JPH0217150A - Purification of methyl methacrylate - Google Patents
Purification of methyl methacrylateInfo
- Publication number
- JPH0217150A JPH0217150A JP16658488A JP16658488A JPH0217150A JP H0217150 A JPH0217150 A JP H0217150A JP 16658488 A JP16658488 A JP 16658488A JP 16658488 A JP16658488 A JP 16658488A JP H0217150 A JPH0217150 A JP H0217150A
- Authority
- JP
- Japan
- Prior art keywords
- column
- methyl methacrylate
- distillation
- methanol
- azeotropic
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004821 distillation Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 5
- 238000010533 azeotropic distillation Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明はメタクリル酸メチルの精製方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for purifying methyl methacrylate.
(従来の技術)
メタクリル酸メチル(以下、MMAと記す)・を精製す
る方法として、■MMAとメタノールの水含有混合物に
メタノールと共沸混合物を形成する共沸形成剤を添加し
共沸蒸留してメタノールを分離する方法(特開昭58−
180457号)や■メタノール、水、MMAよりなる
混合液を蒸留精製する場合、炭素数6ないし7の飽和炭
化水素を存在させて蒸留を行ない塔頂から飽和炭化水素
とメタノールを留出せしめ、塔下部からデカンタ−によ
りMMAと水とを分離して別々に抜き出す方法(特開昭
57−9740号)がすでに知られている。しかしなが
らこれらの方法は次のような問題点を有している。すな
わち、■の方法では、塔底残留物中には依然として水が
存在するためこの分離のためにさらに蒸留などの処理が
必要である、また■では、塔頂留出物が二液分離しない
場合がありその際は共沸溶剤とメタノールとを分離する
ため抽出などの別途処理を要することになる。(Prior art) As a method for purifying methyl methacrylate (hereinafter referred to as MMA), an azeotrope-forming agent that forms an azeotrope with methanol is added to a water-containing mixture of MMA and methanol, and azeotropic distillation is performed. A method for separating methanol using
180457) or ■ When purifying a mixed solution consisting of methanol, water, and MMA by distillation, distillation is performed in the presence of a saturated hydrocarbon having 6 to 7 carbon atoms, and the saturated hydrocarbon and methanol are distilled out from the top of the column. A method of separating MMA and water from the lower part using a decanter and extracting them separately is already known (Japanese Patent Laid-Open No. 57-9740). However, these methods have the following problems. In other words, in method (■), since water still exists in the bottom residue, further treatment such as distillation is required to separate this water, and in method (2), when the top distillate is not separated into two liquids, In this case, separate treatment such as extraction is required to separate the azeotropic solvent and methanol.
さらに■の方法においては、塔下部から層分離により水
とMMA等を分離するため、MMA中に水が最大溶解変
分まで含まれ(MMAに対する水の溶解度は例えば25
℃で1.2%)この水分を除くためさらに蒸留等の操作
が必要となる。Furthermore, in method (2), since water and MMA are separated from the bottom of the column by layer separation, water is contained in MMA up to the maximum solubility variation (for example, the solubility of water in MMA is 25
(1.2% at °C) Further operations such as distillation are required to remove this moisture.
(発明が解決しようとする課題)
一般に、MMAはメタクリル酸、メタクリル酸アミド、
メタクリロニトリル等を酸性触媒の存在下に過剰量のメ
タノールと反応させることにより製造される。これらの
エステル化反応によって生成したMMAは藤発、抽出、
層分離等の方法で主として水、メタノールおよびMMA
から成る混合物としてエステル化反応液から分離される
。この混合物は相互に共沸組成物を形成するため、目的
成分であるMMAをその他の不純物から効果的に分離す
るためには繁雑な操作を要し、未だ満足すべき方法が見
出されていない。(Problem to be solved by the invention) Generally, MMA contains methacrylic acid, methacrylic acid amide,
It is produced by reacting methacrylonitrile or the like with an excess amount of methanol in the presence of an acidic catalyst. MMA produced by these esterification reactions is extracted by Fujihata,
Mainly water, methanol and MMA are separated by layer separation etc.
