JP2000026357A - Production of dimerized aldehyde - Google Patents
Production of dimerized aldehydeInfo
- Publication number
- JP2000026357A JP2000026357A JP10194118A JP19411898A JP2000026357A JP 2000026357 A JP2000026357 A JP 2000026357A JP 10194118 A JP10194118 A JP 10194118A JP 19411898 A JP19411898 A JP 19411898A JP 2000026357 A JP2000026357 A JP 2000026357A
- Authority
- JP
- Japan
- Prior art keywords
- aldehyde
- basic catalyst
- aqueous solution
- oil phase
- dimerized
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 54
- 239000012071 phase Substances 0.000 claims abstract description 23
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000006482 condensation reaction Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical group CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- PYLMCYQHBRSDND-UHFFFAOYSA-N 2-ethyl-2-hexenal Chemical compound CCCC=C(CC)C=O PYLMCYQHBRSDND-UHFFFAOYSA-N 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001893 (2R)-2-methylbutanal Substances 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QJJLGDXUAXOUBP-UHFFFAOYSA-N 2,2,4-trimethylpent-3-enal Chemical compound CC(C)=CC(C)(C)C=O QJJLGDXUAXOUBP-UHFFFAOYSA-N 0.000 description 1
- GADNZGQWPNTMCH-UHFFFAOYSA-N 2-propylhept-2-enal Chemical compound CCCCC=C(C=O)CCC GADNZGQWPNTMCH-UHFFFAOYSA-N 0.000 description 1
- 101710114762 50S ribosomal protein L11, chloroplastic Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101150013553 CD40 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000851376 Homo sapiens Tumor necrosis factor receptor superfamily member 8 Proteins 0.000 description 1
- 102100040245 Tumor necrosis factor receptor superfamily member 5 Human genes 0.000 description 1
- 102100036857 Tumor necrosis factor receptor superfamily member 8 Human genes 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアルデヒドを塩基性
触媒の存在下に縮合反応及び脱水反応させて二量化アル
デヒドを製造する方法に関する。詳しくは、アルデヒド
の縮合反応及び脱水反応において、アルデヒド三量体等
の望ましくない高沸点化合物の生成を抑制し、二量化ア
ルデヒドを高選択で製造する方法に関するものである。The present invention relates to a method for producing a dimerized aldehyde by subjecting an aldehyde to a condensation reaction and a dehydration reaction in the presence of a basic catalyst. More specifically, the present invention relates to a method for suppressing the formation of undesired high-boiling compounds such as aldehyde trimers in the aldehyde condensation reaction and dehydration reaction, and for producing a dimerized aldehyde with high selectivity.
【０００２】[0002]
【従来の技術】苛性ソーダ水溶液等の存在下に、アルデ
ヒドを縮合反応及び脱水反応させて、二量化アルデヒド
を製造することは公知である。例えばｎ−ブチルアルデ
ヒドを縮合脱水反応させると２−エチルヘキセナールが
得られる。この方法の問題点の一つは、目的物である二
量化アルデヒドが更に反応して三量体、四量体などの望
ましくない高沸点化合物を生成することである。これら
の高沸点化合物の生成は、結果的に二量化アルデヒドの
収率を低下させるので、その回避策が種々提案されてい
る。例えば特公昭３９−２４７８７号公報には、ｎ−ブ
チルアルデヒドとアルカリ水溶液とを充填塔や目皿塔で
向流接触させ、かつ塔に脈動を与えてｎ−ブチルアルデ
ヒドをアルカリ水溶液中に微粒として分散させることが
記載されている。しかし、この方法では２−エチルヘキ
セナールの収率はせいぜい９４％である。2. Description of the Related Art It is known that an aldehyde is subjected to a condensation reaction and a dehydration reaction in the presence of an aqueous solution of caustic soda to produce a dimerized aldehyde. For example, when n-butyraldehyde is subjected to a condensation dehydration reaction, 2-ethylhexenal is obtained. One of the problems with this method is that the desired dimerized aldehyde further reacts to produce undesirable high-boiling compounds such as trimers and tetramers. Since the formation of these high-boiling compounds results in a decrease in the yield of dimerized aldehyde, various measures have been proposed to avoid this. For example, Japanese Patent Publication No. 39-24787 discloses that n-butyraldehyde and an aqueous alkali solution are brought into countercurrent contact with a packed tower or a perforated tower, and pulsation is applied to the tower to convert n-butyraldehyde into fine particles in the aqueous alkali solution. Dispersing is described. However, in this method, the yield of 2-ethylhexenal is at most 94%.
