Nothing Special   »   [go: up one dir, main page]

JP3211396B2 - Recovery method of acrylic acid and acetic acid - Google Patents

Recovery method of acrylic acid and acetic acid

Info

Publication number
JP3211396B2
JP3211396B2 JP22706392A JP22706392A JP3211396B2 JP 3211396 B2 JP3211396 B2 JP 3211396B2 JP 22706392 A JP22706392 A JP 22706392A JP 22706392 A JP22706392 A JP 22706392A JP 3211396 B2 JP3211396 B2 JP 3211396B2
Authority
JP
Japan
Prior art keywords
acetic acid
distillation column
acrylic acid
line
column
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP22706392A
Other languages
Japanese (ja)
Other versions
JPH0672944A (en
Inventor
恭輔 河崎
博 吉村
邦彦 重松
稔 安田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP22706392A priority Critical patent/JP3211396B2/en
Publication of JPH0672944A publication Critical patent/JPH0672944A/en
Application granted granted Critical
Publication of JP3211396B2 publication Critical patent/JP3211396B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、プロピレン及び/又は
アクロレインを分子状酸素で接触酸化してアクリル酸を
製造する際に、副生する酢酸をアクリル酸と共に純度良
く回収する方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering acetic acid by-produced together with acrylic acid with high purity when producing acrylic acid by catalytically oxidizing propylene and / or acrolein with molecular oxygen.

【0002】[0002]

【従来の技術】プロピレンおよび/またはアクロレイン
を水蒸気の存在下に固体触媒を用いて分子状酸素にて気
相接触酸化することによって得られる反応生成ガスは、
通常、冷却、洗浄されて水溶液として回収される。この
水溶液には主成分のアクリル酸のほかに、アクロレイ
ン、酢酸、その他のアルデヒド類等が含まれている。こ
のうち、アクロレインはアクリル酸と沸点差が大きいた
めに簡単に分離できる。また、その他のアルデヒド類は
生成量が極めて少なく、実用上の問題となることはほと
んどない。しかしながら、酢酸はアクリル酸に対して、
酸化触媒や反応条件によって異なるが、通常、1〜15
wt%程度副生し、これを分離、除去することは有効成
分の回収および廃棄物負荷の低減の観点から重要であ
る。
2. Description of the Related Art A reaction product gas obtained by subjecting propylene and / or acrolein to gas-phase catalytic oxidation with molecular oxygen using a solid catalyst in the presence of steam is as follows:
Usually, it is cooled, washed and recovered as an aqueous solution. This aqueous solution contains acrolein, acetic acid, other aldehydes and the like in addition to acrylic acid as a main component. Of these, acrolein can be easily separated because of its large boiling point difference from acrylic acid. In addition, the amount of other aldehydes produced is extremely small and hardly causes a practical problem. However, acetic acid is
Depending on the oxidation catalyst and reaction conditions, it is usually 1 to 15
It is important to separate and remove by-products of about wt% from the viewpoints of recovery of active ingredients and reduction of waste load.

【0003】アクリル酸と酢酸を分離する方法として、
蒸留で直接分離する方法(特公昭49−24898
号)、アクリル酸を安定化させる効果があるといわれる
トルエン、エチルベンゼン、キシレンなどの共沸溶媒を
使用して共沸蒸留する方法(特開昭49−7216号、
特公昭63−10691号、特開平3−181440
号、特公昭41−11247号)が知られている。
[0003] As a method for separating acrylic acid and acetic acid,
Direct separation by distillation (JP-B-49-24898)
Azeotropic distillation using an azeotropic solvent such as toluene, ethylbenzene or xylene, which is said to have an effect of stabilizing acrylic acid (JP-A-49-7216,
JP-B-63-10691, JP-A-3-181440
No. JP-B-41-11247) is known.

【0004】[0004]

【発明が解決しようとする課題】しかしながら、蒸留で
直接分離する方法は、アクリル酸と酢酸の沸点差が小さ
いことから、蒸留塔の還流比や段数を大幅に増加させな
ければばらず、更に酢酸分離塔においてアクリル酸の重
合物が蒸留塔内で生成しやすいという問題を有してい
る。従来の共沸蒸留する方法は、酢酸をアクリル酸から
分離することはできるが、酢酸を排水中に捨てることに
なり、排水負荷が大きくなり、また、方法によっては回
収酢酸中にアクリル酸が混入し、純度が低下すると同時
に、アクリル酸がロスしてしまい好ましい方法とは言い
難い。
However, in the direct separation method by distillation, since the boiling point difference between acrylic acid and acetic acid is small, the reflux ratio and the number of stages in the distillation column must be greatly increased. There is a problem that a polymer of acrylic acid is easily formed in the distillation column in the separation column. With the conventional azeotropic distillation method, acetic acid can be separated from acrylic acid, but acetic acid is discarded in the wastewater, which increases the drainage load, and depending on the method, acrylic acid is mixed in the recovered acetic acid. However, at the same time as the purity is reduced, acrylic acid is lost, which is not a preferable method.

【0005】本発明者はかかる問題のない粗アクリル酸
水溶液から精製アクリル酸及び酢酸を分離回収すること
を目的として鋭意検討した結果、第一蒸留塔で粗アクリ
ル酸水溶液から共沸脱水によって水を分離し、第二蒸留
塔で塔底からアクリル酸を取り出し、第三蒸留塔で実質
的にアクリル酸を含まない酢酸を留出させ、塔底液は第
一蒸留塔又は第二蒸留塔に循環し、第四蒸留塔で水を加
えて溶媒を留去し、塔底より酢酸を取り出すことによ
り、効率良く、高純度のアクリル酸及び酢酸を回収でき
ることを見出し、本発明に至った。
The inventors of the present invention have conducted intensive studies for the purpose of separating and recovering purified acrylic acid and acetic acid from a crude acrylic acid aqueous solution free from such problems, and as a result, water was removed from the crude acrylic acid aqueous solution by azeotropic dehydration in the first distillation column. Separate, take out acrylic acid from the bottom in the second distillation column, distill acetic acid substantially free of acrylic acid in the third distillation column, circulate the bottom liquid to the first distillation column or the second distillation column Then, the present inventors have found that high-purity acrylic acid and acetic acid can be efficiently recovered by adding water in a fourth distillation column to distill off the solvent and removing acetic acid from the bottom of the column, thereby leading to the present invention.

