JPWO2003078015A1 - Purification device and purification method for easily polymerizable substances - Google Patents

Purification device and purification method for easily polymerizable substances Download PDF

Info

Publication number
JPWO2003078015A1
JPWO2003078015A1 JP2003576066A JP2003576066A JPWO2003078015A1 JP WO2003078015 A1 JPWO2003078015 A1 JP WO2003078015A1 JP 2003576066 A JP2003576066 A JP 2003576066A JP 2003576066 A JP2003576066 A JP 2003576066A JP WO2003078015 A1 JPWO2003078015 A1 JP WO2003078015A1
Authority
JP
Japan
Prior art keywords
easily polymerizable
polymerizable substance
polymerization inhibitor
purification
tower
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.)
Withdrawn
Application number
JP2003576066A
Other languages
Japanese (ja)
Inventor
宮崎　誠司
誠司 宮崎
靖弘 加峯
靖弘 加峯
芳行 谷口
芳行 谷口
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.)
Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Chemical Corp
Mitsubishi Rayon 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 Mitsubishi Chemical Corp, Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Chemical Corp
Publication of JPWO2003078015A1 publication Critical patent/JPWO2003078015A1/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

易重合性物質を蒸留して精製する際に、精製塔内の重合を防止するとともに、重合防止剤の精製塔からの留出を防止して品質の高い製品を得ることができる易重合性物質の精製装置および精製方法を提供する。易重合性物質を連続的に蒸留して精製する精製塔１１を具備する易重合性物質の精製装置１０において、第１の重合防止剤を精製塔１１内に導入する重合防止剤導入部２７が、精製塔１１の中間部２６に設けられている。重合防止剤導入部２７は、重合防止剤導入部２７から塔頂部１５までの理論段数Ｈ２が、０．１×Ｈ１≦Ｈ２＜Ｈ１を満たすような位置に設けられていることが好ましい。（ここで、Ｈ１は、易重合性物質導入部２５から塔頂部１５までの理論段数を示す。）When purifying the easily polymerizable substance by distillation, it prevents polymerization in the purification tower and prevents the polymerization inhibitor from distilling out of the purification tower to obtain a high-quality polymerizable substance. And a purification method for the same. In the purification apparatus for easily polymerizable substances 10 including the purification tower 11 for continuously distilling and purifying the easily polymerizable substances, the polymerization inhibitor introduction unit 27 for introducing the first polymerization inhibitor into the purification tower 11 is provided. , Provided in the intermediate section 26 of the purification tower 11. The polymerization inhibitor introduction section 27 is preferably provided at a position where the theoretical plate number H2 from the polymerization inhibitor introduction section 27 to the tower top 15 satisfies 0.1 × H1 ≦ H2 <H1. (Here, H1 indicates the theoretical plate number from the easily polymerizable substance introduction section 25 to the tower top section 15.)

