JPH0426652A - Production of dicarboxylic acid ester from butadiene, carbon monoxide and alcohol - Google Patents
Production of dicarboxylic acid ester from butadiene, carbon monoxide and alcoholInfo
- Publication number
- JPH0426652A JPH0426652A JP2130520A JP13052090A JPH0426652A JP H0426652 A JPH0426652 A JP H0426652A JP 2130520 A JP2130520 A JP 2130520A JP 13052090 A JP13052090 A JP 13052090A JP H0426652 A JPH0426652 A JP H0426652A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- dicarboxylic acid
- butadiene
- pyridine
- alcohol
- 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.)
- Granted
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- -1 dicarboxylic acid ester Chemical class 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 239000012188 paraffin wax Substances 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- UMLQAWUDAFCGGS-HWKANZROSA-N ethyl (e)-pent-3-enoate Chemical compound CCOC(=O)C\C=C\C UMLQAWUDAFCGGS-HWKANZROSA-N 0.000 description 6
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 5
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 5
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、コバルトカルボニルを触媒としてブタジェン
と一酸化炭素およびアルコールからジカルボン酸エステ
ルを収率よく製造する方法に関するものである。アルコ
ールとしてはメタノール、エタノール、Ｎ−プロパツー
ルを用いることができ、それぞれ相当するジカルボン酸
エステルが製造される。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing dicarboxylic acid esters in good yield from butadiene, carbon monoxide, and alcohol using cobalt carbonyl as a catalyst. As the alcohol, methanol, ethanol, and N-propanol can be used, and corresponding dicarboxylic acid esters are produced.
近年非分解性プラスチックによる環境汚染が社会問題化
するにつれて、生分解性を有するプラスチックの開発が
求められている。生分解性プラスチックの有力候補物質
の一群として脂肪族ジカルボン酸とジオールから誘導さ
れるポリエステル類があり、ポリエチレンアジパー１〜
等が生分解性を有することはすでに明らかにされている
。したがって脂肪族ポリエステルの原料である脂肪族ジ
カルボン酸またはそのエステルの経済的新規製造法雪−
一′
ゝ−迂咋の要請に応える基本技術として重要である。In recent years, as environmental pollution caused by non-degradable plastics has become a social issue, there is a need for the development of biodegradable plastics. One group of potential candidates for biodegradable plastics are polyesters derived from aliphatic dicarboxylic acids and diols, including polyethylene adiper 1~
It has already been revealed that these materials are biodegradable. Therefore, a new and economical method for producing aliphatic dicarboxylic acids or their esters, which are raw materials for aliphatic polyesters.
1' ゝ - It is important as a basic technology that responds to requests for circumvention.
従来、アジピン酸はベンゼンを原料として、シクロヘキ
サンの酸化を経る多段階の工程により製造されているが
、ベンゼン価格の上昇のため、より安価な製造方法が求
められている。本発明は従来法と異なり、比較的安価な
ブタジェンと一酸化炭素、およびアルコールを原料とし
てアジピン酸を主成分とするＣ６−ジカルボン酸のエス
テルを８５％の高収率で一挙に製造する方法であり、経
済的に有利である。Conventionally, adipic acid has been produced using benzene as a raw material through a multi-step process of oxidizing cyclohexane, but due to the rising price of benzene, a cheaper production method is required. The present invention differs from conventional methods in that it uses relatively inexpensive butadiene, carbon monoxide, and alcohol as raw materials to produce C6-dicarboxylic acid esters containing adipic acid as the main component all at once with a high yield of 85%. Yes, it is economically advantageous.