【0006】[0006]

【課題を解決するための手段】すなわち本発明は、
(1)プロピレン及び/又はアクロレインを分子状酸素
で接触酸化して生成するガスを冷却及び/又は水に吸収
して得られる粗アクリル水溶液又は該水溶液中のアルデ
ヒド類をストリッピングにより除去した水溶液及び酢酸
と水のそれぞれと共沸する溶媒を第一蒸留塔に供給し、
(2)第一蒸留塔の塔頂より供給液に含まれる実質的に
全ての水を同伴する一部の酢酸と共に留去し、酢酸及び
アクリル酸を塔底液として抜き出して第二蒸留塔に供給
し、(3)第二蒸留塔にて残り全ての酢酸とアクリル酸
の一部を塔頂より留出させて第三蒸留塔に供給し、塔底
より精製アクリル酸を回収し、(4)第三蒸留塔にて塔
頂より実質的にアクリル酸を含まない酢酸を留出させて
第四蒸留塔に供給し、塔底より酢酸及びアクリル酸を抜
き出して第一蒸留塔又は第二蒸留塔に循環し、(5)第
四蒸留塔にて塔頂に水を供給して溶媒を留去し、塔底よ
り精製酢酸を回収することを特徴とするアクリル酸及び
酢酸の回収方法である。
That is, the present invention provides:
(1) a crude acrylic aqueous solution obtained by cooling and / or absorbing gas produced by catalytically oxidizing propylene and / or acrolein with molecular oxygen, and / or an aqueous solution obtained by removing aldehydes in the aqueous solution by stripping; A solvent that azeotropes with each of acetic acid and water is supplied to the first distillation column,
(2) From the top of the first distillation column, substantially all of the water contained in the feed solution is distilled off together with a portion of the accompanying acetic acid, and acetic acid and acrylic acid are withdrawn as a bottom solution and passed to the second distillation column. (3) In the second distillation column, all remaining acetic acid and part of acrylic acid are distilled off from the top and supplied to the third distillation column, and purified acrylic acid is recovered from the bottom of the column. ) Distilling acetic acid substantially free of acrylic acid from the top of the third distillation column and supplying it to the fourth distillation column, extracting acetic acid and acrylic acid from the bottom of the column, and removing the acetic acid and acrylic acid from the first distillation column or the second distillation column (5) A method for recovering acrylic acid and acetic acid, comprising: supplying water to the top of a fourth distillation column to distill off the solvent, and recovering purified acetic acid from the bottom of the column. .

【0007】プロピレンまたはアクロレインを水蒸気の
存在下に固体触媒を用いて分子状酸素にて気相接触酸化
するとアクリル酸の他に、アクロレイン、酢酸やその他
のアルデヒド類が生成する。通常、反応生成ガスは冷却
及び/または水に吸収して粗アクリル酸水溶液として回
収される。用いる触媒の種類や反応条件によって異なる
が、酢酸はアクリル酸に対して約1〜15%程度含まれ
る。
When propylene or acrolein is oxidized in the gas phase with molecular oxygen using a solid catalyst in the presence of water vapor, acrolein, acetic acid and other aldehydes are produced in addition to acrylic acid. Usually, the reaction product gas is cooled and / or absorbed in water and recovered as a crude acrylic acid aqueous solution. Acetic acid is included in about 1 to 15% of acrylic acid, depending on the type of catalyst used and reaction conditions.

【0008】酢酸と水のそれぞれと共沸する溶媒として
は、ベンゼン、トルエン、キシレン、エチルベンゼン、
シクロヘキサン、シクロヘキセン、メチルシクロヘキサ
ン、ヘプタン、オクタン及びこれらの混合物が用いられ
る。
The solvents azeotropic with acetic acid and water include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, cyclohexene, methylcyclohexane, heptane, octane and mixtures thereof are used.

【0009】以下、本発明の実施態様を示す図1により
説明する。粗アクリル酸水溶液をライン5から、水と酢
酸のそれぞれと共沸する溶媒をライン7から第一蒸留塔
1に供給し共沸脱水蒸留を行う。塔頂より供給液に含ま
れる実質的に全ての水、一部の酢酸及び溶媒、さらには
少量のアクリル酸が同伴して留出する。留出液の溶媒層
は蒸留塔に還流し、水層はライン8から廃棄する。留出
した酢酸は水層に入り、廃棄される。その量は蒸留条件
にもよるが、第一蒸留塔に供給される量の25〜35%
程度になる。
FIG. 1 shows an embodiment of the present invention. A crude acrylic acid aqueous solution is supplied to the first distillation column 1 from a line 5 and a solvent azeotropic with water and acetic acid from a line 7 to perform azeotropic dehydration distillation. From the top of the column, substantially all of the water, part of acetic acid and the solvent contained in the feed, and a small amount of acrylic acid are distilled off. The solvent layer of the distillate is refluxed to the distillation column, and the aqueous layer is discarded from the line 8. Distilled acetic acid enters the aqueous layer and is discarded. The amount depends on the distillation conditions, but 25 to 35% of the amount supplied to the first distillation column.
About.

【0010】アクリル酸、酢酸および溶媒からなる塔底
液はライン6から第二蒸留塔2に供給し、更に第三蒸留
塔3の塔底液をライン12を経て循環、供給し、留出液
を一部還流しながら蒸留し、塔頂から第二蒸留塔2へ供
給した酢酸及び溶媒の実質的に全量をアクリル酸の一部
と共に留出させる。塔底液は酢酸及び溶媒を殆ど含まな
い精製アクリル酸であり、ライン10から抜き出し、必
要により更に精製して製品のアクリル酸とする。
A bottom solution comprising acrylic acid, acetic acid and a solvent is supplied from a line 6 to a second distillation column 2, and the bottom solution of a third distillation column 3 is circulated and supplied via a line 12, and a distillate Is distilled under partial reflux, and substantially all of the acetic acid and the solvent supplied from the top to the second distillation column 2 are distilled off together with a part of acrylic acid. The bottom liquid is purified acrylic acid containing almost no acetic acid and solvent and is withdrawn from the line 10 and, if necessary, further purified to obtain acrylic acid as a product.

