JP2001322968A - Method for purifying methacrylic acid ester - Google Patents
Method for purifying methacrylic acid esterInfo
- Publication number
- JP2001322968A JP2001322968A JP2000140550A JP2000140550A JP2001322968A JP 2001322968 A JP2001322968 A JP 2001322968A JP 2000140550 A JP2000140550 A JP 2000140550A JP 2000140550 A JP2000140550 A JP 2000140550A JP 2001322968 A JP2001322968 A JP 2001322968A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- acid ester
- liquid
- column
- 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
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イソブタン、イソ
ブチレン、第３級ブチルアルコール、メタクロレイン等
を気相接触酸化反応して得られるメタクリル酸を低級ア
ルコールとエステル化反応させて得られるメタクリル酸
エステルの精製方法に関する。The present invention relates to a methacrylic acid ester obtained by subjecting methacrylic acid obtained by subjecting isobutane, isobutylene, tertiary butyl alcohol, methacrolein and the like to a gaseous phase catalytic oxidation reaction with a lower alcohol and esterifying it. And a method for purifying the same.
【０００２】[0002]
【従来の技術】従来、メタクリル酸エステルの製造方法
として、イソブタン、イソブチレン、第３級ブチルアル
コール、メタクロレイン等を気相接触酸化反応し、反応
物を抽出や蒸留等の手段により精製してメタクリル酸を
得た後、さらにこのメタクリル酸を低級アルコールとエ
ステル化反応させ、次に、メタクリル酸エステルを含む
反応液を、抽出や蒸留などの通常の手段により精製して
メタクリル酸エステルを得る方法が知られている。この
方法では比較的純度の高いメタクリル酸エステルが得ら
れるが、エステル化反応時に低級アルコールが高沸化合
物化した物質（以下、アルコール付加物という）が副生
する。このアルコール付加物については特定はできてい
ないが、メタクリル酸エステルと共に精製塔へ送られる
と加熱されることにより精製塔でアルコール付加物の一
部が分解し低級アルコールを発生し、メタクリル酸エス
テル中に低級アルコールが含まれる原因となる。低級ア
ルコールはメタクリル酸エステルの重合反応および重合
物の性質に悪影響を与えるなど様々な問題を引き起こし
ている。2. Description of the Related Art Conventionally, as a method for producing a methacrylic acid ester, isobutane, isobutylene, tertiary butyl alcohol, methacrolein and the like are subjected to a gas phase catalytic oxidation reaction, and the reaction product is purified by means such as extraction or distillation to obtain methacrylic acid. After obtaining the acid, the methacrylic acid is further subjected to an esterification reaction with a lower alcohol, and then the reaction solution containing the methacrylic ester is purified by ordinary means such as extraction or distillation to obtain a methacrylic ester. Are known. According to this method, a methacrylic acid ester having a relatively high purity can be obtained, but a substance obtained by converting a lower alcohol into a high-boiling compound during the esterification reaction (hereinafter, referred to as an alcohol adduct) is produced as a by-product. Although it is not possible to specify the alcohol adduct, it is heated when sent to the purification tower together with the methacrylic acid ester, whereby part of the alcohol adduct is decomposed in the purification tower to generate lower alcohol, and the methacrylic acid ester May contain lower alcohols. Lower alcohols cause various problems such as adversely affecting the polymerization reaction of methacrylic acid esters and the properties of the polymer.
【０００３】特公平６−１１７３２号公報には、エステ
ル化反応生成物を第１工程でメタクリル酸メチル、メタ
ノールおよび水を主成分とする留出液と未反応のメタク
リル酸を主成分とする缶出液とに蒸留分離し、留出液は
第２工程のメタノール抽出器で未反応メタノールを水で
抽出分離し、メタノール抽出器上部から得られるメタク
リル酸メチル相を脱水塔、低沸分離塔、メタクリル酸メ
チル精製塔の蒸留塔３塔でメタクリル酸メチルを精製す
る方法が記載されている。[0003] Japanese Patent Publication No. 6-11732 discloses that, in a first step, a distillate containing methyl methacrylate, methanol and water as main components and an unreacted methacrylic acid as a main component in a first step. The distillate is separated by distillation, and the unreacted methanol is extracted and separated with water in the methanol extractor in the second step, and the methyl methacrylate phase obtained from the upper part of the methanol extractor is subjected to a dehydration tower, a low-boiling separation tower, A method for purifying methyl methacrylate in three distillation towers of a methyl methacrylate purification tower is described.