さて、ブタジェンと一酸化炭素およびアルコールとをコ
バルトカルボニル触媒とピリジンの存在下に１２０℃か
ら１６０℃よりも低い温度で反応させることにより３−
ペンテン酸エステルを製造し、ついで得られた３−ペン
テン酸エステルと一酸化炭素およびアルコールとをコバ
ルトカルボニル触媒とピリジンの存在下に１６０℃〜２
００℃の反応温度で反応させることによりアジピン酸エ
ステルが得られることは特許第７６１２２６号に％、、
（−一１
−よ］公知である。このように反応温度を２段階に分け
て反応させるにあたり、同特許の実施例１〜３において
は第１段の反応を溶媒量のピリジンの存在下に６００気
圧、１３０℃で反応させたのち、３−ペンテン酸エステ
ルを蒸留により単離し７、得られた３−ペンテン酸エス
テルを異なる溶媒の存在下に１３０〜２００気圧、１６
０〜２００℃の条件で再び一酸化炭素及びアルコールと
反応させることにより、ブタジェンからの収率６４〜５
６％でアジピン酸エステルを製造している。ここでもし
中間体の３−ペンテン酸エステルを分離することなく、
温度（および圧力）を２段階に変えるだけでアジピン酸
エステルを直接製造することができれば、工程の節約に
なり有利であるが、同特許の実施例４〜７によると、こ
のような直接的方法を実施した場合のアジピン酸エステ
ルのブタジェンからの収率は４０〜４９％にすぎなかっ
た。Now, by reacting butadiene with carbon monoxide and alcohol in the presence of a cobalt carbonyl catalyst and pyridine at a temperature lower than 120°C to 160°C, 3-
A pentenoic acid ester is produced, and then the obtained 3-pentenoic acid ester, carbon monoxide and alcohol are heated at 160°C to 2°C in the presence of a cobalt carbonyl catalyst and pyridine.
It is disclosed in Japanese Patent No. 761226 that adipic acid ester can be obtained by reacting at a reaction temperature of 00°C.
(-11-yo) is publicly known. In carrying out the reaction by dividing the reaction temperature into two stages, in Examples 1 to 3 of the same patent, the first stage reaction was carried out in the presence of a solvent amount of pyridine. After reacting at 600 atm and 130°C, the 3-pentenoate ester was isolated by distillation7, and the obtained 3-pentenoate ester was reacted at 130-200 atm at 16 °C in the presence of different solvents.
By reacting with carbon monoxide and alcohol again under the conditions of 0 to 200°C, the yield from butadiene was 64 to 5.
Adipic acid ester is produced at 6%. Here, if the intermediate 3-pentenoate ester is not separated,
It would be advantageous if the adipate ester could be produced directly by changing the temperature (and pressure) in two steps, but according to Examples 4 to 7 of the patent, such a direct method is not possible. The yield of adipic acid ester from butadiene was only 40-49%.
本発明者らは、ブタジェンと一酸化炭素およびアルコー
ルを反応させ、中間体の３−ペンテン酸ゞ９抜チルを分
離せずに温度（および圧力）を２段階に変化させるだけ
でアジピン酸エステルを直接合成する方法について鋭意
検討を重ねた結果、第１段および第２段の反応を行わせ
たのち、生成液にパラフィンを注入すると触媒錯体の大
部分が生成物層から分離すること、および分離した錯体
をアセトンに溶かして次回の反応にリサイクルすること
により、ジカルボン酸エステルの収率が著しく増大する
ことを見出し、この知見に基づき本発明をなすに至った
。The present inventors reacted butadiene with carbon monoxide and alcohol, and produced adipic acid ester by simply changing the temperature (and pressure) in two steps without separating the intermediate 9-butyl 3-pentenoate. As a result of extensive research into the method of direct synthesis, we found that when paraffin is injected into the product solution after the first and second stage reactions, most of the catalyst complex is separated from the product layer, and separation. It has been found that the yield of dicarboxylic acid ester can be significantly increased by dissolving the resulting complex in acetone and recycling it to the next reaction, and based on this finding, the present invention has been completed.
本発明の方法は、ブタジェンと一酸化炭素およびアルコ
ールとをコバルトカルボニルとピリジンの存在下に１２
０℃から１６０℃よりも低い温度で第１段の反応を行わ
せることにより３−ペンテン酸エステルを製造し、つい
でそのまま反応温度を」二げて１６０℃から２００℃で
第２段の反応を行わせてジカルボン酸エステルを製造す
るにあたり、第２段の反応後の生成物にパラフィンを加
えて触媒のピリジン錯体を分離し、分離したピリジクル
使用することを特徴とするジカルボン酸エステルの製造
方法である。The method of the present invention involves combining butadiene, carbon monoxide, and alcohol in the presence of cobalt carbonyl and pyridine.