【0011】アクリル酸、酢酸および溶媒からなる第二
蒸留塔の留出液はライン11から第三蒸留塔3に供給
し、留出液を一部還流しながら蒸留し、塔頂から実質的
にアクリル酸を含まない酢酸と溶媒をほぼ共沸組成に近
い組成で留出させる。留出液にアクリル酸が混入すると
アクリル酸がロスになるだけでなく酢酸の純度低下につ
ながるので出来るだけ留出させないようにする必要があ
る。アクリル酸、酢酸および溶媒からなる塔底液はライ
ン12から第一蒸留塔又は第二蒸留塔へ循環する。何れ
の塔へ循環するかは蒸留塔の分離能力、エネルギー使用
量等を勘案して適宜選択される。
The distillate of the second distillation column comprising acrylic acid, acetic acid and a solvent is supplied from a line 11 to a third distillation column 3, and the distillate is partially distilled under reflux, and substantially distilled from the top of the column. Acrylic acid-free acetic acid and a solvent are distilled off at a composition close to the azeotropic composition. If acrylic acid is mixed in the distillate, acrylic acid is lost as well as the purity of acetic acid is reduced. Therefore, it is necessary to avoid distilling as much as possible. A bottoms liquid composed of acrylic acid, acetic acid and a solvent is circulated from a line 12 to a first distillation column or a second distillation column. Which column to circulate is appropriately selected in consideration of the separation capacity of the distillation column, the amount of energy used, and the like.

【0012】酢酸と溶媒からなる第三蒸留塔の留出液は
ライン13から第四蒸留塔に供給し、溶媒を水と共沸除
去させるためにライン16から水を供給して蒸留を行
い、塔頂から第四蒸留塔に供給される実質的にすべての
溶媒と水を留出させ、水は蒸留塔へ還流し、溶媒はライ
ン17からライン7を経て第一蒸留塔へ循環する。塔底
のライン15から精製酢酸を取り出す。酢酸の濃度は9
5%以上、更には98%以上にすることが可能である。
The distillate from the third distillation column comprising acetic acid and a solvent is supplied to a fourth distillation column from a line 13, and water is supplied from a line 16 to azeotropically remove the solvent with water, and distillation is performed. Substantially all of the solvent and water fed to the fourth distillation column from the top are distilled off, the water is refluxed to the distillation column, and the solvent is circulated from line 17 through line 7 to the first distillation column. The purified acetic acid is taken out from the bottom line 15. Acetic acid concentration is 9
It can be 5% or more, and even 98% or more.

【0013】第二蒸留塔の塔底液である精製アクリル酸
に酢酸の混入するのを出来るだけ少なくするために、ラ
イン9で示す第一蒸留塔の塔底液の供給位置よりも下部
に溶媒を追加してもよい。また、第三蒸留塔において、
アクリル酸の留出を抑制しつつ溶媒の留出を促進するた
めに、ライン14で示すように回収した酢酸の一部を第
三蒸留塔に循環してもよい。
In order to minimize the incorporation of acetic acid into the purified acrylic acid, which is the bottom liquid of the second distillation column, the solvent is placed below the supply position of the bottom liquid of the first distillation column shown in line 9. May be added. In the third distillation column,
In order to promote the distillation of the solvent while suppressing the distillation of acrylic acid, a part of the collected acetic acid may be circulated to the third distillation column as shown by the line 14.

【0014】[0014]

【発明の効果】本発明の方法により、プロピレン及び/
又はアクロレインの酸化生成物から効率的に純度良くア
クリル酸及び酢酸を回収することができる。
According to the method of the present invention, propylene and / or
Alternatively, acrylic acid and acetic acid can be efficiently and efficiently recovered from the oxidation product of acrolein.

【0015】[0015]

【実施例】以下、本発明を実施例で詳細に説明するが、
本発明はこの実施例に限定されない。 実施例1 図1に示すフローでアクリル酸及び酢酸の回収を行う。
アクリル酸57.5wt%、酢酸2.9wt%を含む粗
アクリル酸水溶液を第一蒸留塔1にライン5から10.
9kg/Hで、同時に共沸溶媒としてトルエンをライン
7から0.58kg/Hで供給し、塔頂圧力160mm
Hg、塔頂温度46℃で蒸留を行う。留出液の溶媒層は
蒸留塔へ還流し、水層はライン8から4.4kg/Hで
抜き出す。水層にはトルエンが0.5%、酢酸が1.9
%、アクリル酸が0.05%含まれる。
Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to this embodiment. Example 1 Acrylic acid and acetic acid are collected according to the flow shown in FIG.
The crude acrylic acid aqueous solution containing 57.5% by weight of acrylic acid and 2.9% by weight of acetic acid was introduced into the first distillation column 1 through lines 5 to 10.
At the same time, toluene was supplied at 0.58 kg / H from line 7 as an azeotropic solvent at a pressure of 160 mm
Distillation is carried out at Hg and at an overhead temperature of 46 ° C. The solvent layer of the distillate is refluxed to the distillation column, and the aqueous layer is withdrawn from line 8 at 4.4 kg / H. 0.5% of toluene and 1.9 of acetic acid in the aqueous layer
% Acrylic acid and 0.05%.

【0016】塔底液はトルエンを7.9%、酢酸を3.
3%、アクリル酸を88.8%含み、ライン6を経由し
て第二蒸留塔2へ供給する。更に、トルエンを48.7
%、酢酸を18.0%、アクリル酸を33.1%を含む
第三蒸留塔の塔底液を第二蒸留塔に循環、供給し、塔頂
圧力80mmHg、塔頂温度52℃、還流比3.5で蒸
留を行う。トルエン67.7%、酢酸9.4wt%、ア
クリル酸22.8%を含む留出液を3.1kg/Hで、
塔底からは酢酸濃度が3000ppm以下の精製アクリ
ル酸を6.3kg/Hで得る。
The bottom liquid is 7.9% of toluene and 3.09% of acetic acid.
It contains 3% and 88.8% of acrylic acid and is supplied to the second distillation column 2 via the line 6. Further, toluene was added to 48.7.
%, Acetic acid 18.0%, acrylic acid 33.1%, the bottom liquid of the third distillation column is circulated and supplied to the second distillation column, the top pressure is 80 mmHg, the top temperature is 52 ° C., and the reflux ratio is Distill at 3.5. A distillate containing 67.7% of toluene, 9.4% by weight of acetic acid, and 22.8% of acrylic acid at 3.1 kg / H,
6.3 kg / H of purified acrylic acid having an acetic acid concentration of 3000 ppm or less is obtained from the bottom of the column.