【０００４】しかしながら、この方法ではエステル化反
応器とメタクリル酸回収塔の間に高沸物が蓄積する、メ
タクリル酸回収塔においてメタクリル酸メチルに加えて
エステル化の副生物である水と未反応のメタノールの全
てを留出させているので加熱に多くの熱量を要する、低
沸除去用に２塔の蒸留塔を要するので設備費が嵩む等の
問題がある。また、該公報には高沸物であるアルコール
付加物について一切記載されていない。However, in this method, high boiling substances accumulate between the esterification reactor and the methacrylic acid recovery tower. In the methacrylic acid recovery tower, unreacted water, which is a by-product of esterification, in addition to methyl methacrylate. Since all of methanol is distilled off, there is a problem that a large amount of heat is required for heating, and two distillation columns are required for low boiling removal, so that the equipment cost is increased. Further, this publication does not disclose any high-boiling alcohol adduct.
【０００５】本発明者らは先に特公昭６１−４３７８号
公報において、エステル化反応により生成したメタクリ
ル酸エステルを含む反応液を抽出塔に送液し未反応の低
級アルコールを除去した後、蒸留により低沸除去を行
い、その後メタクリル酸エステルを精製する方法を開示
した。この方法によればエステル化反応液から未反応の
低級アルコールや副生した水を蒸発させるためのフラッ
シュ塔や蒸留塔を用いずに、経済的にメタクリル酸エス
テルを製造することができる。The present inventors have previously disclosed in Japanese Patent Publication No. 61-4378, a reaction solution containing a methacrylic acid ester formed by an esterification reaction was sent to an extraction column to remove unreacted lower alcohol, and then distilled. A method for performing low-boiling removal by the method described above and thereafter purifying the methacrylic acid ester was disclosed. According to this method, a methacrylic acid ester can be economically produced without using a flash tower or a distillation tower for evaporating unreacted lower alcohol or by-produced water from the esterification reaction liquid.
【０００６】[0006]
【発明が解決しようとする課題】しかし、昨今メタクリ
ル酸エステルの重合物は、光ファイバーなどの通信用に
まで用途が拡大してきており、そのモノマーであるメタ
クリル酸エステルに対して従来よりもさらに高純度のも
のが要求されるようになってきた。However, in recent years, the use of polymers of methacrylic acid esters has been expanded to use in communications such as optical fibers, and the purity of methacrylic acid ester, which is a monomer thereof, is higher than before. Things have come to be required.
【０００７】本発明は、このような従来の問題点に鑑み
てなされたものであり、低級アルコールを実質的に含ま
ない高純度なメタクリル酸エステルを、しかも経済的に
得る精製方法を提供することを目的とする。The present invention has been made in view of such conventional problems, and provides a purification method for economically obtaining a high-purity methacrylate ester substantially containing no lower alcohol. With the goal.
【０００８】[0008]
【課題を解決するための手段】本発明は、メタクリル酸
と低級アルコールとを液相中でエステル化反応させて生
成したメタクリル酸エステルを精製する方法において、
（１ａ）エステル化反応で得られた反応液から、抽剤を
用いて未反応アルコールを抽出分離する工程と、（１
ｂ）前記（１ａ）の工程により未反応アルコールが分離
された液を蒸留し、メタクリル酸エステルを含有する液
を留出させることにより、液中から高沸物を除去する工
程と、（１ｃ）前記（１ｂ）の工程にて高沸物が除去さ
れた反応液を蒸留し、低沸物を留出させて除去し、メタ
クリル酸エステルを含有する缶出液を取り出す工程と、
（１ｄ）前記（１ｃ）の工程で取り出した缶出液を蒸留
してメタクリル酸エステルを留出させる工程とを有する
メタクリル酸エステルの精製方法に関する。SUMMARY OF THE INVENTION The present invention provides a method for purifying a methacrylic acid ester produced by subjecting methacrylic acid and a lower alcohol to an esterification reaction in a liquid phase.
(1a) a step of extracting and separating unreacted alcohol from the reaction solution obtained by the esterification reaction using an extractant;
b) a step of distilling a liquid from which unreacted alcohol has been separated in the step (1a) and distilling a liquid containing a methacrylic acid ester to remove high-boiling substances from the liquid; and (1c) Distilling the reaction solution from which high-boiling substances have been removed in the step (1b), distilling and removing low-boiling substances, and removing a bottom liquid containing methacrylic acid ester;
(1d) a step of distilling the bottoms taken out in the step (1c) to distill out the methacrylic acid ester.