【０００３】また、特公昭５２−４３８１０号公報に
は、ｎ−ブチルアルデヒドとアルカリ水溶液とを、撹拌
混合器及び管型反応器の２つの反応器を用いて、１２０
〜１３０℃、４〜５ｋｇ／ｃｍ2 Ｇで反応させることが
記載されている。しかしこの方法でも、相当量の高沸点
化合物が生成し、かつ未反応のｎ−ブチルアルデヒドも
残存するので、二量化アルデヒドの収率は満足すべきも
のではない。Further, Japanese Patent Publication No. 52-43810 discloses that n-butyraldehyde and an aqueous alkali solution are mixed in an aqueous solution using two reactors, a stirring mixer and a tubular reactor.
It is described that the reaction is performed at 130 ° C. and 4 to 5 kg / cm 2 G. However, even in this method, a considerable amount of a high-boiling compound is produced, and unreacted n-butyraldehyde remains, so that the yield of dimerized aldehyde is not satisfactory.
【０００４】更にフランス特許第２０５８５３２号明細
書には、苛性ソーダ水溶液を用いてアセトアルデヒドを
縮合させ、かつ脱水反応が生起する前に反応系に酢酸を
添加して反応を停止させることが記載されている。しか
し、この方法では苛性ソーダ水溶液の循環使用が不可能
である。また、特公昭３９−２４９５２号公報や特公昭
３９−１７９０７号公報には、副生した高沸点化合物を
もとのアルデヒドと不飽和アルデヒドとに分解すること
が提案されている。しかし、これらの方法は、高沸点化
合物を分解するための特別の装置が必要であり、工業的
には採用し難い。Further, French Patent No. 2,058,532 discloses that acetaldehyde is condensed using an aqueous solution of caustic soda and the reaction is stopped by adding acetic acid to the reaction system before a dehydration reaction occurs. . However, in this method, it is impossible to recycle the aqueous solution of caustic soda. JP-B-39-24952 and JP-B-39-17907 propose decomposition of a high-boiling compound produced as a by-product into an original aldehyde and an unsaturated aldehyde. However, these methods require a special device for decomposing high-boiling compounds, and are difficult to employ industrially.
【０００５】[0005]
【発明が解決しようとする課題】上記したように、従来
提案されているいずれの方法も、二量化アルデヒドの製
造方法として満足すべきものではない。従って本発明
は、工業的実施が容易であり、かつ高沸点化合物の副生
が著しく少ない二量化アルデヒドの製造方法を提供せん
とするものである。As described above, none of the conventionally proposed methods is satisfactory as a method for producing a dimerized aldehyde. Accordingly, an object of the present invention is to provide a method for producing a dimerized aldehyde which is easy to carry out on an industrial scale and has very few by-products of a high-boiling compound.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、原料ア
ルデヒドを塩基性触媒水溶液の存在下に縮合反応及び脱
水反応させて二量化アルデヒドを生成させるに際し、塩
基性触媒水溶液からなる水相中に、原料アルデヒドを含
む油相を、下記式で定義される平均径（ｄｓ）が５００
μｍ以下となるように液滴として分散させて反応させる
ことにより、高沸点化合物の副生を抑制して高収率で二
量化アルデヒドを製造することができる。 平均径（ｄｓ）＝ΣＸｉ3 Ｎｉ／ΣＸｉ2 Ｎｉ Ｘｉ：液滴の最大径（μｍ） Ｎｉ：最大径がＸｉである液滴の個数According to the present invention, when a starting aldehyde is subjected to a condensation reaction and a dehydration reaction in the presence of a basic catalyst aqueous solution to form a dimerized aldehyde, an aqueous phase comprising the basic catalyst aqueous solution is used. First, the oil phase containing the raw material aldehyde has an average diameter (ds) defined by the following formula of 500.