3-pentenoic acid ester is produced by carrying out the first stage reaction at a temperature lower than 160 °C from 0 °C, then the reaction temperature is raised as it is, and the second stage reaction is carried out at 160 °C to 200 °C. A method for producing a dicarboxylic acid ester, which comprises adding paraffin to the product after the second stage reaction to separate the pyridine complex of the catalyst, and using the separated pyridine. be.
本発明で用いられるピリジンとしては、α−置換基を持
たないピリジンが有効であり、ピリジン、イソキノリン
、４−メチルピリジン、３，５−ジメチルピリジン等が
使用される。これらのピリジンの中では３，５−ジメチ
ルピリジンが最も有効である。使用するピリジンと触媒
として用いるコバル１−のモル比はピリジン：Ｃｏ＝２
〜７：１の範囲であり、好ましくはピリジン：Ｃｏ＝２
．５〜４−１である。アセトンの使用量はブタジェン１
モル当り０．１〜１モルの範囲である。第１段の反応圧
力は２００〜３００気圧、第２段の圧力は１００〜３０
０気圧が好ましい。アルコールとしてはメタノール、エ
タノール、Ｎ−プロパツール等の第１アルコールを用い
ることができる。ただしメタノールを用いると第２段の
反応の途中で触媒が活性劣化を起こし易く、また触媒と
生成物（シｊ
１玉応後の分離にも、問題があるため、触媒のリサイク
ルが必ずしも容易ではない。したがってアルコールとし
てはメタノールよりエタノールまたはＮ−プロパツール
が好ましく、特にエタノールが最適である。As the pyridine used in the present invention, pyridine without an α-substituent is effective, and pyridine, isoquinoline, 4-methylpyridine, 3,5-dimethylpyridine, etc. are used. Among these pyridines, 3,5-dimethylpyridine is the most effective. The molar ratio of pyridine used and cobal 1- used as a catalyst is pyridine:Co=2
~7:1, preferably pyridine:Co=2
．． 5 to 4-1. The amount of acetone used is Butadiene 1
It ranges from 0.1 to 1 mole per mole. The reaction pressure in the first stage is 200-300 atm, and the pressure in the second stage is 100-30 atm.
Zero atmosphere is preferred. As the alcohol, primary alcohols such as methanol, ethanol, and N-propanol can be used. However, if methanol is used, the activity of the catalyst tends to deteriorate during the second stage reaction, and there are also problems in separating the catalyst and products after the reaction, so it is not always easy to recycle the catalyst. Therefore, as the alcohol, ethanol or N-propanol is preferable to methanol, and ethanol is particularly suitable.
本発明に従うとブタジェンと一酸化炭素およびアルコー
ルからジカルボン酸エステルを８０％以」−の高収率で
一挙に製造することができ、従来技術の欠点である「ｆ
＠媒の分離、回収、再生を含む工程の煩雑さ」が大巾に
軽減されるので、工業的ジカルボン酸エステルの製造方
法として好適である。According to the present invention, dicarboxylic acid esters can be produced all at once from butadiene, carbon monoxide, and alcohol with a high yield of 80% or more.
This method is suitable as an industrial method for producing dicarboxylic acid esters because the complexity of steps including separation, recovery, and regeneration of the medium is greatly reduced.
次に実施例および比較例により、本発明をさらに詳細に
説明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１゜
内容積約３００弗のかきまぜ器付ステンレス鋼製オー１
〜クレープを用いた。比較例１（実施例１の後に記載す
る）で生成物から分離した触媒錯体の一部１．０．８ｇ
（Ｃｏｏ、０１６ｍｏｌ、３゜ＪｇＰジメチルピリジ
ン０．０２１−・１、およびジカルボン酸エステル０．
００８８ｍｏｌを含む）をアセトン０．１．７ｍｏ］に
溶かしてオー１−クレープにリサイクルした。この外に
ジコバルトオクタカルボニル０．００２ｍｏｌを３，５
−ジメチルピリジン０．０５９ｍｏｌとエタノール０．
４ｍｏｌに溶かしたもの船追加し、全コバルト量を０．
０２ｍｏｌ、３，５−ジメチルピリジン／Ｃ。Example 1 Stainless steel oven with a stirrer with an internal volume of about 300 liters
-Used crepe. 1.0.8 g of the portion of the catalyst complex separated from the product in Comparative Example 1 (described after Example 1)
(Coo, 016 mol, 3゜JgP dimethylpyridine 0.021-.1, and dicarboxylic acid ester 0.