【０００９】また本発明は、メタクリル酸と低級アルコ
ールとを液相中でエステル化反応させて生成したメタク
リル酸エステルを精製する方法において、（２ａ）エス
テル化反応で得られた反応液を向流型抽出塔に導いて、
反応液と抽剤を向流接触させて未反応アルコールを抽出
分離する工程と、（２ｂ）前記（２ａ）の工程により未
反応アルコールが分離された液を第１の蒸留塔（高沸除
去塔）に送り、液中から高沸物を蒸留塔の塔底より缶出
させ、塔頂からメタクリル酸エステルを含有する液を留
出させる工程と、（２ｃ）前記（２ｂ）の工程にて塔頂
から留出させた液を第２の蒸留塔（低沸除去塔）に送
り、低沸物を留出させて除去し、塔底からメタクリル酸
エステルを含有する缶出液を取り出す工程と、（２ｄ）
前記（２ｃ）の工程で塔底から取り出した缶出液を第３
の蒸留塔（精製塔）に送り、塔頂からメタクリル酸エス
テルを留出させる工程とを有するメタクリル酸エステル
の精製方法に関する。The present invention also relates to a method for purifying a methacrylic acid ester produced by subjecting methacrylic acid and a lower alcohol to an esterification reaction in a liquid phase, wherein (2a) the reaction solution obtained in the esterification reaction is subjected to a countercurrent flow. To the extraction tower,
(2b) extracting and separating the unreacted alcohol by countercurrently contacting the reaction liquid and the extractant; and (2b) separating the liquid from which the unreacted alcohol has been separated in the step (2a) into a first distillation column (high boiling removal column) ) To remove high-boiling substances from the liquid from the bottom of the distillation column and to distill the liquid containing methacrylic acid ester from the top of the column; (2c) the column in the step (2b) Sending the liquid distilled off from the top to a second distillation column (low-boiling column), distilling out and removing low-boiling substances, and removing a bottoms containing methacrylic acid ester from the bottom of the column; (2d)
The bottoms removed from the bottom of the column in the step (2c) is
And a step of distilling the methacrylic acid ester from the top of the column.
【００１０】本発明において、前記エステル化反応は、
固体酸性触媒を用いて行うことができる。In the present invention, the esterification reaction comprises:
It can be carried out using a solid acidic catalyst.
【００１１】[0011]
【発明実施の形態】本発明において、メタクリル酸をエ
ステル化して反応液（以下、エステル化反応液とい
う。）を得るまでは通常の方法に従うことができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a conventional method can be used until esterification of methacrylic acid to obtain a reaction solution (hereinafter referred to as an esterification reaction solution).
【００１２】即ち、例えばまずイソブタン、イソブチレ
ン、第３級ブチルアルコール、メタクロレイン等を、公
知の触媒の存在下に気相接触酸化反応してメタクリル酸
とした後、抽出や蒸留等の公知の技術により精製してメ
タクリル酸を得る。次に、得られたメタクリル酸と低級
アルコールを固体酸性触媒の存在下でエステル化反応さ
せることでメタクリル酸エステルを含むエステル化反応
液を得る。That is, for example, first, isobutane, isobutylene, tertiary butyl alcohol, methacrolein and the like are subjected to a gas phase catalytic oxidation reaction in the presence of a known catalyst to give methacrylic acid, and then known techniques such as extraction and distillation are used. To obtain methacrylic acid. Next, the obtained methacrylic acid and lower alcohol are subjected to an esterification reaction in the presence of a solid acidic catalyst to obtain an esterification reaction solution containing a methacrylic acid ester.
【００１３】エステル化反応において使用する酸性固体
触媒は、ポリスチレン系スルホン酸型カチオン交換樹脂
が好ましく、例えばＡｍｂｅｒｌｉｔｅ ＩＲ−１１
８、ＩＲ−１２０、ＩＲ−２００（Ｒｏｈｍ ＆ Ｈａ
ａｓ社製）、ダイヤイオンＰＫ−２０８、ＰＫ−２２
８、ＳＫ−１０２（三菱化成社製）、ＤＯＷ−５０（Ｄ
ＯＷ社製）等が挙げられる。The acidic solid catalyst used in the esterification reaction is preferably a polystyrene sulfonic acid type cation exchange resin, for example, Amberlite IR-11.
8, IR-120, IR-200 (Rohm & Ha
as), Diaion PK-208, PK-22
8, SK-102 (manufactured by Mitsubishi Kasei), DOW-50 (D
OW).
【００１４】エステル化の際に使用される低級アルコー
ルは、炭素数８以下、特に炭素数４以下のものが好まし
く、具体的にはメタノール、エタノール、イソプロパノ
ール、ｎ−ブタノール、イソブタノールを挙げることが
できる。エステル化反応におけるメタクリル酸の反応率
や反応に関する条件は、特公昭６１−４３７８号公報に
記載の条件を参考にする事ができる。The lower alcohol used in the esterification preferably has 8 or less carbon atoms, particularly preferably 4 or less carbon atoms. Specific examples include methanol, ethanol, isopropanol, n-butanol and isobutanol. it can. The conditions relating to the conversion and reaction of methacrylic acid in the esterification reaction can be referred to the conditions described in JP-B-61-4378.