It is separated from the esterification reaction solution as a mixture consisting of: Since this mixture mutually forms an azeotrope, complicated operations are required to effectively separate the target component MMA from other impurities, and no satisfactory method has yet been found. .
本発明の目的とするところは、MMAを精製する際、主
な不純物となる水、メタノールをより効率的に蒸留分離
する方法を従供するにある。An object of the present invention is to provide a method for more efficiently distilling and separating water and methanol, which are the main impurities when purifying MMA.
(課題を解決するための手段)
このような目的は、本発明によれば、主として水、メタ
ノールおよびMMAよりなる混合物を蒸留塔に供給して
M M Aを蒸留精製するに際し、共沸溶剤として炭素
数6の炭化水素(以下、C6炭化水素と記す)を蒸留塔
濃縮部に存在させ、塔頂部より水およびメタノールを0
6炭化水素の共沸混合物として留出せしめ、塔底からM
MAを抜き出すことを特徴とするMMAの精製法により
達成される。(Means for Solving the Problems) According to the present invention, when a mixture mainly consisting of water, methanol and MMA is supplied to a distillation column to purify MMA by distillation, MMA is used as an azeotropic solvent. Hydrocarbons having 6 carbon atoms (hereinafter referred to as C6 hydrocarbons) are present in the concentration section of the distillation column, and water and methanol are removed from the top of the column.
It is distilled out as an azeotropic mixture of 6 hydrocarbons, and M
This is achieved by an MMA purification method characterized by extracting MA.
(作用)
本発明は、水、メタノールおよびMMAの混合物を蒸留
塔に供給してMMAを蒸留精製する際、共沸溶剤として
C6炭化水素を蒸留塔濃縮部に存在させるものである。(Function) According to the present invention, when a mixture of water, methanol and MMA is supplied to a distillation column to purify MMA by distillation, a C6 hydrocarbon is present as an azeotropic solvent in the concentration section of the distillation column.
ここで水、メタノールおよびMMAの混合物には、これ
ら以外にMMAに対して低沸点および高沸点不純物が含
まれているのが通常である。また当該混合物は液状また
はベーパー状で蒸留塔に供給される。本発明において共
沸溶剤として用いられるC6炭化水素とはn−ヘキサン
、シクロヘキサン、ベンゼン等であるが、n−ヘキサン
がよりすぐれた作用を示すので好ましい。In addition to these, the mixture of water, methanol, and MMA usually contains impurities with low boiling points and high boiling points relative to MMA. Further, the mixture is supplied to the distillation column in liquid or vapor form. The C6 hydrocarbons used as an azeotropic solvent in the present invention include n-hexane, cyclohexane, benzene, etc., and n-hexane is preferred because it exhibits better effects.
本発明において最も特徴とするところは、蒸留に際し、
水およびメタノールと各々共沸混合物を形成するC6炭
化水素を蒸留塔の濃縮部に存在させることにより、水お
よびメタノールを06炭化水素の共沸混合物として塔頂
より一挙に留出せしめることができる点にある。The most distinctive feature of the present invention is that during distillation,
By allowing C6 hydrocarbons that form azeotropic mixtures with water and methanol to exist in the concentration section of the distillation column, water and methanol can be distilled out at once from the top of the column as an azeotropic mixture of 06 hydrocarbons. It is in.
この塔頂留出液はデカンタ−により容易に層分離し、上
層部は実質的にC6炭化水素として蒸留塔塔頂に還流さ
れる。一方、下層液はメタノール水溶液として系外に除
かれるが、必要に応じエステル化原料として適宜回収さ
れる。This column overhead distillate is easily separated into layers using a decanter, and the upper layer is refluxed to the top of the distillation column as substantially C6 hydrocarbons. On the other hand, the lower layer liquid is removed from the system as an aqueous methanol solution, but is appropriately recovered as an esterification raw material if necessary.