0088 mol) was dissolved in 0.1.7 mo of acetone and recycled to O-1-crepe. In addition to this, add 0.002 mol of dicobalt octacarbonyl to 3.5
-0.059 mol of dimethylpyridine and 0.05 mol of ethanol.
Add 4 mol of dissolved cobalt and reduce the total amount of cobalt to 0.
02 mol, 3,5-dimethylpyridine/C.
比を４に調節した。つぎにブタジェン０．１７ｍｏ１を
オー１〜クレープに仕込んだ。オートクレーブを一酸化
炭素で加圧し、加熱して２５０気圧、１２０℃として一
定条件で第１段の反応を６．５時間行わせると、ガスの
吸収が終了した。この時ブタジェンから８５％の収率で
３−ペンテン酸エチルが生成していた。つぎに残ガスの
一部を抜き出し、さらに加熱することにより２００気圧
、１−８０°Ｃとして、一定条件で第２段の反応を３．
５時間行わせた。その結果ブタジェンからの収率はアジ
ピン酸ジエチル５９．７％、分岐ジカルボン酸ジエチル
エステル２０．４％、したがってジカト！シ
ルボン酸エステルの総合収率は８０．１％、３ペンテン
酸エチル７．４％、吉草酸エチル９．２％であった。生
成液にＮ−ヘキサン１２０ｇを加えて振りまぜるとジカ
ルボン酸エステルの９３゜４％はＮ−ヘキサン層に移行
し、触媒錯体が分離した。生成物中に含まれるジカルボ
ン酸エステルの６．１％はリサイクル錯体に含まれてい
たものであるから、実施例１で生成したジカルボン酸エ
ステルのＮ−ヘキサンによる抽出率は９９％である。コ
バルトの分離率は９８％であった。The ratio was adjusted to 4. Next, 0.17 mo1 of butadiene was charged into the O1 crepe. The autoclave was pressurized with carbon monoxide and heated to 250 atm and 120° C., and the first stage reaction was carried out under constant conditions for 6.5 hours, and gas absorption was completed. At this time, ethyl 3-pentenoate was produced from butadiene with a yield of 85%. Next, a part of the remaining gas is extracted and further heated to 200 atm and 1-80°C, and the second stage reaction is carried out under certain conditions.
I let it run for 5 hours. As a result, the yield from butadiene was 59.7% diethyl adipate, 20.4% branched dicarboxylic acid diethyl ester, and therefore dicato! The overall yield of silboxylic acid ester was 80.1%, ethyl 3-pentenoate 7.4%, and ethyl valerate 9.2%. When 120 g of N-hexane was added to the resulting solution and the mixture was shaken, 93.4% of the dicarboxylic acid ester was transferred to the N-hexane layer, and the catalyst complex was separated. Since 6.1% of the dicarboxylic acid ester contained in the product was contained in the recycled complex, the extraction rate of the dicarboxylic acid ester produced in Example 1 with N-hexane was 99%. The cobalt separation rate was 98%.
比較例］
実施例１で記載したと同様なオートクレーブにジコバル
トオクタカルボニルＯ，Ｏ１ｍｏｌ、３゜５−ジメチル
ピリジン０．０８ｍｏ１．、エタノール０．４ｍｏ１．
、アセトン０．１．７ｍｏｉおよびブタジェン０．１７
ｍｏｌを仕込み、リサイクル錯体を用いなかった外は実
施例１と同様にして第１段および第２段の反応を行わせ
た。その結果ブタジェンからの収率はアジピン酸ジエチ
ル５５゜７％、分岐ジカルボン酸ジエチルエステル１６
゜ｉ、したがってジカルボン酸エステルの総合収率は７
２．０％、３−ペンテン酸エチル３．１％、吉草酸エチ
ル１２．４％であった。生成物にＮ−ヘキサン１２０ｇ
を加えて振りまぜることによりコバルトの９８％は触媒
錯体として分離した。Comparative Example] In an autoclave similar to that described in Example 1, 1 mol of dicobalt octacarbonyl O, O, and 0.08 mol of 3°5-dimethylpyridine were added. , ethanol 0.4mol.