【００１５】このような反応の結果、精製する前のエス
テル化反応液には、通常メタクリル酸エステル３０〜７
５質量％、低級アルコール１０〜４０質量％、メタクリ
ル酸１０〜３０質量％、水６〜１５質量％、その他の化
合物０．５〜５質量％が含まれている。As a result of such a reaction, the esterification reaction solution before purification usually contains 30 to 7 methacrylic acid esters.
It contains 5% by mass, 10 to 40% by mass of lower alcohol, 10 to 30% by mass of methacrylic acid, 6 to 15% by mass of water, and 0.5 to 5% by mass of other compounds.
【００１６】以下、本発明のメタクリル酸エステルの精
製方法の一例を図１を参照しながら説明する。Hereinafter, an example of a method for purifying a methacrylic acid ester of the present invention will be described with reference to FIG.
【００１７】（１）エステル化反応器２１にメタクリル
酸および低級アルコールをそれぞれメタクリル酸供給ラ
イン１、低級アルコール供給ライン２から供給し、固体
酸触媒の存在下で反応させる。(1) Methacrylic acid and lower alcohol are supplied to the esterification reactor 21 from the methacrylic acid supply line 1 and the lower alcohol supply line 2, respectively, and reacted in the presence of a solid acid catalyst.
【００１８】（２）エステル化反応器２１から反応後の
エステル化反応液をライン３により抜き出す。この反応
液は、特に処理することなくそのままアルコール抽出塔
２２の下部に供給することができる。一方、アルコール
抽出塔２２に、ライン４から主に水からなる抽剤を導入
し、エステル化反応液と抽剤を向流接触させる。アルコ
ールを分離したメタクリル酸エステル相を、アルコール
抽出塔２２の上部からライン６を通して高沸除去塔２３
へ送る。一方、アルコール抽出液はアルコール抽出塔の
下部に設けたライン５から抜き出し、アルコール回収塔
（図示せず）で低級アルコールを回収し、再びエステル
化原料として用いる。尚、ここでアルコール抽出に用い
る装置は、特に制限はないが、効率の点から向流型が好
ましく、例えば、充填塔型、多孔板型、バッフル型、ミ
キサーセトラー型、回転円盤型等の装置を挙げることが
できる。また、抽出剤としては、メタクリル酸エステル
から低級アルコールを抽出できるものであればよく、水
を主成分として、必要により、メタクリル酸等を含むこ
とができる。(2) The esterification reaction solution after the reaction is withdrawn from the esterification reactor 21 through the line 3. This reaction solution can be directly supplied to the lower portion of the alcohol extraction column 22 without any particular treatment. On the other hand, an extractant mainly composed of water is introduced into the alcohol extraction tower 22 from the line 4, and the esterification reaction liquid and the extractant are brought into countercurrent contact. The methacrylic acid ester phase from which the alcohol has been separated is passed through the line 6 from the upper part of the alcohol extraction column 22 to the high boiling removal column 23.
Send to On the other hand, the alcohol extract is withdrawn from the line 5 provided at the lower part of the alcohol extraction tower, and the lower alcohol is recovered in an alcohol recovery tower (not shown) and used again as an esterification raw material. The apparatus used for alcohol extraction is not particularly limited, but is preferably of a countercurrent type from the viewpoint of efficiency. For example, a packed tower type, a perforated plate type, a baffle type, a mixer settler type, a rotating disk type, etc. Can be mentioned. The extractant may be any one that can extract a lower alcohol from a methacrylic acid ester, and may contain water as a main component and, if necessary, methacrylic acid or the like.
【００１９】（３）アルコールが分離されたメタクリル
酸エステル相が送られる高沸除去塔２３は蒸留塔であ
り、ここで、主としてメタクリル酸エステルと水からな
る留出物と、メタクリル酸やアルコール付加物などの高
沸物とに分離する。即ち、高沸除去塔の塔頂から主とし
てメタクリル酸エステルと水からなる留出物を、凝集器
３２にて凝集させ、凝縮液をデカンター２６に送る。デ
カンターで、主として水からなる下相と、主としてメタ
クリル酸エステルからなる上相の二相に分離させる。主
に水からなる下相は、ライン７を通して系外に抜き出
し、主にメタクリル酸エステルからなる上相の一部は塔
頂に還流し、残りの上相はライン８により低沸除去塔２
４に送る。(3) The high-boiling removal column 23 to which the methacrylic acid ester phase from which the alcohol has been separated is sent is a distillation column, in which a distillate mainly composed of methacrylic acid ester and water, and methacrylic acid and alcohol addition Separated into high-boiling substances such as substances. That is, the distillate mainly composed of methacrylic acid ester and water is aggregated in the aggregator 32 from the top of the high boiling removal tower, and the condensate is sent to the decanter 26. The decanter separates into two phases, a lower phase mainly composed of water and an upper phase mainly composed of methacrylate. The lower phase mainly composed of water is drawn out of the system through the line 7, a part of the upper phase mainly composed of methacrylic acid ester is refluxed to the top of the column, and the remaining upper phase is reduced by the line 8 to the low boiling removal column 2.