共沸溶剤であるC6炭化水素の還流量は、メタノールと
06炭化水素との共沸組成ならびに水と06炭化水素と
の共沸組成を形成するに必要なC6炭化水素の量である
。例えばn−ヘキサンの場合は第1表の如き共沸組成を
示す。The reflux amount of C6 hydrocarbon, which is an azeotropic solvent, is the amount of C6 hydrocarbon necessary to form an azeotropic composition of methanol and 06 hydrocarbon and an azeotropic composition of water and 06 hydrocarbon. For example, n-hexane has an azeotropic composition as shown in Table 1.
第 1 表
なお通常は上記共沸組成理論量より若干過剰の量で管理
されている。Table 1 Note that the azeotropic composition is usually controlled in an amount slightly in excess of the theoretical amount of the azeotropic composition.
(実施例) 以下本発明の方法を実施例により説明する。(Example) The method of the present invention will be explained below with reference to Examples.
蒸留塔として内径50n、段数30段のオールダーショ
ウ型蒸留塔を用いた。塔頂から15段目に原料供給口が
設置されており、一方塔頂からの留出液はデカンタ−で
層分離し、上層液は塔頂へ還流され、下N液は系外へ除
去された。塔底部には丸型フラスコが接続されており、
油浴に浸されている。As the distillation column, an Oldershaw type distillation column having an inner diameter of 50 nm and 30 plates was used. A raw material supply port is installed at the 15th stage from the top of the column, while the distillate from the top of the column is separated into layers in a decanter, the upper layer liquid is refluxed to the top of the column, and the lower N liquid is removed from the system. Ta. A round flask is connected to the bottom of the tower.
Immersed in an oil bath.
原料混合液として、メタクリル酸メチル97.3シロ、
メタノール8.0%、水12.7%、フェッチアジア0
.01%の組成を有する液を135g/時の流量で供給
して常圧蒸留を行った。As a raw material mixture, 97.3 shiro of methyl methacrylate,
Methanol 8.0%, Water 12.7%, Fetch Asia 0
.. Atmospheric distillation was carried out by supplying a liquid having a composition of 0.01% at a flow rate of 135 g/hour.
一方、デカンタ−内には、あらかじめn−ヘキサンと水
が仕込まれており、蒸留開始と同時にデカンタ−よりn
−ヘキサンを塔頂へ350 g/時で還流させた。蒸留
塔の定常運転時の塔頂温度は58℃、塔底温度は105
℃であった。On the other hand, n-hexane and water have been charged in advance in the decanter, and at the same time as the distillation starts, n-hexane and water are poured into the decanter.
-Hexane was refluxed to the top of the column at 350 g/h. During steady operation of the distillation column, the top temperature is 58℃, and the bottom temperature is 105℃.
It was ℃.
この蒸留操作により水、メタノールはn−ヘキサンとの
共沸混合物として塔頂から留去され、水およびメタノー
ルはデカンタ−下層液として系外へ除去することができ
た。塔底からはメタノール18ppmおよび水130p
pmを含有するMMAが105g/時で得られた。Through this distillation operation, water and methanol were distilled off from the top of the column as an azeotropic mixture with n-hexane, and water and methanol could be removed from the system as a decanter bottom liquid. 18ppm of methanol and 130p of water from the bottom of the tower
105 g/h of MMA containing pm was obtained.
(効果)
本発明の方法により、主な不純物である水、メタノール
がC6炭化水素との共沸蒸留により一挙に塔頂から留去
せしめることができ、ついで層分離によりC6炭化水素
と分離され、系外に除去しうるというすぐれた効果を示
す。(Effects) According to the method of the present invention, water and methanol, which are the main impurities, can be distilled off at once from the top of the column by azeotropic distillation with C6 hydrocarbons, and then separated from C6 hydrocarbons by layer separation. It shows an excellent effect in that it can be removed from the system.