, acetone 0.1.7 moi and butadiene 0.17
The first and second stage reactions were carried out in the same manner as in Example 1, except that mol was charged and the recycled complex was not used. As a result, the yield from butadiene was 55.7% for diethyl adipate, and 16% for branched diethyl dicarboxylate.
゜i, therefore the total yield of dicarboxylic acid ester is 7
2.0%, ethyl 3-pentenoate 3.1%, and ethyl valerate 12.4%. 120g of N-hexane to the product
By adding and shaking, 98% of the cobalt was separated as a catalyst complex.
実施例２
実施例１−で生成物から分離した触媒錯体の一部１２．
５ｇ （Ｃｏｏ、Ｏ］、７５ｍｏ ］、］３，５−ジメ
チルピリジン０．０２２９ｍｏｌおよびジカルボン酸エ
ステル０．０１２５ｍｏｌを含む）をアセトン０．１７
ｍｏｌに溶かしてオートクレーブにリサイクルした。こ
の外にジコバルトオクタカルボニル０．００３７５ｍｏ
ｌを３，５−ジメチルピリジン０．０３９６ｍｏｌとエ
タノール０．４ｍｏｌに溶かしたものを追加し、全コバ
ルト量を０．０２５ｍｏｌ、３，５−ジメチルピリジン
／ Ｃｏ比を２．５に調節した。つぎにブタジェン０．
１７ｍｏｌをオートクレーブに仕込み。Example 2 Part of the catalyst complex separated from the product in Example 1 12.
5g (Coo, O], 75mo],] containing 0.0229 mol of 3,5-dimethylpyridine and 0.0125 mol of dicarboxylic acid ester) was mixed with 0.17 mol of acetone.
It was dissolved in a mol and recycled into an autoclave. In addition to this, 0.00375 mo of dicobalt octacarbonyl
1 dissolved in 0.0396 mol of 3,5-dimethylpyridine and 0.4 mol of ethanol was added to adjust the total amount of cobalt to 0.025 mol and the 3,5-dimethylpyridine/Co ratio to 2.5. Next, butadiene 0.
Pour 17 mol into an autoclave.
−酸化炭素で加圧し、加熱して２５０気圧、１２０ ’
Ｃの反応条件とした。第１段の反応を一定条件ぎに残ガ
スの一部を抜出し、温度を上げて２００気圧、１８０
℃として一定条件で第２段の反応を２．５時間行わせた
。その結果ブタジェンからの収率はアジピン酸ジエチル
５９．９％、分岐ジカルボン酸ジエチルエステル１６．
２％、したがってジカルボン酸エステルの総合収率は７
６．３％、３−ペンテン酸エステル２．９％、吉草酸エ
チル１０．６％であった。生成液にＮ−ヘキサン１２０
ｇを加えてふりまぜるとジカルボン酸エステルの８８．
０％はＮ−ヘキサン層に移行し、触媒錯体が分離した。- Pressurized with carbon oxide and heated to 250 atm, 120'
The reaction conditions were set as C. Part of the residual gas was extracted from the first stage reaction under certain conditions, and the temperature was raised to 200 atm and 180 atm.
The second stage reaction was carried out at constant temperature for 2.5 hours. As a result, the yield from butadiene was 59.9% diethyl adipate and 16.9% diethyl adipate.
2%, so the overall yield of dicarboxylic acid ester is 7
6.3%, 3-pentenoic acid ester 2.9%, and ethyl valerate 10.6%. Add 120% N-hexane to the product solution.
Add 88.g of dicarboxylic acid ester and mix well.
0% was transferred to the N-hexane layer and the catalyst complex was separated.
生成液中に含まれるジカルボン酸エステルの８．８％は
リサイクル細体中に含まれていたものであるから、生成
ジカルボン酸エステルのＮ−ヘキサンによる抽出率は９
６．５％である。コバルトの分離率は９９％であった。Since 8.8% of the dicarboxylic acid ester contained in the product liquid was contained in the recycled particles, the extraction rate of the generated dicarboxylic acid ester with N-hexane was 9.