Send to 4.
【００２０】一方、メタクリル酸やアルコール付加物な
どの高沸物は、高沸除去塔２３の塔底から抜き出し、一
部は再加熱器３１で加熱して高沸除去塔に戻し、残りを
ライン９を通してメタクリル酸回収塔（図示せず）に導
いてメタクリル酸を回収し再びエステル化原料として用
いる。On the other hand, high-boiling substances such as methacrylic acid and alcohol adducts are extracted from the bottom of the high-boiling removal tower 23, a part of the high-boiling substance is heated by the reheater 31 and returned to the high-boiling removal tower. The mixture is led to a methacrylic acid recovery tower (not shown) through 9 to recover methacrylic acid and use it again as a raw material for esterification.
【００２１】この高沸除去塔による操作により、アルコ
ール付加物等を含む高沸物が除去されるので、後の工程
において、精製塔でアルコール付加物が分解し精製メタ
クリル酸エステル中に低級アルコールが混入することを
防止できる。Since the high-boiling substances including the alcohol adducts and the like are removed by the operation using the high-boiling removal tower, the alcohol adducts are decomposed in the purification tower in the subsequent step, and the lower alcohol is contained in the purified methacrylic acid ester. Mixing can be prevented.
【００２２】（４）低沸除去塔２４は、蒸留塔であり、
主として低沸物と水からなる留出物と、メタクリル酸エ
ステルとを分離する。(4) The low-boiling removal column 24 is a distillation column,
The distillate consisting mainly of low-boiling substances and water is separated from methacrylic acid esters.
【００２３】即ち、塔頂から留出物を凝集器３４にて凝
集させ、凝集液をデカンター２７に送る。デカンター２
７で、主としてメタクリル酸エステルからなる上相と、
主に水およびその他の低沸物等を含む下相とに分離す
る。主に水からなる下相と共に低沸物をライン１０から
抜き出し、上相は全て塔頂へ還流する。That is, the distillate is coagulated from the top of the column in the coagulator 34, and the coagulated liquid is sent to the decanter 27. Decanter 2
7, an upper phase mainly composed of methacrylic acid ester;
It mainly separates into a lower phase containing water and other low-boiling substances. Low boilers are withdrawn from line 10 along with the lower phase, which consists primarily of water, and all the upper phase is refluxed to the top.
【００２４】一方、低沸除去塔２４の塔底からは、低沸
物と水が除去された主にメタクリル酸エステルを含む缶
出液を抜き出し、一部は再加熱器３３で加熱して低沸除
去塔に戻し、残りをライン１１を通して精製塔２５に送
る。精製塔に送られる液中からは、低沸物が十分に除去
されている。On the other hand, from the bottom of the low-boiling removal tower 24, a bottom liquid containing mainly methacrylic acid ester from which low-boiling substances and water have been removed is withdrawn, and a part of the bottom liquid is heated by the reheater 33 to reduce the bottom liquid. It is returned to the boiling removal tower, and the remainder is sent to the purification tower 25 through the line 11. Low boiling substances are sufficiently removed from the liquid sent to the purification tower.
【００２５】（５）精製塔２５は、蒸留塔であり、再加
熱器３５、および凝集器３６を備えており、塔頂からの
留出物を凝集器３６で凝集し、一部を還流し、残りをラ
イン１２より抜き出して高純度のメタクリル酸エステル
を得る。一方、ライン１３から重合物等の高沸物を含む
液を抜き出す。(5) The refining tower 25 is a distillation tower, and is provided with a reheater 35 and an aggregator 36. The distillate from the top of the tower is agglomerated by the aggregator 36, and a part is refluxed. And the rest is withdrawn from the line 12 to obtain a high-purity methacrylate. On the other hand, a liquid containing a high-boiling substance such as a polymer is extracted from the line 13.