【0017】第二蒸留塔の留出液をライン11を経て第
三蒸留塔へ供給し、塔頂圧力240mmHg、塔頂温度
71℃、還流比4.0で蒸留を行う。塔頂からトルエン
を70.5%、酢酸を29.2%を含み、アクリル酸が
300ppm以下の留出液を0.8kg/Hで、トルエ
ンを48.7%、酢酸を18.0%、アクリル酸を3
3.1%を含む塔底液を得る。塔底液はライン12をへ
て第二蒸留塔へ循環する。
The distillate from the second distillation column is supplied to the third distillation column via the line 11, and distillation is performed at a top pressure of 240 mmHg, a top temperature of 71 ° C., and a reflux ratio of 4.0. A distillate containing 70.5% of toluene and 29.2% of acetic acid from the top of the column, and a distillate containing 300 ppm or less of acrylic acid at 0.8 kg / H, 48.7% of toluene, 18.0% of acetic acid, 3 acrylic acid
A bottoms liquid containing 3.1% is obtained. The bottom liquid is circulated through line 12 to the second distillation column.

【0018】第三蒸留塔の留出液を第四蒸留塔へ供給
し、共沸剤として水0.14kg/Hをライン16から
塔頂に供給して塔頂圧力300mmHgで蒸留し、留出
液の水層は蒸留塔へ還流し、溶媒はライン17からライ
ン7を経て第一蒸留塔へ循環する。塔底のライン15か
ら水1.8wt%を含む純度98wt%以上の酢酸を
0.23kg/Hで回収する。なお、回収酢酸中のアク
リル酸は0.1wt%以下である。
The distillate from the third distillation column is supplied to the fourth distillation column, and 0.14 kg / H of water as an azeotropic agent is supplied from the line 16 to the top of the column to distill it at a top pressure of 300 mmHg. The aqueous layer of the liquid is refluxed to the distillation column, and the solvent is circulated from the line 17 to the first distillation column via the line 7. Acetic acid having a purity of 98% by weight or more and containing 1.8% by weight of water is recovered from the bottom line 15 at a rate of 0.23 kg / H. In addition, acrylic acid in the recovered acetic acid is 0.1 wt% or less.

【0019】実施例2 図1に示すフローで実施例1と同様にアクリル酸及び酢
酸の回収を行う。アクリル酸57.5wt%、酢酸2.
9wt%を含む粗アクリル酸水溶液を第一蒸留塔1にラ
イン5から10.9kg/Hで、同時に共沸溶媒として
トルエンをライン7から0.58kg/Hで供給し、塔
頂圧力160mmHg、塔頂温度46℃で蒸留を行う。
留出液の溶媒層は蒸留塔へ還流し、水層はライン8から
4.4kg/Hで抜き出す。水層にはトルエンが0.5
%、酢酸が1.9%、アクリル酸が0.05%含まれ
る。
Example 2 Acrylic acid and acetic acid are recovered in the same manner as in Example 1 according to the flow shown in FIG. Acrylic acid 57.5 wt%, acetic acid 2.
A crude acrylic acid aqueous solution containing 9 wt% is supplied to the first distillation column 1 from the line 5 at 10.9 kg / H, and at the same time, toluene is supplied as an azeotropic solvent from the line 7 at 0.58 kg / H. Distillation is carried out at a top temperature of 46 ° C.
The solvent layer of the distillate is refluxed to the distillation column, and the aqueous layer is withdrawn from line 8 at 4.4 kg / H. 0.5 parts toluene in water layer
%, Acetic acid 1.9% and acrylic acid 0.05%.

【0020】塔底液はトルエンを7.9%、酢酸を3.
3%、アクリル酸を88.8%含み、ライン6を経由し
て第二蒸留塔2へ、トルエンを57.4%、酢酸を3.
0%、アクリル酸を39.6%を含む第三蒸留塔の塔底
液を第二蒸留塔に循環、供給する。更に、ライン9から
トルエンを0.5kg/Hで供給し、塔頂圧力80mm
Hg、塔頂温度54℃、還流比3.2で蒸留を行う。ト
ルエン67.7%、酢酸9.4wt%、アクリル酸2
2.8%を含む留出液を3.1kg/Hで、塔底からは
酢酸濃度が1000ppm以下の精製アクリル酸を6.
3kg/Hで得る。
The bottom liquid is 7.9% toluene and acetic acid 3.
Containing 38.8% of acrylic acid and 88.8% of acrylic acid;
The bottom liquid of the third distillation column containing 0% and 39.6% of acrylic acid is circulated and supplied to the second distillation column. Further, toluene was supplied at a rate of 0.5 kg / H from a line 9 and a top pressure was 80 mm.
Distillation is carried out at Hg, a top temperature of 54 ° C. and a reflux ratio of 3.2. Toluene 67.7%, acetic acid 9.4 wt%, acrylic acid 2
3.1 kg / H of a distillate containing 2.8% and purified acrylic acid having an acetic acid concentration of 1000 ppm or less from the bottom of the column.
Obtained at 3 kg / H.

【0021】第二蒸留塔の留出液をライン11を経て第
三蒸留塔へ、更にライン14を経て酢酸を0.2kg/
Hで供給し、塔頂圧力240mmHg、塔頂温度69
℃、還流比5.3で蒸留を行う。塔頂からトルエンを6
9.3%、酢酸を30.5%を含み、アクリル酸が30
0ppm以下の留出液を1.5kg/Hで、トルエンを
57.4%、酢酸を3.0%、アクリル酸を39.6%
を含む塔底液を得た。塔底液はライン12をへて第二蒸
留塔へ循環する。
The distillate of the second distillation column is sent to the third distillation column via the line 11 and 0.2 kg / acetic acid is further fed via the line 14.
H, top pressure 240 mmHg, top temperature 69
The distillation is carried out at a temperature of 5.3 ° C. and a reflux ratio of 5.3. 6 toluene from top
9.3%, acetic acid 30.5%, acrylic acid 30
A distillate of 0 ppm or less is 1.5 kg / H, 57.4% of toluene, 3.0% of acetic acid, and 39.6% of acrylic acid.
Was obtained. The bottom liquid is circulated through line 12 to the second distillation column.