It is 6.5%. The cobalt separation rate was 99%.
実施例３
実施例２で分離した錯体触媒の一部」。４．１ｇ（Ｇ
ｏ ０ 、０２１ ｍ ｏ ］、］３，５−ジメチルピ
リジン０．０２１ｍｏｌおよびジカルボン酸ニス−しＩ
−テアし０．Ｏ１５３ｍｏｌを含む）をアセトン０゜１
７ｍｏｌに溶かしてオートクレーブにリサイクルした。Example 3 Part of the complex catalyst isolated in Example 2. 4.1g (G
o 0 , 021 m o ], ] 0.021 mol of 3,5-dimethylpyridine and 0.021 mol of dicarboxylic acid varnish and I-tear. (containing 153 mol of O) in acetone 0°1
It was dissolved to 7 mol and recycled to the autoclave.
この外にジコバルトオクタカルボニル０゜００４、５
ｍ ｏ １を３，５−ジメチルピリジン０゜０５４ｍｏ
］とエタノール０．４−ｍｏｌに溶かしたものを追加
し、全ＣＯ量を０．０３ｍｏｌ、３゜５−ジメチルピリ
ジン／ Ｃｏ比を２．５に調節した。その他は実施例１
と同様にして一酸化炭素の２５０気圧下、１−２０℃で
第１段の反応を５時間行わせた。この時点でガスの吸収
は終了し、ブタジェンから８４％の収率で３−ペンテン
酸エチルが生成した。つぎに第２段の反応温度を実施例
１より低温の１６０℃に変えて、２００気圧下に８時間
反応させた。その結果ブタジェンからの収率はアジピン
酸ジエチル５３．０％、分岐ジカルボン酸エステル２７
．８％、したがってジカルボン酸エステルの総合収率は
８０．８％、３−ペンテン酸エチル７゜６％、吉草酸エ
チル５．８％であった。生成物にＮ−ヘキサン１２０ｇ
を加えて振りまぜるとジカルボン酸エステルの８６．６
％はＷ、キサン層に移行し、触媒錯体が分離した。In addition to this, dicobalt octacarbonyl 0°004,5
m o 1 to 3,5-dimethylpyridine 0°054 mo
] and 0.4-mol of ethanol were added to adjust the total amount of CO to 0.03 mol and the 3°5-dimethylpyridine/Co ratio to 2.5. Others are Example 1
In the same manner as above, the first stage reaction was carried out under 250 atmospheres of carbon monoxide at 1-20°C for 5 hours. At this point, gas absorption ceased, and ethyl 3-pentenoate was produced from butadiene in a yield of 84%. Next, the reaction temperature in the second stage was changed to 160° C., which is lower than that in Example 1, and the reaction was carried out under 200 atmospheres for 8 hours. As a result, the yield from butadiene was 53.0% diethyl adipate and 27% branched dicarboxylic acid ester.
．． 8%, thus the overall yield of dicarboxylic acid ester was 80.8%, ethyl 3-pentenoate 7.6%, and ethyl valerate 5.8%. 120g of N-hexane to the product
When added and shaken, 86.6 of the dicarboxylic acid ester
% of W was transferred to the xane layer, and the catalyst complex was separated.
生成物中に含まれるジカルボン酸エステルの１０゜０％
はリサイクル錯体中に含まれていたものであるから、Ｎ
−ヘキサンによる生成ジカルボン酸エステルの抽出率は
９６．２％である。コバルトの分離率は９９％であった
。10°0% of dicarboxylic acid esters contained in the product
was contained in the recycled complex, so N
- The extraction rate of the produced dicarboxylic acid ester with hexane is 96.2%. The cobalt separation rate was 99%.