【００２６】以上の工程（３）〜（５）において用いら
れる各蒸留装置は、上記目的に合うものから適宜選択で
きるものであり、また操作条件についても適宜設定する
ことができる。Each of the distillation apparatuses used in the above steps (3) to (5) can be appropriately selected from those meeting the above-mentioned objects, and the operating conditions can be appropriately set.
【００２７】このようにして、エステル化反応液から、
まず未反応の低級アルコールを抽出除去した後に高沸物
を除去することで、アルコール付加物を確実に除去する
ことができる。その結果、精製塔でアルコール付加物が
分解し精製メタクリル酸エステル中に低級アルコールが
混入することを回避できる。さらに未反応の低級アルコ
ールや副生した水を全て蒸発させずに経済的に有利にメ
タクリル酸エステルを精製することができる。従って、
本発明の一連の工程による精製方法では、高純度のメタ
クリル酸エステルを経済的に得ることができる。Thus, from the esterification reaction solution,
First, the unreacted lower alcohol is extracted and removed, and then the high-boiling substance is removed, whereby the alcohol adduct can be reliably removed. As a result, it is possible to avoid that the alcohol adduct is decomposed in the purification tower and the lower alcohol is mixed into the purified methacrylate. Further, the methacrylic acid ester can be economically and advantageously purified without evaporating any unreacted lower alcohol or by-produced water. Therefore,
In the purification method according to the series of steps of the present invention, high-purity methacrylate can be obtained economically.
【００２８】[0028]
【実施例】以下に実施例を示して、本発明をさらに具体
的に説明する。実施例において％は特に記載がない場合
を除き質量％を表し、圧力は絶対圧を表す。The present invention will be described more specifically with reference to the following examples. In Examples,% represents mass% unless otherwise specified, and pressure represents absolute pressure.
【００２９】［実施例１］実施例１では、図１に示した
精製装置を用いて、前述の（１）〜（５）の工程に従っ
て精製を行った。[Example 1] In Example 1, purification was performed according to the above-mentioned steps (1) to (5) using the purification apparatus shown in FIG.
【００３０】イソブチレンを出発原料として気相接触酸
化によって得られたメタクリル酸を抽出および蒸留によ
り精製し、反応温度８０℃でスルホン酸型カチオン交換
樹脂の存在下、メタノールでエステル化反応を行った。
得られた反応液を塔径４．６ｃｍ、段数４０段の回転円
盤型抽出塔に１．３０ｋｇ／ｈで供給し、抽剤として水
を用い未反応のメタノールを抽出し、抽出塔上部からメ
タノール０．３％、水５．８％、メタクリル酸メチル６
９．８％、メタクリル酸２１．６％、その他の化合物
２．５％を含む粗メタクリル酸メチルを得た。Using isobutylene as a starting material, methacrylic acid obtained by gas phase catalytic oxidation was purified by extraction and distillation, and an esterification reaction was carried out with methanol at a reaction temperature of 80 ° C. in the presence of a sulfonic acid type cation exchange resin.
The obtained reaction liquid was supplied at a rate of 1.30 kg / h to a rotating disk type extraction column having a column diameter of 4.6 cm and 40 stages, and unreacted methanol was extracted using water as an extractant, and methanol was extracted from the upper portion of the extraction column. 0.3%, water 5.8%, methyl methacrylate 6
Crude methyl methacrylate containing 9.8%, 21.6% methacrylic acid and 2.5% of other compounds was obtained.
【００３１】得られた粗メタクリル酸メチルを２０段の
オールダーショウ型蒸留塔（高沸除去塔）に０．９８ｋ
ｇ／ｈで供給した。高沸除去塔の塔頂圧力は１８．４ｋ
Ｐａであり、塔頂温度は４５℃、塔底温度は９３℃であ
った。塔頂部からの留出物を凝集させデカンターに導い
た。そのデカンター上相（メタノール０．２％、水１．
２％、メタクリル酸メチル９８．４％、その他の化合物
０．２％）を０．６３ｋｇ／ｈで抜き出し、３０段のオ
ールダーショウ型蒸留塔（低沸除去塔）に供給した。低
沸除去塔の塔頂圧力は４６．１ｋＰａであり、塔頂温度
は６０℃、塔底温度は８１℃であった。塔底からは低沸
物を除去した缶出液（水０．０１％、メタクリル酸メチ
ル９９．９７％、その他の化合物０．０２％）を０．６
２ｋｇ／ｈで抜き出した。この時、缶出液にメタノー
ル、アクリル酸メチル、酢酸メチルなどの低沸物は検出
されなかった。The obtained crude methyl methacrylate was placed in a 20-stage Oldershaw distillation column (high-boiling column) at 0.98 k.
g / h. The top pressure of the high boiling removal tower is 18.4k
Pa, the top temperature was 45 ° C, and the bottom temperature was 93 ° C. The distillate from the top was aggregated and led to a decanter. The upper phase of the decanter (methanol 0.2%, water 1.