【0022】第三蒸留塔の留出液を第四蒸留塔へ供給
し、共沸剤として水0.26kg/Hをライン16から
塔頂に供給して塔頂圧力300mmHgで蒸留し、留出
液の水層は蒸留塔へ還流し、溶媒はライン17からライ
ン7を経て第一蒸留塔へ循環する。塔底のライン15か
ら水1.8wt%を含む純度98wt%以上の酢酸を
0.46kg/Hで回収した。なお、回収酢酸中のアク
リル酸は0.1wt%以下である。
The distillate from the third distillation column is supplied to the fourth distillation column, and 0.26 kg / H2 of water as an azeotropic agent is supplied from the line 16 to the top of the column to distill it at a top pressure of 300 mmHg. The aqueous layer of the liquid is refluxed to the distillation column, and the solvent is circulated from the line 17 to the first distillation column via the line 7. Acetic acid having a purity of 98% by weight or more and containing 1.8% by weight of water was recovered from line 15 at the bottom of the column at 0.46 kg / H. In addition, acrylic acid in the recovered acetic acid is 0.1 wt% or less.

【0023】実施例3 図1に示すフローでアクリル酸及び酢酸の回収を行う。
アクリル酸57.5wt%、酢酸2.9wt%を含む粗
アクリル酸水溶液を第一蒸留塔1にライン5から10.
9kg/Hで、同時に共沸溶媒としてトルエンをライン
7から0.57kg/Hで供給し、更にトルエンを5
5.8%、酢酸を13.8%、アクリル酸を30.3%
を含む第三蒸留塔の塔底液を第一蒸留塔に循環、供給
し、塔頂圧力160mmHg、塔頂温度46℃で蒸留を
行う。留出液の溶媒層は蒸留塔へ還流し、水層はライン
8から4.4kg/Hで抜き出す。水層にはトルエンが
0.4%、酢酸が2.0%、アクリル酸が0.05%含
まれる。
Example 3 Acrylic acid and acetic acid are recovered according to the flow shown in FIG.
The crude acrylic acid aqueous solution containing 57.5% by weight of acrylic acid and 2.9% by weight of acetic acid was introduced into the first distillation column 1 through lines 5 to 10.
At the same time, toluene was supplied at 0.57 kg / H from line 7 as an azeotropic solvent, and toluene was further added at 5 kg / H.
5.8%, acetic acid 13.8%, acrylic acid 30.3%
Is circulated and supplied to the first distillation column, and distillation is performed at a top pressure of 160 mmHg and a top temperature of 46 ° C. The solvent layer of the distillate is refluxed to the distillation column, and the aqueous layer is withdrawn from line 8 at 4.4 kg / H. The aqueous layer contains 0.4% toluene, 2.0% acetic acid, and 0.05% acrylic acid.

【0024】塔底液はトルエンを18.8%、酢酸を
5.7%、アクリル酸を75.5%含み、ライン6を経
由して第二蒸留塔2へ供給する。塔頂圧力80mmH
g、塔頂温度52℃、還流比4.0で蒸留を行う。トル
エン、酢酸、アクリル酸を含む留出液を2.1kg/H
で、塔底からは酢酸濃度が3000ppm以下の精製ア
クリル酸を6.3kg/Hで得る。
The bottom liquid contains 18.8% of toluene, 5.7% of acetic acid and 75.5% of acrylic acid, and is supplied to the second distillation column 2 via the line 6. Top pressure 80mmH
g, distillation at a top temperature of 52 ° C. and a reflux ratio of 4.0. 2.1 kg / H of distillate containing toluene, acetic acid and acrylic acid
Thus, 6.3 kg / H of purified acrylic acid having an acetic acid concentration of 3000 ppm or less is obtained from the bottom of the column.

【0025】第二蒸留塔の留出液をライン11を経て第
三蒸留塔へ供給し、塔頂圧力240mmHg、塔頂温度
71℃、還流比5.0で蒸留を行う。塔頂からトルエン
を70.5%、酢酸を29.2%を含み、アクリル酸が
300ppm以下の留出液を0.8kg/Hで、トルエ
ンを55.8%、酢酸を13.8%、アクリル酸を3
0.3%を含む塔底液を得る。塔底液はライン12をへ
て第一蒸留塔へ循環する。
The distillate from the second distillation column is supplied to the third distillation column via the line 11, and distillation is performed at a top pressure of 240 mmHg, a top temperature of 71 ° C., and a reflux ratio of 5.0. A distillate containing 70.5% of toluene, 29.2% of acetic acid, and a distillate containing 300 ppm or less of acrylic acid at 0.8 kg / H from the top of the column, 55.8% of toluene, 13.8% of acetic acid, 3 acrylic acid
A bottoms solution containing 0.3% is obtained. The bottom liquid is circulated through line 12 to the first distillation column.

【0026】第三蒸留塔の留出液を第四蒸留塔へ供給
し、共沸剤として水0.14kg/Hをライン16から
塔頂に供給して塔頂圧力300mmHgで蒸留し、留出
液の水層は蒸留塔へ還流し、溶媒はライン17からライ
ン7を経て第一蒸留塔へ循環する。塔底のライン15か
ら水1.8wt%を含む純度98wt%以上の酢酸を
0.23kg/Hで回収する。なお、回収酢酸中のアク
リル酸は0.1wt%以下である。
The distillate from the third distillation column is supplied to the fourth distillation column, and 0.14 kg / H of water as an azeotropic agent is supplied from the line 16 to the top of the column to distill it at a top pressure of 300 mmHg. The aqueous layer of the liquid is refluxed to the distillation column, and the solvent is circulated from the line 17 to the first distillation column via the line 7. Acetic acid having a purity of 98% by weight or more and containing 1.8% by weight of water is recovered from the bottom line 15 at a rate of 0.23 kg / H. In addition, acrylic acid in the recovered acetic acid is 0.1 wt% or less.