実施例４
実施例３で分離した錯体触媒の一部１４．１ｇ（Ｇｏｏ
、０２１ｍｏｌ、３，５−ジメチルピリジン０．０２４
７ｍｏｌ、およびジカルボン酸エステルＯ，Ｏ１５５ｍ
ｏｌを含む）をアセトンＯ０１，７ｍｏｌに溶かしてオ
ートクレーブにリサイクルした。この外にジコバルトオ
クタカルボニル０゜００４５ｍｏｌを３，５−ジメチル
ピリジン０゜０５０３ｍｏ １とエタノール０．４ｍｏ
ｌに溶かしたものを追加し、全ＣＯ量を０．０３ｍｏｌ
、３．５−ジメチルピリジン／ Ｃｏ比を２．５に調節
した。その他は実施例１と同様にして一酸化炭素の２５
０気圧下、１２０℃で第１段の反応を４゜５時間行わせ
たところ、ガスの吸収は終了した。Example 4 A portion of 14.1 g of the complex catalyst separated in Example 3 (Goo
, 021 mol, 3,5-dimethylpyridine 0.024
7 mol, and dicarboxylic acid ester O, O 155m
ol) was dissolved in 1.7 mol of acetone O and recycled to the autoclave. In addition to this, 0°0045 mol of dicobalt octacarbonyl, 0°0503 mol 1 of 3,5-dimethylpyridine and 0.4 mol of ethanol.
Add the dissolved CO to 0.03 mol.
, the 3.5-dimethylpyridine/Co ratio was adjusted to 2.5. The other conditions were the same as in Example 1.
When the first stage reaction was carried out at 120° C. under 0 atmospheric pressure for 4°5 hours, gas absorption was completed.
ｌ
；暑に第２段の反応圧力を実施例１より高圧の２５０気
圧に変えて、２５０気圧下、１８０℃で３゜５時間反応
させた。その結果ブタジェンからの収率はアジピン酸ジ
エチル６３．５％１分岐ジカルボン酸エステル１９．８
％、したがってジカルボン酸エステルの総合収率は８３
．３％、３−ペンテン酸エチル０．５％、吉草酸エチル
９．２％であった。生成物にＮ−ヘキサン１２０ｇを加
えて振りまぜるとジカルボン酸エステルの８６．５％は
Ｎ−ヘキサン層に移行し、触媒錯体が分離した。In the hot weather, the reaction pressure in the second stage was changed to 250 atm, which is higher than in Example 1, and the reaction was carried out at 180° C. for 3.5 hours under 250 atm. As a result, the yield from butadiene was 63.5% diethyl adipate and 19.8% mono-branched dicarboxylic acid ester.
%, thus the overall yield of dicarboxylic acid ester is 83
．． 3%, ethyl 3-pentenoate 0.5%, and ethyl valerate 9.2%. When 120 g of N-hexane was added to the product and shaken, 86.5% of the dicarboxylic acid ester was transferred to the N-hexane layer, and the catalyst complex was separated.
生成物中に含まれるジカルボン酸エステルの９゜９％は
リサイクル錯体中に含まれていたものであるから、Ｎ−
ヘキサンによる生成ジカルボン酸エステルの抽出率は９
６．０％である。コバルトの分離率は９９％であった。Since 9.9% of the dicarboxylic acid ester contained in the product was contained in the recycled complex, N-
The extraction rate of dicarboxylic acid ester produced by hexane is 9
It is 6.0%. The cobalt separation rate was 99%.
Claims (3)
バルトカルボニルとピリジンの存在下に１２０℃から１
６０℃よりも低い温度で第１段の反応を行わせることに
より３−ペンテン酸エステルを製造し、ついでそのまま
反応温度を上げて１６０℃から２００℃で第２段の反応
を行わせてジカルボン酸エステルを製造するにあたり、
第２段の反応後の生成物にパラフィンを加えて触媒のピ
リジン錯体を分離し、分離したピリジン錯体をアセトン
に溶かして次回の反応にリサイクル使用することを特徴
とするジカルボン酸エステルの製造方法。(1) Butadiene, carbon monoxide and alcohol are mixed at 120°C in the presence of cobalt carbonyl and pyridine.
3-pentenoic acid ester is produced by carrying out the first stage reaction at a temperature lower than 60°C, and then the reaction temperature is raised and the second stage reaction is carried out at 160°C to 200°C to produce dicarboxylic acid. In producing ester,
A method for producing a dicarboxylic acid ester, which comprises adding paraffin to the product after the second stage reaction to separate the pyridine complex of the catalyst, dissolving the separated pyridine complex in acetone and recycling it for the next reaction.