By dispersing and reacting as droplets so as to have a particle size of μm or less, by-products of high-boiling compounds can be suppressed, and a dimerized aldehyde can be produced in a high yield. Average diameter (ds) = ΣXi 3 Ni / ΣXi 2 Ni Xi: maximum diameter of droplet (μm) Ni: number of droplets having maximum diameter Xi
【０００７】[0007]
【発明の実施の形態】本発明はα−位に水素原子を有す
る任意のアルデヒドからの二量化アルデヒドの製造に適
用することができる。例えばｎ−ブチルアルデヒド又は
イソブチルアルデヒドからその二量化アルデヒドである
２−エチルヘキセナールや２，２，４−トリメチルペン
テナールの製造に適用することができる。またバレルア
ルデヒドや２−メチルブチルアルデヒドからの、その二
量化アルデヒドである２−プロピルヘプテナールや２，
４−ジメチル−２−エチルヘキセナールの製造に適用す
ることができる。更にはｎ−ブチルアルデヒドとイソブ
チルアルデヒドとの混合物やバレルアルデヒドと２−メ
チルブチルアルデヒドとの混合物からの混合二量化アル
デヒドの製造に適用することもできる。DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to the production of a dimerized aldehyde from any aldehyde having a hydrogen atom at the α-position. For example, the present invention can be applied to the production of 2-ethylhexenal or 2,2,4-trimethylpentenal which is a dimerized aldehyde from n-butyraldehyde or isobutyraldehyde. In addition, 2-propylheptenal, which is a dimerized aldehyde from valeraldehyde and 2-methylbutyraldehyde, and 2,2
It can be applied to the production of 4-dimethyl-2-ethylhexenal. Further, the present invention can be applied to the production of a mixed dimerized aldehyde from a mixture of n-butyraldehyde and isobutyraldehyde or a mixture of valeraldehyde and 2-methylbutyraldehyde.
【０００８】塩基性触媒としては通常は水酸化ナトリウ
ム、水酸化カリウム、水酸化リチウムなどのアルカリ金
属水酸化物が用いられる。これらは通常は単独で用いる
が、所望ならば２種又は３種を併用することもできる。
また、アルカリ金属水酸化物以外にも、水酸化カルシウ
ムなどのアルカリ土類金属水酸化物や、トリメチルアミ
ン、トリエチルアミン、トリプロピルアミン、ジエチル
アミン、ジプロピルアミン、ジブチルアミンなどの各種
アミン、水酸化トリメチルベンジルアンモニウム、水酸
化テトラメチルアンモニウム、水酸化テトラエチルアン
モニウムなどの水酸化第四級アンモニウム化合物などを
用いることもできる。As the basic catalyst, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is usually used. These are usually used alone, but if desired, two or three kinds can be used in combination.
In addition to alkali metal hydroxides, alkaline earth metal hydroxides such as calcium hydroxide, various amines such as trimethylamine, triethylamine, tripropylamine, diethylamine, dipropylamine and dibutylamine, and trimethylbenzyl hydroxide Quaternary ammonium hydroxide compounds such as ammonium, tetramethylammonium hydroxide, and tetraethylammonium hydroxide can also be used.
【０００９】水溶液中の塩基性触媒の濃度は通常０．５
〜２０重量％、好ましくは１〜１０重量％である。触媒
濃度が低過ぎると反応速度が低下する。逆に濃度が高過
ぎると副生物の生成が増加し、目的とする二量化アルデ
ヒドの収率が低下する。水溶液中の塩基性触媒の最も好
ましい濃度は２〜５重量％である。The concentration of the basic catalyst in the aqueous solution is usually 0.5
-20% by weight, preferably 1-10% by weight. If the catalyst concentration is too low, the reaction rate will decrease. Conversely, if the concentration is too high, the generation of by-products increases, and the yield of the desired dimerized aldehyde decreases. The most preferred concentration of the basic catalyst in the aqueous solution is 2-5% by weight.