昭和63年 9月1日September 1, 1986
Claims (3)
ルよりなる混合物を蒸留塔に供給してメタクリル酸メチ
ルを蒸留精製するに際し、共沸溶剤として炭素数6の炭
化水素を蒸留塔濃縮部に存在させ、塔頂より水およびメ
タノールを当該炭化水素の共沸混合物として留出せしめ
、塔底からメタクリル酸メチルを抜き出すことを特徴と
するメタクリル酸メチルの精製法。(1) When supplying a mixture mainly consisting of water, methanol and methyl methacrylate to a distillation column to purify methyl methacrylate by distillation, a hydrocarbon having 6 carbon atoms is present in the distillation column concentration section as an azeotropic solvent, A method for purifying methyl methacrylate, which comprises distilling water and methanol from the top as an azeotropic mixture of the hydrocarbons, and extracting methyl methacrylate from the bottom of the column.
に還流液として戻し、下層液を系外に除去する、特許請
求の範囲第1項記載のメタクリル酸メチルの精製法。(2) A method for purifying methyl methacrylate according to claim 1, wherein the liquid distilled from the top of the column is separated into layers, the upper layer liquid is returned to the top of the column as a reflux liquid, and the lower layer liquid is removed from the system. .
いる特許請求の範囲第1〜2項記載のメタクリル酸メチ
ルの精製法。(3) A method for purifying methyl methacrylate according to claims 1 and 2, in which n-hexane is used as the saturated hydrocarbon having 6 carbon atoms.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63166584A JP2582127B2 (en) | 1988-07-04 | 1988-07-04 | Purification method of methyl methacrylate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63166584A JP2582127B2 (en) | 1988-07-04 | 1988-07-04 | Purification method of methyl methacrylate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0217150A true JPH0217150A (en) | 1990-01-22 |
JP2582127B2 JP2582127B2 (en) | 1997-02-19 |
Family
ID=15833987
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63166584A Expired - Lifetime JP2582127B2 (en) | 1988-07-04 | 1988-07-04 | Purification method of methyl methacrylate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2582127B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5093520A (en) * | 1990-06-21 | 1992-03-03 | Basf Aktiengesellschaft | Preparation of monoethylenically unsaturated carboxylates |
US5187309A (en) * | 1989-08-03 | 1993-02-16 | Elf Atochem S.A. | Process for the continuous preparation of lower acrylates |
JPH08268938A (en) * | 1995-03-29 | 1996-10-15 | Osaka Organic Chem Ind Ltd | Separation of methyl acrylate or methyl methacrylate and methanol |
JP2018537466A (en) * | 2015-12-18 | 2018-12-20 | ローム アンド ハース カンパニーRohm And Haas Company | Process for the purification of methyl methacrylate |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2965476C (en) | 2014-10-31 | 2022-11-29 | Dow Global Technologies Llc | Breaking a methanol/methyl methacrylate azeotrope using pressure swing distillation |
EP3212598B1 (en) | 2014-10-31 | 2018-09-12 | Dow Global Technologies LLC | Separation process |
TW201722903A (en) | 2015-12-18 | 2017-07-01 | 陶氏全球科技責任有限公司 | Process for purification of methyl methacrylate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6419374A (en) * | 1987-07-14 | 1989-01-23 | Konishiroku Photo Ind | Editor |
-
1988
- 1988-07-04 JP JP63166584A patent/JP2582127B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6419374A (en) * | 1987-07-14 | 1989-01-23 | Konishiroku Photo Ind | Editor |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5187309A (en) * | 1989-08-03 | 1993-02-16 | Elf Atochem S.A. | Process for the continuous preparation of lower acrylates |
US5093520A (en) * | 1990-06-21 | 1992-03-03 | Basf Aktiengesellschaft | Preparation of monoethylenically unsaturated carboxylates |
JPH08268938A (en) * | 1995-03-29 | 1996-10-15 | Osaka Organic Chem Ind Ltd | Separation of methyl acrylate or methyl methacrylate and methanol |
JP2018537466A (en) * | 2015-12-18 | 2018-12-20 | ローム アンド ハース カンパニーRohm And Haas Company | Process for the purification of methyl methacrylate |
Also Published As
Publication number | Publication date |
---|---|
JP2582127B2 (en) | 1997-02-19 |
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