とする特許請求の範囲第１項に記載のジカルボン酸エス
テルの製造方法。(2) The method for producing a dicarboxylic acid ester according to claim 1, characterized in that ethanol is used as the alcohol.
を特徴とする特許請求の範囲第１項または第２項に記載
のジカルボン酸エステルの製造方法。(3) The method for producing a dicarboxylic acid ester according to claim 1 or 2, wherein the pyridine is 3,5-dimethylpyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2130520A JPH0764784B2 (en) | 1990-05-21 | 1990-05-21 | Process for producing dicarboxylic acid ester from butadiene, carbon monoxide and alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2130520A JPH0764784B2 (en) | 1990-05-21 | 1990-05-21 | Process for producing dicarboxylic acid ester from butadiene, carbon monoxide and alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426652A true JPH0426652A (en) | 1992-01-29 |
| JPH0764784B2 JPH0764784B2 (en) | 1995-07-12 |
Family
ID=15036263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2130520A Expired - Lifetime JPH0764784B2 (en) | 1990-05-21 | 1990-05-21 | Process for producing dicarboxylic acid ester from butadiene, carbon monoxide and alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764784B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003006416A1 (en) * | 2001-07-13 | 2003-01-23 | Dsm Ip Assets B.V. | Process for the carbonylation of a conjugated diene and use of such process in the preparation of caprolactam or adipic acid |
| US9631752B2 (en) | 2011-03-31 | 2017-04-25 | Mitsubishi Heavy Industries Compressor Corporation | Expansion joint and steam turbine system including the same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4872112A (en) * | 1971-12-28 | 1973-09-29 | ||
| US3778466A (en) * | 1971-06-18 | 1973-12-11 | Agency Ind Science Techn | Method for manufacture of 3-pentenoic acid ester |
| JPS4920177A (en) * | 1972-06-21 | 1974-02-22 | ||
| US3856832A (en) * | 1970-12-07 | 1974-12-24 | Corp Ethyl | Process for recovering cobalt catalyst in an active form from a hydroesterification reaction mixture |
| JPS5062888A (en) * | 1973-10-06 | 1975-05-29 | ||
| JPS5337327A (en) * | 1976-09-17 | 1978-04-06 | Matsushita Electric Ind Co Ltd | Protective device for output circuit |
| US4303589A (en) * | 1979-12-31 | 1981-12-01 | Monsanto Company | Hydroesterification process |
| JPS5872539A (en) * | 1981-10-28 | 1983-04-30 | Japan Synthetic Rubber Co Ltd | Method for producing dicarboxylic acid ester |
-
1990
- 1990-05-21 JP JP2130520A patent/JPH0764784B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856832A (en) * | 1970-12-07 | 1974-12-24 | Corp Ethyl | Process for recovering cobalt catalyst in an active form from a hydroesterification reaction mixture |
| US3778466A (en) * | 1971-06-18 | 1973-12-11 | Agency Ind Science Techn | Method for manufacture of 3-pentenoic acid ester |
| JPS4872112A (en) * | 1971-12-28 | 1973-09-29 | ||
| JPS4920177A (en) * | 1972-06-21 | 1974-02-22 | ||
| JPS5062888A (en) * | 1973-10-06 | 1975-05-29 | ||
| JPS5337327A (en) * | 1976-09-17 | 1978-04-06 | Matsushita Electric Ind Co Ltd | Protective device for output circuit |
| US4303589A (en) * | 1979-12-31 | 1981-12-01 | Monsanto Company | Hydroesterification process |
| JPS5872539A (en) * | 1981-10-28 | 1983-04-30 | Japan Synthetic Rubber Co Ltd | Method for producing dicarboxylic acid ester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003006416A1 (en) * | 2001-07-13 | 2003-01-23 | Dsm Ip Assets B.V. | Process for the carbonylation of a conjugated diene and use of such process in the preparation of caprolactam or adipic acid |
| US9631752B2 (en) | 2011-03-31 | 2017-04-25 | Mitsubishi Heavy Industries Compressor Corporation | Expansion joint and steam turbine system including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764784B2 (en) | 1995-07-12 |
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