2%, methyl methacrylate 98.4%, and other compounds 0.2%) were withdrawn at 0.63 kg / h and supplied to a 30-stage Oldershaw distillation column (low boiling removal column). The top pressure of the low boiling removal tower was 46.1 kPa, the top temperature was 60 ° C, and the bottom temperature was 81 ° C. 0.6% of bottom product (0.01% water, 99.97% of methyl methacrylate, 0.02% of other compounds) from which low boiling substances were removed from the bottom of the column.
It was withdrawn at 2 kg / h. At this time, low-boiling substances such as methanol, methyl acrylate, and methyl acetate were not detected in the bottoms.
【００３２】得られた缶出液を３０段のオールダーショ
ウ型蒸留塔（精製塔）に供給した。精製塔の塔頂圧力は
１９．７ｋＰａであり、塔頂温度は５６℃、塔底温度は
６６℃であり、精製塔塔頂から９９．９８％のメタクリ
ル酸メチルを０．６０ｋｇ／ｈで得ることができた。The bottom product obtained was supplied to a 30-stage Oldershaw distillation column (purification column). The top pressure of the purification tower is 19.7 kPa, the top temperature is 56 ° C., the bottom temperature is 66 ° C., and 99.98% methyl methacrylate is obtained at 0.60 kg / h from the top of the purification tower. I was able to.
【００３３】メタクリル酸メチル中のメタノールの分析
を行ったところ２ｐｐｍ以下であった。The analysis of methanol in methyl methacrylate showed that it was 2 ppm or less.
【００３４】［比較例１］実施例１において、高沸除去
塔を用いることなく、抽出分離工程までで得られた粗メ
タクリル酸メチルを低沸除去塔に直接送ることにより、
高沸除去工程を省いた以外は実施例１と同様の方法で精
製を行った。[Comparative Example 1] In Example 1, the crude methyl methacrylate obtained up to the extraction / separation step was directly sent to the low boiling removal column without using the high boiling removal column.
Purification was performed in the same manner as in Example 1 except that the high boiling removal step was omitted.
【００３５】メタクリル酸メチルを０．６４ｋｇ／ｈで
得ることができたが、メタクリル酸メチル中に含まれる
メタノールは１２１ｐｐｍであった。Although methyl methacrylate was obtained at 0.64 kg / h, methanol contained in methyl methacrylate was 121 ppm.
【００３６】[0036]
【発明の効果】本発明の一連の工程からなる精製方法を
適用することにより、アルコール付加物の分解により生
成する低級アルコールの製品中への混入を、低コストに
て効果的に防止することが可能になるので、高純度のメ
タクリル酸エステルを経済的に得ることができる。By applying the purification method comprising a series of steps of the present invention, it is possible to effectively prevent the lower alcohol produced by the decomposition of the alcohol adduct into the product at low cost. As a result, high-purity methacrylate can be economically obtained.
【図１】本発明に用いられるメタクリル酸エステル精製
装置の１例である。FIG. 1 is an example of an apparatus for purifying methacrylic ester used in the present invention.