【0027】実施例4 図1に示すフローで実施例1と同様にアクリル酸及び酢
酸の回収を行う。アクリル酸56.3wt%、酢酸3.
2wt%を含む粗アクリル酸水溶液を第一蒸留塔1にラ
イン5から0.39kg/Hで、同時に共沸溶媒として
トルエンをライン7から0.03kg/Hで供給し、塔
頂圧力160mmHg、塔頂温度46℃で蒸留を行う。
留出液の溶媒層は蒸留塔へ還流し、水層はライン8から
0.16kg/Hで抜き出す。水層の酢酸は2.0%、
アクリル酸が0.3%以下である。
Example 4 Acrylic acid and acetic acid are recovered in the same manner as in Example 1 according to the flow shown in FIG. 56.3 wt% acrylic acid, acetic acid 3.
A crude acrylic acid aqueous solution containing 2 wt% is supplied to the first distillation column 1 from the line 5 at 0.39 kg / H, and at the same time, toluene is supplied as an azeotropic solvent from the line 7 at 0.03 kg / H. Distillation is carried out at a top temperature of 46 ° C.
The solvent layer of the distillate is refluxed to the distillation column, and the aqueous layer is withdrawn from line 8 at 0.16 kg / H. Acetic acid in the aqueous layer is 2.0%,
Acrylic acid is 0.3% or less.

【0028】塔底液0.26kg/Hはトルエンを1
1.3%、酢酸を3.6%、アクリル酸を77.3%含
み、ライン6を経由して第二蒸留塔2へ、トルエンを5
5.4%、酢酸を3.8%、アクリル酸を40.8%を
含む第三蒸留塔の塔底液0.077kg/Hを第二蒸留
塔に循環、供給する。更に、ライン9からトルエンを
0.015kg/Hで供給し、塔頂圧力80mmHg、
塔頂温度55℃、還流比4.0で蒸留を行う。トルエン
66.6%、酢酸9.1wt%、アクリル酸24.2%
を含む留出液を0.13kg/Hで、塔底からは酢酸濃
度が0.1%以下の精製アクリル酸を0.3kg/Hで
得る。
The bottom liquid of 0.26 kg / H contains 1 part of toluene.
1.3%, acetic acid 3.6%, acrylic acid 77.3%, toluene 5 to the second distillation column 2 via line 6
0.077 kg / H of the bottom liquid of the third distillation column containing 5.4%, 3.8% of acetic acid and 40.8% of acrylic acid is circulated and supplied to the second distillation column. Further, toluene was supplied at 0.015 kg / H from the line 9 and the pressure at the top of the column was 80 mmHg.
Distillation is performed at an overhead temperature of 55 ° C. and a reflux ratio of 4.0. Toluene 66.6%, acetic acid 9.1 wt%, acrylic acid 24.2%
Is obtained at 0.13 kg / H, and purified acrylic acid having an acetic acid concentration of 0.1% or less is obtained at 0.3 kg / H from the bottom of the column.

【0029】第二蒸留塔の留出液をライン11を経て第
三蒸留塔へ、更にライン14を経て酢酸を0.01kg
/Hで供給し、塔頂圧力240mmHg、塔頂温度70
℃、還流比7.0で蒸留を行う。塔頂からトルエンを6
9.9%、酢酸を30.0%を含み、アクリル酸が50
0ppm以下の留出液を0.063kg/Hで、トルエ
ンを55.4%、酢酸を3.8%、アクリル酸を40.
8%を含む塔底液を得る。塔底液はライン12をへて第
二蒸留塔へ循環する。
The distillate from the second distillation column is sent to the third distillation column via the line 11, and 0.01 kg of acetic acid is sent via the line 14.
/ H, overhead pressure 240 mmHg, overhead temperature 70
Distillation is carried out at a temperature of 70 ° C. and a reflux ratio of 7.0. 6 toluene from top
Contains 9.9%, 30.0% acetic acid, 50% acrylic acid
0.063 kg / H of a distillate of 0 ppm or less, 55.4% of toluene, 3.8% of acetic acid, and 40.
A bottoms liquid containing 8% is obtained. The bottom liquid is circulated through line 12 to the second distillation column.

【0030】第三蒸留塔の留出液を第四蒸留塔へ供給
し、共沸剤として水をライン16から塔頂に供給して塔
頂圧力300mmHgで蒸留し、留出液の水層は蒸留塔
へ還流し、溶媒はライン17からライン7を経て第一蒸
留塔へ循環する。塔底のライン15から水1.8wt%
を含む純度98wt%以上の酢酸を0.018kg/H
で得る。なお、回収酢酸中のアクリル酸は0.2wt%
以下である。
The distillate from the third distillation column is supplied to the fourth distillation column, water is supplied as an azeotropic agent from the line 16 to the top and distilled at a top pressure of 300 mmHg. Reflux to the distillation column and the solvent circulates from line 17 via line 7 to the first distillation column. 1.8 wt% of water from the bottom line 15
Acetic acid with a purity of 98 wt% or more containing 0.018 kg / H
Get in. Acrylic acid in the recovered acetic acid was 0.2 wt%
It is as follows.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明の実施態様を示す図である。FIG. 1 is a diagram showing an embodiment of the present invention.

【符号の説明】[Explanation of symbols]

1 第一蒸留塔 2 第二蒸留塔 3 第三蒸留塔 4 第四蒸留塔 5 第一蒸留塔への供給ライン 6 第一蒸留塔塔底液の抜き出しライン 7 溶媒の供給ライン 8 水の排出ライン 9 溶媒の追加供給ライン 10 第二蒸留塔塔底液(精製アクリル酸)の抜き出し
ライン 11 第三蒸留塔への供給ライン 12 第三蒸留塔塔底液の抜き出しライン 13 第四蒸留塔への供給ライン 14 酢酸の循環ライン 15 第四蒸留塔塔底液(精製酢酸)の抜き出しライン 16 水の供給ライン 17 溶媒の取り出しライン
DESCRIPTION OF SYMBOLS 1 1st distillation tower 2 2nd distillation tower 3 3rd distillation tower 4 4th distillation tower 5 Supply line to 1st distillation tower 6 Extraction line of bottom liquid of 1st distillation tower 7 Solvent supply line 8 Water discharge line 9 Additional supply line of solvent 10 Extraction line of bottom liquid (purified acrylic acid) of second distillation column 11 Supply line to third distillation column 12 Extraction line of bottom liquid of third distillation column 13 Supply to fourth distillation column Line 14 Circulation line of acetic acid 15 Fourth distillation tower bottom liquid (purified acetic acid) extraction line 16 Water supply line 17 Solvent extraction line

