can ethylhexenal be obtained, but the process wastewater does not contain alkaline content, making it easy to treat the wastewater. It is also free from operational troubles caused by alkali contamination in the oil layer, allowing for industrially stable operation. It becomes possible.
本発明方法に用いられる触媒はニオブ酸であ
る。ニオブ酸は含水酸化ニオブとも呼ばれる固体
酸であり、その性質については第３回固体酸プロ
セス化研究会講演予稿集P.1〜４（触媒学会、昭和
58年11月30日）に記載されている。ニオブ酸は強
い酸性質を有しており、エチレンの水和反応やエ
ステル化反応に活性があることが報告されている
がその他の反応に対する触媒作用についてはほと
んど知られていない。 The catalyst used in the process of the invention is niobic acid. Niobic acid is a solid acid, also called hydrous niobium oxide.
(November 30, 1958). Niobic acid has strong acid properties, and it has been reported that it has activity in the hydration reaction and esterification reaction of ethylene, but little is known about its catalytic effect on other reactions.
本発明者らはこのようなニオブ酸を触媒として
ブチルアルデヒドの脱水縮合反応を行なつたとこ
ろ、収率よく２−エチルヘキセナールが得られる
ことを見い出したものである。 The present inventors have discovered that 2-ethylhexenal can be obtained in good yield when a dehydration condensation reaction of butyraldehyde is carried out using such niobic acid as a catalyst.
本発明方法の反応形態としてはニオブ酸のペレ
ツトを断熱または等温型反応器に充填し、そこに
ブチルアルデヒドを通じるいわゆる固定床流通反
応で２−エチルヘキセナールの製造を行なつても
よいし、またはニオブ酸の粉末をブチルアルデヒ
ド中に懸濁させて反応を行なわしめてもよい。固
定床流通反応はプロセスがシンプルで、また運転
も容易であり本発明方法の好ましい実施形態であ
る。 As for the reaction mode of the method of the present invention, 2-ethylhexenal may be produced by filling an adiabatic or isothermal reactor with niobic acid pellets and passing butyraldehyde therein by a so-called fixed bed flow reaction, or The reaction may be carried out by suspending niobic acid powder in butyraldehyde. The fixed bed flow reaction is a simple process and easy to operate, and is a preferred embodiment of the method of the present invention.
固定床流通反応で反応を行なう場合、気相で反
応させてもよいし、液相で反応を行なつてもよく
特に限定されないが、液相反応が好ましく用いら
れる。 When the reaction is carried out in a fixed bed flow reaction, the reaction may be carried out in a gas phase or in a liquid phase, and is not particularly limited, but a liquid phase reaction is preferably used.
固定床流通反応の場合、原料供給速度は通常
LHSV換算で１〜10hr-1、懸濁法の場合触媒の使
用量は反応形式によつて異なるが、通常原料ブチ
ルアルデヒドに対し0.1〜10重量％である。 In the case of fixed bed flow reaction, the raw material feed rate is usually
In the suspension method, the amount of catalyst used varies depending on the reaction type, but is usually 0.1 to 10 % by weight based on the butyraldehyde starting material.
反応温度は通常80〜250℃で行なわれ、好まし
くは120〜200℃である。この温度より低い温度で
は反応速度が小さくなり、またこの温度より高い
温度では２−エチルヘキセナールの高縮合生成物
が増加する。 The reaction temperature is usually 80 to 250°C, preferably 120 to 200°C. At temperatures below this temperature, the reaction rate decreases, and at temperatures above this temperature, high condensation products of 2-ethylhexenal increase.
本発明方法によればニオブ酸を触媒として用い
ることにより、工業的に有利な方法でブチルアル
デヒドから収率よく２−エチルヘキセナールを製
造することができる。すなわち本発明方法におい
てはニオブ酸触媒によつて反応を行なつた後の反
応液から油水分離によつて分離される脱水によつ
て生成した水の中にはアルカリが含まれておら
ず、PH調整操作が不要である等その排水処理は非
常に簡単である。また油水分離によつて分離され
る油層中にアルカリが含まれることもなく精留時
のアルカリのスケーリングによるトラブル発生の
可能性もない。 According to the method of the present invention, 2-ethylhexenal can be produced in good yield from butyraldehyde in an industrially advantageous manner by using niobic acid as a catalyst. That is, in the method of the present invention, the water produced by dehydration, which is separated from the reaction solution by oil-water separation after the reaction is carried out using a niobic acid catalyst, does not contain alkali, and the PH The wastewater treatment is very simple as no adjustment is required. In addition, no alkali is contained in the oil layer separated by oil-water separation, and there is no possibility of trouble occurring due to alkali scaling during rectification.