【００１０】本発明では、上述の塩基性触媒水溶液中
に、原料アルデヒドを微細な液滴として分散させる。本
発明者らの知見によれば、原料アルデヒドの縮合及び脱
水反応は、塩基性触媒が存在する水相中で進行する。従
って原料アルデヒドは先ず塩基性触媒水溶液中に移動し
なければならない。また三量体や四量体などの高沸点副
生物の生成もこの水相中で進行する。すなわち水相中で
生成した二量化アルデヒドが、水相中の原料アルデヒド
と更に縮合反応して高沸点化合物が生成する。従って水
相中の二量化アルデヒドの濃度を低下させる、すなわち
生成した二量化アルデヒドを速やかに水相から油相に移
行させることができれば、高沸点化合物の生成は抑制し
得るものと考えられる。なお、水相中の原料アルデヒド
の濃度を低下させることは、二量化アルデヒドの生成そ
のものを抑制することになるので、好ましくない。本発
明者らはこのような考えのもとに検討を重ねた結果、水
相中に油相を下記式で定義される平均径（ｄｓ）が５０
０μｍ以下となるように分散させて反応させれば、高沸
点化合物の生成を抑制し得ることを見出したものであ
る。 平均径（ｄｓ）＝ΣＸｉ3 Ｎｉ／ΣＸｉ2 Ｎｉ Ｘｉ：液滴の最大径（μｍ） Ｎｉ：最大径がＸｉである液滴の個数In the present invention, the raw material aldehyde is dispersed as fine droplets in the basic catalyst aqueous solution. According to the findings of the present inventors, the condensation and dehydration reactions of the starting aldehyde proceed in an aqueous phase in which a basic catalyst is present. Therefore, the starting aldehyde must first be transferred into the aqueous basic catalyst solution. The production of high-boiling by-products such as trimers and tetramers also proceeds in this aqueous phase. That is, the dimerized aldehyde generated in the aqueous phase further undergoes a condensation reaction with the raw material aldehyde in the aqueous phase to generate a high-boiling compound. Therefore, if the concentration of the dimerized aldehyde in the aqueous phase is reduced, that is, if the generated dimerized aldehyde can be promptly transferred from the aqueous phase to the oil phase, it is considered that the generation of the high boiling point compound can be suppressed. In addition, it is not preferable to lower the concentration of the raw material aldehyde in the aqueous phase, because it suppresses the production of dimerized aldehyde itself. As a result of repeated studies based on such a concept, the present inventors have found that an oil phase in an aqueous phase has an average diameter (ds) defined by the following formula of 50.
It has been found that, when dispersed and reacted so as to be 0 μm or less, generation of a high boiling point compound can be suppressed. Average diameter (ds) = ΣXi 3 Ni / ΣXi 2 Ni Xi: maximum diameter of droplet (μm) Ni: number of droplets having maximum diameter Xi
【００１１】一般に液滴として分散している油相の平均
径が小さいほど高沸点化合物の副生量は少ない傾向があ
る。しかし液滴の平均径が小さくなるほど、そのような
分散状態を形成するのは困難となる。従って一般には液
滴の平均径が０．１〜５００μｍとなるように水相中に
油相を分散させるのが好ましい。水相中に油相を分散さ
せるには、水相と油相とを機械的撹拌部を備えた撹拌槽
に装入して撹拌する方法、静的撹拌機を備えた管式反応
器に水相と油相とを連続的に供給する方法、水相中にス
プレーノズルから油相を噴出させる方法など、公知の任
意の方法を採用することができる。分散液滴の安定性の
観点からして、水相と油相との合計に占める油相の容積
の比は０．６以下、特に０．５以下が好ましい。なお、
油相は原料アルデヒドに加えて、生成する二量化アルデ
ヒドを溶解する疎水性の有機溶媒、例えばベンゼン、ト
ルエン等の炭化水素溶媒を含んでいてもよい。有機溶媒
は原料アルデヒドとの溶液として分散に供してもよく、
また原料アルデヒドと平行して分散装置に供給してもよ
い。縮合及び脱水反応は常用の温度、圧力で行うことが
できる。一般には常圧から１０ｋｇ／ｃｍ2 Ｇの圧力範
囲で反応が行われる。反応温度は圧力により任意に設定
でき、例えば大気圧においては４０〜１５０℃の範囲で
行われる。In general, the smaller the average diameter of the oil phase dispersed as droplets, the smaller the amount of by-products of high-boiling compounds tends to be. However, the smaller the average diameter of the droplet, the more difficult it is to form such a dispersed state. Therefore, it is generally preferable to disperse the oil phase in the aqueous phase so that the average diameter of the droplets is 0.1 to 500 μm. In order to disperse the oil phase in the aqueous phase, a method in which the aqueous phase and the oil phase are charged into a stirring tank equipped with a mechanical stirrer and stirred, and Any known method such as a method of continuously supplying a phase and an oil phase, and a method of ejecting an oil phase from a spray nozzle into an aqueous phase can be adopted. From the viewpoint of the stability of the dispersed droplets, the ratio of the volume of the oil phase to the total of the water phase and the oil phase is preferably 0.6 or less, particularly preferably 0.5 or less. In addition,
The oil phase may contain, in addition to the raw aldehyde, a hydrophobic organic solvent that dissolves the dimerized aldehyde to be formed, for example, a hydrocarbon solvent such as benzene and toluene. The organic solvent may be subjected to dispersion as a solution with the raw material aldehyde,
Further, it may be supplied to a dispersion device in parallel with the raw material aldehyde. The condensation and dehydration reactions can be performed at ordinary temperatures and pressures. Generally, the reaction is carried out in a pressure range from normal pressure to 10 kg / cm 2 G. The reaction temperature can be arbitrarily set depending on the pressure.