───────────────────────────────────────────────────── フロントページの続き (72)発明者 安田 稔 愛媛県新居浜市惣開町5番1号 住友化 学工業株式会社内 (56)参考文献 特開 平3−181440(JP,A) 特開 昭56−90034(JP,A) (58)調査した分野(Int.Cl.7,DB名) C07C 51/46 C07C 53/08 C07C 57/07 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Yasuda 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Industries, Ltd. (56) References JP-A-3-181440 (JP, A) JP-A Sho 56-90034 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 51/46 C07C 53/08 C07C 57/07

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 (1)プロピレン及び/又はアクロレイ
ンを分子状酸素で接触酸化して生成するガスを冷却及び
/又は水に吸収して得られる粗アクリル水溶液又は該水
溶液中のアルデヒド類をストリッピングにより除去した
水溶液及び酢酸と水のそれぞれと共沸する溶媒を第一蒸
留塔に供給し、(2)第一蒸留塔の塔頂より供給液に含
まれる実質的に全ての水を同伴する一部の酢酸と共に留
去し、酢酸及びアクリル酸を塔底液として抜き出して第
二蒸留塔に供給し、(3)第二蒸留塔にて残り全ての酢
酸とアクリル酸の一部を塔頂より留出させて第三蒸留塔
に供給し、塔底より精製アクリル酸を回収し、(4)第
三蒸留塔にて塔頂より実質的にアクリル酸を含まない酢
酸を留出させて第四蒸留塔に供給し、塔底より酢酸及び
アクリル酸を抜き出して第一蒸留塔又は第二蒸留塔に循
環し、(5)第四蒸留塔にて塔頂に水を供給して溶媒を
留去し、塔底より精製酢酸を回収することを特徴とする
アクリル酸及び酢酸の回収方法。
1. A method for stripping a crude acrylic aqueous solution obtained by cooling and / or absorbing a gas generated by catalytically oxidizing propylene and / or acrolein with molecular oxygen and / or water, or an aldehyde in the aqueous solution. (2) supplying the aqueous solution removed by the method and a solvent azeotropic with each of acetic acid and water to the first distillation column, and (2) entraining substantially all of the water contained in the feed liquid from the top of the first distillation column. Of acetic acid and acrylic acid are withdrawn as a bottom liquid and supplied to the second distillation column. (3) In the second distillation column, all remaining acetic acid and acrylic acid are partially removed from the top of the column. Distilled and supplied to the third distillation column, purified acrylic acid is recovered from the bottom of the column, and (4) acetic acid substantially free of acrylic acid is distilled from the top of the third distillation column to form the fourth Feed to distillation column and extract acetic acid and acrylic acid from bottom of column (5) supplying water to the top of the fourth distillation column to distill off the solvent, and recovering purified acetic acid from the bottom of the fourth distillation column. Method for recovering acrylic acid and acetic acid.
【請求項2】 第一蒸留塔の塔底液の第二蒸留塔への供
給位置よりも下部に溶媒を追加供給すること及び/又は
第四蒸留塔の塔底の精製酢酸の一部を第三蒸留塔に循環
することを特徴とする請求項1記載のアクリル酸及び酢
酸の回収方法。
2. A solvent is additionally supplied below a position at which a bottom liquid of the first distillation column is supplied to the second distillation column, and / or a part of the purified acetic acid at the bottom of the fourth distillation column is removed. 2. The method for recovering acrylic acid and acetic acid according to claim 1, wherein the acrylic acid and acetic acid are circulated through a tristillation column.
【請求項3】 溶媒がトルエンである請求項1又は請求
項2記載の酢酸の回収方法。
3. The method for recovering acetic acid according to claim 1, wherein the solvent is toluene.
【請求項4】 精製酢酸の濃度が95%以上である請求
項1又は請求項2記載の酢酸の回収方法。
4. The method for recovering acetic acid according to claim 1, wherein the concentration of the purified acetic acid is 95% or more.
JP22706392A 1992-08-26 1992-08-26 Recovery method of acrylic acid and acetic acid Expired - Fee Related JP3211396B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22706392A JP3211396B2 (en) 1992-08-26 1992-08-26 Recovery method of acrylic acid and acetic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22706392A JP3211396B2 (en) 1992-08-26 1992-08-26 Recovery method of acrylic acid and acetic acid

Publications (2)

Publication Number Publication Date
JPH0672944A JPH0672944A (en) 1994-03-15
JP3211396B2 true JP3211396B2 (en) 2001-09-25

Family

ID=16854952

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22706392A Expired - Fee Related JP3211396B2 (en) 1992-08-26 1992-08-26 Recovery method of acrylic acid and acetic acid

Country Status (1)

Country Link
JP (1) JP3211396B2 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273559B2 (en) 2004-10-28 2007-09-25 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7282151B2 (en) 2003-06-05 2007-10-16 Eastman Chemical Company Process for removal of impurities from mother liquor in the synthesis of carboxylic acid using pressure filtration
US7291270B2 (en) 2004-10-28 2007-11-06 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7351396B2 (en) 2003-06-05 2008-04-01 Eastman Chemical Company Extraction process for removal of impurities from an aqueous mixture
US7381386B2 (en) 2003-06-05 2008-06-03 Eastman Chemical Company Extraction process for removal of impurities from mother liquor in the synthesis of carboxylic acid
US7402694B2 (en) 2005-08-11 2008-07-22 Eastman Chemical Company Process for removal of benzoic acid from an oxidizer purge stream
US7410632B2 (en) 2003-06-05 2008-08-12 Eastman Chemical Company Extraction process for removal of impurities from mother liquor in the synthesis of carboxylic acid
US7452522B2 (en) 2003-06-05 2008-11-18 Eastman Chemical Company Extraction process for removal of impurities from an oxidizer purge stream in the synthesis of carboxylic acid
US7494641B2 (en) 2003-06-05 2009-02-24 Eastman Chemical Company Extraction process for removal of impurities from an oxidizer purge stream in the synthesis of carboxylic acid
US7556784B2 (en) 2004-09-02 2009-07-07 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids
US7569722B2 (en) 2005-08-11 2009-08-04 Eastman Chemical Company Process for removal of benzoic acid from an oxidizer purge stream
US7759516B2 (en) 2006-03-01 2010-07-20 Eastman Chemical Company Versatile oxidation byproduct purge process
US7863481B2 (en) 2006-03-01 2011-01-04 Eastman Chemical Company Versatile oxidation byproduct purge process
US7880032B2 (en) 2006-03-01 2011-02-01 Eastman Chemical Company Versatile oxidation byproduct purge process
US7888530B2 (en) 2004-09-02 2011-02-15 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids
US7897808B2 (en) 2006-03-01 2011-03-01 Eastman Chemical Company Versatile oxidation byproduct purge process
US7897810B2 (en) 2004-09-02 2011-03-01 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2122941B1 (en) * 1997-05-29 1999-07-01 Esteve Quimica Sa PROCEDURE FOR OBTAINING QUINAPRIL CHLORHYDRATE AND SOLVATES USEFUL FOR THE ISOLATION AND PURIFICATION OF QUINAPRIL CHLORHYDRATE.
KR100988313B1 (en) * 2007-01-19 2010-10-18 주식회사 엘지화학 Recovery method of acetic acid and acetic acid recovered by the method
EP2760598B1 (en) * 2011-09-27 2016-04-27 Rohm and Haas Company Method for cleaning a (meth) acrylate ester process tank
CN105753688B (en) * 2016-03-29 2018-01-05 黄河三角洲京博化工研究院有限公司 A kind of method of acrylic acid dimer in reduction acrylic acid
CN110088075A (en) * 2016-12-22 2019-08-02 伊士曼化工公司 Propionic acid and acrylic acid are separated via azeotropic distillation