１ メタクリル酸供給ライン ２ 低級アルコール供給ライン ３、４、５、６、７、８、９、１０、１１、１２、１３
ライン ２１ エステル化反応器 ２２ アルコール抽出塔 ２３ 高沸除去塔 ２４ 低沸除去塔 ２５ 精製塔 ２６ デカンター ２７ デカンター ３１ 再加熱器 ３２ 凝集器 ３３ 再加熱器 ３４ 凝集器 ３５ 再加熱器 ３６ 凝集器1 methacrylic acid supply line 2 lower alcohol supply line 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13
Line 21 Esterification reactor 22 Alcohol extraction tower 23 High boiling removal tower 24 Low boiling removal tower 25 Purification tower 26 Decanter 27 Decanter 31 Reheater 32 Coagulator 33 Reheater 34 Coagulator 35 Reheater 36 Coagulator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹沢 英泰 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央技術研究所内 (72)発明者 日野 智道 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央技術研究所内 Ｆターム(参考） 4H006 AA02 AC48 AD11 AD16 BC50 BD82 BD84 DA64 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Hideyasu Takezawa, Inventor 20-1, Miyukicho, Otake-shi, Hiroshima Prefecture, Central Research Institute of Mitsubishi Rayon Co., Ltd. (72) Tomomichi Hino 20-1, Miyukicho, Otake-shi, Hiroshima Pref. No. F-term in Central Research Laboratory of Mitsubishi Rayon Co., Ltd. (Reference) 4H006 AA02 AC48 AD11 AD16 BC50 BD82 BD84 DA64
Claims (3)
中でエステル化反応させて生成したメタクリル酸エステ
ルを精製する方法において、 （１ａ）エステル化反応で得られた反応液から、抽剤を
用いて未反応アルコールを抽出分離する工程と、 （１ｂ）前記（１ａ）の工程により未反応アルコールが
分離された液を蒸留し、メタクリル酸エステルを含有す
る液を留出させることにより、液中から高沸物を除去す
る工程と、 （１ｃ）前記（１ｂ）の工程にて高沸物が除去された反
応液を蒸留し、低沸物を留出させて除去し、メタクリル
酸エステルを含有する缶出液を取り出す工程と、 （１ｄ）前記（１ｃ）の工程で取り出した缶出液を蒸留
してメタクリル酸エステルを留出させる工程とを有する
メタクリル酸エステルの精製方法。1. A method for purifying a methacrylic acid ester produced by subjecting methacrylic acid and a lower alcohol to an esterification reaction in a liquid phase, comprising: (1a) using an extractant from a reaction solution obtained by the esterification reaction; (1b) distilling the liquid from which the unreacted alcohol has been separated in the step (1a), and distilling out the liquid containing methacrylic acid ester, from the liquid. (1c) distilling the reaction solution from which the high-boiling substances have been removed in the step (1b), distilling out the low-boiling substances and removing them, and containing a methacrylic acid ester; A method for purifying a methacrylic ester, comprising: a step of extracting a bottom liquid; and (1d) a step of distilling the bottom liquid extracted in the step (1c) to distill a methacrylic ester.
中でエステル化反応させて生成したメタクリル酸エステ
ルを精製する方法において、 （２ａ）エステル化反応で得られた反応液を向流型抽出
塔に導いて、反応液と抽剤を向流接触させて未反応アル
コールを抽出分離する工程と、 （２ｂ）前記（２ａ）の工程により未反応アルコールが
分離された液を第１の蒸留塔（高沸除去塔）に送り、液
中から高沸物を蒸留塔の塔底より缶出させ、塔頂からメ
タクリル酸エステルを含有する液を留出させる工程と、 （２ｃ）前記（２ｂ）の工程にて塔頂から留出させた液
を第２の蒸留塔（低沸除去塔）に送り、低沸物を留出さ
せて除去し、塔底からメタクリル酸エステルを含有する
缶出液を取り出す工程と、 （２ｄ）前記（２ｃ）の工程で塔底から取り出した缶出
液を第３の蒸留塔（精製塔）に送り、塔頂からメタクリ
ル酸エステルを留出させる工程とを有するメタクリル酸
エステルの精製方法。2. A method for purifying a methacrylic acid ester produced by subjecting methacrylic acid and a lower alcohol to an esterification reaction in a liquid phase, comprising: (2a) a countercurrent extraction column comprising: (2b) extracting and separating the unreacted alcohol by countercurrently contacting the reaction liquid and the extractant; and (2b) separating the liquid from which the unreacted alcohol has been separated in the step (2a) into a first distillation column ( (2) removing the liquid containing methacrylic acid ester from the top of the distillation column, and distilling a liquid containing a methacrylate ester from the top of the column. The liquid distilled from the top in the process is sent to a second distillation column (low-boiling column) to distill and remove low-boiling substances, and the bottoms containing methacrylic acid ester is removed from the bottom of the column. (2d) from the bottom of the tower in the step (2c) Ri out bottoms and the feed to the third distillation column (purification column), the purification method of the methacrylic acid ester and a step of distilling a methacrylic acid ester from the column top.
用いて行われる請求項１または２記載のメタクリル酸エ
ステルの精製方法。3. The method according to claim 1, wherein the esterification reaction is performed using a solid acidic catalyst.
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|---|---|---|---|
| JP2000140550A JP3999926B2 (en) | 2000-05-12 | 2000-05-12 | Method for purifying methacrylate ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000140550A JP3999926B2 (en) | 2000-05-12 | 2000-05-12 | Method for purifying methacrylate ester |
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| Publication Number | Publication Date |
|---|---|
| JP2001322968A true JP2001322968A (en) | 2001-11-20 |
| JP2001322968A5 JP2001322968A5 (en) | 2005-07-14 |
| JP3999926B2 JP3999926B2 (en) | 2007-10-31 |
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|---|---|---|---|
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| CN114292186A (en) * | 2022-01-14 | 2022-04-08 | 万华化学集团股份有限公司 | Preparation method of high-purity MMA |
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