【００１２】[0012]
【実施例】以下に実施例により本発明を更に具体的に説
明するが、本発明はその要旨を超えない限り、以下の実
施例に限定されるものではない。 実施例 内径５４ｍｍ、液深９０ｍｍの円筒形で、内壁に幅５．
４ｍｍのバッフルが４枚取付けられており、且つ翼径３
１ｍｍの１段６枚タービン翼を有する撹拌機を備えたも
のを２個直列に接続して反応器とした。この反応器に、
ｎ−ブチルアルデヒド、トルエン及び２％水酸化ナトリ
ウム水溶液を、それぞれ２２９ｇ／ｈｒ、１１４ｇ／ｈ
ｒ及び４２９ｇ／ｈｒで連続的に供給し、８６℃で縮合
及び脱水反応させた。反応器流出物は冷却したのち油水
分離器により水相と油相とに分離した。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the present invention. Example A cylindrical shape having an inner diameter of 54 mm and a liquid depth of 90 mm, and a width of 5. mm on the inner wall.
Four 4 mm baffles are attached and the wing diameter is 3
Two reactors equipped with a stirrer having 1-mm six-stage turbine blades were connected in series to form a reactor. In this reactor,
n-butyraldehyde, toluene and a 2% aqueous sodium hydroxide solution were respectively 229 g / hr and 114 g / h
The mixture was continuously supplied at r and 429 g / hr, and was subjected to a condensation and dehydration reaction at 86 ° C. After cooling, the reactor effluent was separated into an aqueous phase and an oil phase by an oil-water separator.
【００１３】撹拌機の回転数を変化させて平均液滴径を
変化させ、平均液滴径と２−エチルヘキセナールの選択
率との関係を調べた。結果を図１に示す。なお、液滴径
の測定はＬａｓｅｎｔｅｃ社製ＰＶＭ８００（プローブ
型ＣＣＤカメラ）を用いて行った。２−エチルヘキセナ
ール及び高沸点物の選択率は、油水分離器から得られた
油相をガスクロマトグラフで分析することにより求め
た。図１から明らかなように、液滴の平均径が小さいほ
ど二量化アルデヒドの選択率が向上する。The relationship between the average droplet diameter and the selectivity of 2-ethylhexenal was examined by changing the average droplet diameter by changing the rotation speed of the stirrer. The results are shown in FIG. In addition, the measurement of the droplet diameter was performed using PVM800 (probe type CCD camera) manufactured by Lasertec. The selectivities of 2-ethylhexenal and high-boiling substances were determined by analyzing the oil phase obtained from the oil-water separator by gas chromatography. As is clear from FIG. 1, the selectivity of dimerized aldehyde is improved as the average diameter of the droplet is smaller.