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452522B2 (en) 2003-06-05 2008-11-18 Eastman Chemical Company Extraction process for removal of impurities from an oxidizer purge stream in the synthesis of carboxylic acid
US7282151B2 (en) 2003-06-05 2007-10-16 Eastman Chemical Company Process for removal of impurities from mother liquor in the synthesis of carboxylic acid using pressure filtration
US7494641B2 (en) 2003-06-05 2009-02-24 Eastman Chemical Company Extraction process for removal of impurities from an oxidizer purge stream in the synthesis of carboxylic acid
US7351396B2 (en) 2003-06-05 2008-04-01 Eastman Chemical Company Extraction process for removal of impurities from an aqueous mixture
US7381386B2 (en) 2003-06-05 2008-06-03 Eastman Chemical Company Extraction process for removal of impurities from mother liquor in the synthesis of carboxylic acid
US7470370B2 (en) 2003-06-05 2008-12-30 Eastman Chemical Company Process for removal of impurities from mother liquor in the synthesis of carboxylic acid using pressure filtration
US7410632B2 (en) 2003-06-05 2008-08-12 Eastman Chemical Company Extraction process for removal of impurities from mother liquor in the synthesis of carboxylic acid
US7888530B2 (en) 2004-09-02 2011-02-15 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids
US7556784B2 (en) 2004-09-02 2009-07-07 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids
US7959879B2 (en) 2004-09-02 2011-06-14 Grupo Petrotemex, S.A. De C.V. Optimized production of aromatic dicarboxylic acids
US7897810B2 (en) 2004-09-02 2011-03-01 Eastman Chemical Company Optimized production of aromatic dicarboxylic acids
US7273559B2 (en) 2004-10-28 2007-09-25 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7291270B2 (en) 2004-10-28 2007-11-06 Eastman Chemical Company Process for removal of impurities from an oxidizer purge stream
US7569722B2 (en) 2005-08-11 2009-08-04 Eastman Chemical Company Process for removal of benzoic acid from an oxidizer purge stream
US7402694B2 (en) 2005-08-11 2008-07-22 Eastman Chemical Company Process for removal of benzoic acid from an oxidizer purge stream
US7880032B2 (en) 2006-03-01 2011-02-01 Eastman Chemical Company Versatile oxidation byproduct purge process
US7863481B2 (en) 2006-03-01 2011-01-04 Eastman Chemical Company Versatile oxidation byproduct purge process
US7897808B2 (en) 2006-03-01 2011-03-01 Eastman Chemical Company Versatile oxidation byproduct purge process
US7759516B2 (en) 2006-03-01 2010-07-20 Eastman Chemical Company Versatile oxidation byproduct purge process
US7902395B2 (en) 2006-03-01 2011-03-08 Eastman Chemical Company Versatile oxidation byproduct purge process
US7956215B2 (en) 2006-03-01 2011-06-07 Grupo Petrotemex, S.A. De C.V. Versatile oxidation byproduct purge process

Also Published As

Publication number Publication date
JPH0672944A (en) 1994-03-15

Similar Documents

Publication Publication Date Title
JP3211396B2 (en) Recovery method of acrylic acid and acetic acid
JP3232678B2 (en) Acetic acid recovery method
EP0551111B1 (en) Process for purifying acrylic acid to high purity in the production of acrylic acid
US4140588A (en) Purification of propylene oxide by extractive distillation
US3433831A (en) Separation and purification of acrylic acid from acetic acid by solvent extraction and azeotropic distillation with a two component solvent-entrainer system
US3838020A (en) Process for purifying alkylene oxides by extractive distillation with a plural solvent mixture
JPH0840974A (en) Method for purifying acrylic acid
ZA200205200B (en) Process for the epoxidation of olefins.
JPH05246941A (en) Method for purifying acrylic acid in high yield in production of acrylic acid
JPH03291246A (en) Removal of impurity form mixture of cylcohexanone and cyclohexanol
JP3684197B2 (en) Method for separating and purifying an aqueous mixture consisting of the main components acetic acid and formic acid
KR100375780B1 (en) Method for recovering acrylic acid
JPS5944337A (en) Purification of methacrylic acid
JP2001515057A (en) Purification of the methanol stream
US3828099A (en) Process for separating methacrolein
JPH09151158A (en) Purification of acetic acid
JP6602490B2 (en) Method for recovering (meth) acrylic acid
JP2924563B2 (en) Purification method of ethyl acetate
JPS6310691B2 (en)
US4379025A (en) Water removal from butylene oxides by liquid extraction with selected extractive solvents
JPH0244296B2 (en)
JP3312566B2 (en) Method for separating acetic acid from acrylic acid
JP3832868B2 (en) Acrylic acid purification method
JPS60104034A (en) Recovery of methacrylic acid
CN109851591B (en) Method and apparatus for purifying alkylene oxide

Legal Events

Date Code Title Description
S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080719

Year of fee payment: 7

RD05 Notification of revocation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: R3D05

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090719

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100719

Year of fee payment: 9

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110719

Year of fee payment: 10

LAPS Cancellation because of no payment of annual fees