以下に実施例によつて本発明方法をさらに具体
的に説明するが本発明の範囲はこれによつて制限
を受けるものではない。 The method of the present invention will be explained in more detail below with reference to Examples, but the scope of the present invention is not limited thereby.
実施例 １
内容積200mlの電磁撹拌器付オートクレーブ中
にブチルアルデヒド100ｇとニオブ酸（CBMM社
製、水分含量７重量％、粉末状）２ｇを入れた。
窒素ガスで置換を行なつた後160℃で２時間反応
を行なつた。反応終了後反応生成物をガスクロマ
トグラフイーにより分析し下記の結果を得た。Example 1 100 g of butyraldehyde and 2 g of niobic acid (manufactured by CBMM, water content 7% by weight, powder) were placed in an autoclave with an internal volume of 200 ml and equipped with a magnetic stirrer.
After purging with nitrogen gas, the reaction was carried out at 160°C for 2 hours. After the reaction was completed, the reaction product was analyzed by gas chromatography and the following results were obtained.
ｎ−ブチルアルデヒド転化率 92.3％
２−エチルヘキセナール選択率 95.5％
実施例 ２
ニオブ酸ペレツト（CBMM社製、水分含有量
７重量％、円柱状）50mlを内径20mmの垂直に配置
した反応管内に充填し、温度160℃、圧力20気圧
の条件下、ｎ−ブチルアルデヒドを160ｇ／hr
（LHSV＝4hr-1）の供給速度で反応器に導入し反
応を行ない下記の結果を得た。n-Butyraldehyde conversion rate 92.3% 2-ethylhexenal selectivity 95.5% Example 2 50 ml of niobic acid pellets (manufactured by CBMM, water content 7% by weight, cylindrical shape) were filled into a vertically arranged reaction tube with an inner diameter of 20 mm. 160g/hr of n-butyraldehyde under the conditions of temperature 160℃ and pressure 20atm.
(LHSV=4hr -1 ) was introduced into the reactor and the reaction was carried out, and the following results were obtained.
ｎ−ブチルアルデヒド転化率 91.4％ ２−エチルヘキセナール選択率 93.7％。n-butyraldehyde conversion rate 91.4% 2-Ethylhexenal selectivity 93.7%.
Claims (1)
ルヘキセナールを製造する方法において、触媒と
してニオブ酸を用いることを特徴とする２−エチ
ルヘキセナールの製造方法。1. A method for producing 2-ethylhexenal by condensation and dehydration of butyraldehyde, the method comprising using niobic acid as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60010227A JPS61167634A (en) | 1985-01-22 | 1985-01-22 | Production of 2-ethylhexenal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60010227A JPS61167634A (en) | 1985-01-22 | 1985-01-22 | Production of 2-ethylhexenal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61167634A JPS61167634A (en) | 1986-07-29 |
| JPH055820B2 true JPH055820B2 (en) | 1993-01-25 |
Family
ID=11744392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60010227A Granted JPS61167634A (en) | 1985-01-22 | 1985-01-22 | Production of 2-ethylhexenal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61167634A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3026790U (en) * | 1995-09-18 | 1996-07-23 | マコト商事株式会社 | Multi-function stereo amplifier and helmet headset, microphone for helmet, speaker for helmet |
| JP2013177365A (en) * | 2011-12-28 | 2013-09-09 | Dow Global Technologies Llc | Catalyst and process for producing branched unsaturated aldehyde |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625065A (en) * | 1992-07-09 | 1994-02-01 | Sumitomo Chem Co Ltd | Aldol condensation process by vapor-phase reaction |
| DE19956410A1 (en) * | 1999-11-24 | 2001-05-31 | Oxeno Olefinchemie Gmbh | Process for performing aldol condensations |
-
1985
- 1985-01-22 JP JP60010227A patent/JPS61167634A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3026790U (en) * | 1995-09-18 | 1996-07-23 | マコト商事株式会社 | Multi-function stereo amplifier and helmet headset, microphone for helmet, speaker for helmet |
| JP2013177365A (en) * | 2011-12-28 | 2013-09-09 | Dow Global Technologies Llc | Catalyst and process for producing branched unsaturated aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61167634A (en) | 1986-07-29 |
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