【図１】撹拌機を備えた反応器に、ｎ−ブチルアルデヒ
ド、トルエン及び２％水酸化ナトリウム水溶液を連続滴
に供給して縮合及び脱水反応させた場合の、平均液滴径
と二量化アルデヒドの選択率との関係の１例を示すグラ
フである。FIG. 1 shows the average droplet diameter and dimerized aldehyde when n-butyraldehyde, toluene and a 2% aqueous sodium hydroxide solution are continuously supplied to a reactor equipped with a stirrer to cause condensation and dehydration reactions. 6 is a graph showing an example of a relationship between the selection rate and the selection rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江本 浩樹 岡山県倉敷市潮通三丁目10番地 三菱化学 株式会社水島事業所内 Ｆターム(参考） 4G069 AA06 BA47A BB05A BB05B BC02A BC02B BC03A BC04A CB21 CB25 CB46 CB72 DA02 FC08 4H006 AA02 AC21 AC25 BA02 BA03 BA29 BA69 BB11 BB31 BC15 BC33 BC35 BC37 4H039 CA29 CD30 CD40 CF30 CL11 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroki Emoto 3-10, Utsudori, Kurashiki-shi, Okayama Mitsubishi Chemical Corporation Mizushima Works F-term (reference) 4G069 AA06 BA47A BB05A BB05B BC02A BC02B BC03A BC04A CB21 CB25 CB46 CB72 DA02 FC08 4H006 AA02 AC21 AC25 BA02 BA03 BA29 BA69 BB11 BB31 BC15 BC33 BC35 BC37 4H039 CA29 CD30 CD40 CF30 CL11
Claims (7)
在下に縮合反応及び脱水反応させて二量化アルデヒドを
生成させる二量化アルデヒドの製造方法において、塩基
性触媒水溶液からなる水相中に、原料アルデヒドを含む
油相を、下記式で定義される平均径（ｄｓ）が５００μ
ｍ以下となるように液滴として分散させて反応を行うこ
とを特徴とする方法。 平均径（ｄｓ）＝ΣＸｉ3 Ｎｉ／ΣＸｉ2 Ｎｉ Ｘｉ：液滴の最大径（μｍ） Ｎｉ：最大径がＸｉである液滴の個数1. A method for producing a dimerized aldehyde, wherein a raw material aldehyde is subjected to a condensation reaction and a dehydration reaction in the presence of a basic catalyst aqueous solution to produce a dimerized aldehyde. The average diameter (ds) defined by the following equation is 500 μ
m, wherein the reaction is carried out by dispersing as droplets so as to be not more than m. Average diameter (ds) = ΣXi 3 Ni / ΣXi 2 Ni Xi: maximum diameter of droplet (μm) Ni: number of droplets having maximum diameter Xi
ド、イソブチルアルデヒド又はこれらの混合物であるこ
とを特徴とする請求項１記載の方法。2. The method according to claim 1, wherein the starting aldehyde is n-butyraldehyde, isobutyraldehyde or a mixture thereof.
−メチル−ブチルアルデヒド又はこれらの混合物である
ことを特徴とする請求項１記載の方法。3. The raw material aldehyde is valeraldehyde, 2
2. The method according to claim 1, wherein the compound is methyl-butyraldehyde or a mixture thereof.
ルデヒドを含む油相との合計容積に対する油相の容積の
比が０．６以下であることを特徴とする請求項１ないし
３のいずれかに記載の方法。4. The method according to claim 1, wherein the ratio of the volume of the oil phase to the total volume of the aqueous phase comprising the basic catalyst aqueous solution and the oil phase containing the starting aldehyde is 0.6 or less. The method described in Crab.
が０．５〜２０重量％であることを特徴とする請求項１
ないし４のいずれかに記載の方法。5. The method according to claim 1, wherein the concentration of the basic catalyst in the basic catalyst aqueous solution is 0.5 to 20% by weight.
5. The method according to any one of items 1 to 4.
カリウム及び水酸化リチウムよりなる群から選ばれたも
のであることを特徴とする請求項１ないし５のいずれか
に記載の方法。6. The method according to claim 1, wherein the basic catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
デヒドと有機溶媒とからなることを特徴とする請求項１
ないし６のいずれかに記載の方法。7. An oil phase containing a raw material aldehyde, comprising a raw material aldehyde and an organic solvent.
7. The method according to any one of items 6 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10194118A JP2000026357A (en) | 1998-07-09 | 1998-07-09 | Production of dimerized aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10194118A JP2000026357A (en) | 1998-07-09 | 1998-07-09 | Production of dimerized aldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000026357A true JP2000026357A (en) | 2000-01-25 |
Family
ID=16319224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10194118A Pending JP2000026357A (en) | 1998-07-09 | 1998-07-09 | Production of dimerized aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000026357A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110128302A (en) * | 2009-03-17 | 2011-11-29 | 에보니크 옥세노 게엠베하 | METHOD FOR PRODUCING α,β-UNSATURATED C10-ALDEHYDES |
-
1998
- 1998-07-09 JP JP10194118A patent/JP2000026357A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110128302A (en) * | 2009-03-17 | 2011-11-29 | 에보니크 옥세노 게엠베하 | METHOD FOR PRODUCING α,β-UNSATURATED C10-ALDEHYDES |
| JP2012520838A (en) * | 2009-03-17 | 2012-09-10 | エボニック オクセノ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Process for producing α, β-unsaturated C10 aldehyde |
| KR101712218B1 (en) | 2009-03-17 | 2017-03-03 | 에보니크 데구사 게엠베하 | - method for producing -unsaturated 10-aldehydes |
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