Description

技術分野
本発明は、ビニル型重合性単量体などの易重合性物質の精製装置および精製方法に関する。
本出願は、日本国特許出願２００２−７９３６９号を基礎としており、その内容を本明細書に組み込む。
背景技術
ビニル型重合性単量体などの易重合性物質は、精製塔を用いて蒸留して精製する際に、精製塔内で非常に重合しやすいため、従来から、精製塔内に各種の重合防止剤を導入して蒸留精製する方法が提案されている。例えば、ハイドロキノンや、フェノール類、アミン類、フェノチアジン、Ｎ−オキシル型化合物などの重合防止剤を精製塔内に導入する方法が知られており、さらに上述した重合防止剤を数種類組み合わせて用いる方法などが提案されている。
重合防止剤を導入する位置としては、精製塔から排出した易重合性物質の蒸気を凝縮させる凝縮器、凝縮させた易重合性物質を精製塔に還流させる配管、精製塔の塔頂部などが提案されている。これらの方法は、精製塔内の重合防止に対しては非常に有効であった。
しかしながら、上述したいずれの重合防止剤の導入位置においても、一部が易重合性物質とともに精製塔から留出し、易重合性物質の製品中に重合防止剤が混入することがあった。その結果、重合防止剤が着色の原因となって易重合性物質の製品を着色させることがあった。また、重合防止剤が混入しているために、易重合性物質の製品を重合させて重合体とする際の易重合性物質の重合性が変化して、安定した重合体を得ることが困難となっていた。
また、重合防止剤の導入方法としては、精製塔に導入される未精製の易重合性物質に重合防止剤を添加する方法が提案されている。しかしながら、この方法では、重合防止剤の留出を防止できる反面、精製塔内の塔頂部近傍に重合物が生成することが観察され、精製塔内の重合を十分に抑制することができなかった。また、未精製の易重合性物質を精製塔内に導入する位置に重合防止剤を同時に導入する方法も考えられるが、この方法は、未精製の易重合性物質に重合防止剤を添加することと実質的に同じであり、精製塔内での重合を十分に抑制できなかった。
発明の開示
本発明は、前記事情を鑑みてなされたものであり、易重合性物質を蒸留して精製する際に、精製塔内の重合を防止するとともに、重合防止剤の精製塔からの必要以上の留出を抑制して品質の高い製品を得ることができる易重合性物質の精製装置および精製方法を提供することを目的とする。
本発明の易重合性物質の精製装置は、易重合性物質を連続的に蒸留して精製する精製塔を具備する易重合性物質の精製装置において、易重合性物質導入部が精製塔に設けられており、これとは別に第１の重合防止剤を精製塔内に導入する重合防止剤導入部が精製塔の中間部に設けられている。
ここで、精製塔の中間部とは、易重合性物質導入部から塔頂部までの部分のことである。また、易重合性物質導入部とは、未精製の易重合性物質を精製塔内に導入する部分のことである。
本発明の易重合性物質の精製装置において、精製塔塔頂部から易重合性物質導入部までの理論段数Ｈ１と精製塔塔頂部から重合防止剤導入部までの理論段数Ｈ２との関係が下記式（１）を満たす位置に易重合性物質導入部と重合防止剤導入部が設けられていることが好ましい。
０．１×Ｈ１≦Ｈ２＜Ｈ１ （１）
また、本発明の易重合性物質の精製装置において、前記易重合性物質が、（メタ）アクリル酸または（メタ）アクリル酸エステルであることが好ましい。
また、本発明の易重合性物質の精製方法は、易重合性物質導入部が精製塔に設けられており、これとは別に重合防止剤導入部が精製塔の中間部に設けられている精製塔を使用する易重合性物質の精製方法であって、易重合性物質導入部から易重合性物質を連続的に導入し、重合防止剤導入部から第１の重合防止剤を精製塔内に導入する段階を有する。
本発明の易重合性物質の精製方法において、精製塔が、精製塔塔頂部から易重合性物質導入部までの理論段数Ｈ１と精製塔塔頂部から重合防止剤導入部までの理論段数Ｈ２との関係が下記式（１）を満たす位置に易重合性物質導入部と重合防止剤導入部が設けられている精製塔であることが好ましい。
０．１×Ｈ１≦Ｈ２＜Ｈ１ （１）
また、本発明の易重合性物質の精製方法において、前記易重合性物質が、（メタ）アクリル酸または（メタ）アクリル酸エステルであることが好ましい。
本発明の易重合性物質の精製方法は、塔頂から取得した精製された易重合性物質に第１の重合防止剤と異なる第２の重合防止剤を添加する段階を更に有することができる。
発明を実施するための最良の形態
以下、本発明について詳細に述べる。
本発明の易重合性物質の精製装置を、図１を参照しながら説明する。この易重合性物質の精製装置１０は、易重合性物質を連続的に蒸留して精製する精製塔１１と、未精製の易重合性物質を精製塔１１に供給する易重合性物質供給管１２と、第１の重合防止剤を精製塔１１に供給する重合防止剤供給管１３と、精製塔１１から排出された易重合性物質蒸気を凝縮する凝縮器１４とを有して概略構成される。
さらに、精製塔１１には、蒸気化した易重合性物質を塔頂部１５から導出させる塔頂部導出管１６と、凝縮器１４から塔頂部１５に還流させる還流管１７と、精製塔１１の底部１８から易重合性物質を導出させる底部導出管１９と、底部導出管１９を介して送られた易重合性物質の一部を加熱するリボイラ２０と、リボイラ２０で発生した易重合性物質の蒸気を精製塔１１内に再導入する再導入管２１と、底部導出管１８を介して送られてきた易重合性物質の残りの一部を排出する不純物排出管２２とが取り付けられている。
また、凝縮器１４には、次工程に送液する次工程送液管２３が取り付けられている。
精製塔１１としては、易重合性物質を蒸留して精製できるものであれば特に制限されず、例えば、棚段塔型精製塔、充填塔型精製塔などが使用される。また、精製塔１１は、減圧可能とすることができる。
精製塔１１の適切な位置に易重合性物質供給管１２が接続された易重合性物質導入部２５が設けられる。易重合性物質導入部２５の位置は、易重合性物質中の分離したい不純物の種類や量により易重合性物質導入部２５から塔頂部１５までの理論段数Ｈ１を求め、決定することができる。すなわち、精製塔１１には、易重合性物質導入部２５から塔頂部１５までの間に、不純物を分離するのに必要な理論段数Ｈ１を有する棚段もしくは充填層が設けられる。
この精製塔１１には、精製塔１１内での易重合性物質の重合を防止することを目的として、その中間部２６に、重合防止剤供給管１３が接続され、第１の重合防止剤を精製塔１１内に導入する重合防止剤導入部２７が設けられる。重合防止剤導入部２７が設けられる位置は、精製塔１１の性能、処理する易重合性物質の液物性、精製塔１１の上下方向における重合防止剤分布のバランスなどにより、精製塔１１の中間部２６の範囲内で適宜決定されるが、重合防止剤導入部２７から塔頂部１５までの理論段数Ｈ２が下記式（１）を満たすような位置であることが好ましい。
０．１×Ｈ１≦Ｈ２＜Ｈ１ （１）
（ここで、Ｈ１は、易重合性物質導入部２５から精製塔１１の塔頂部１５までの理論段数を示す。）
特に、重合防止剤導入部２７は、重合防止剤導入部２７から精製塔塔頂部１５までの理論段数Ｈ２が下記式（２）を満たすような位置に設けられたことが好ましい。
０．２×Ｈ１≦Ｈ２≦０．７×Ｈ１ （２）
なお、０．１×Ｈ１＞Ｈ２を満たす位置に、重合防止剤導入部２７を設けた場合には、重合防止剤導入部２７から塔頂部１５までの理論段数が少なく、第１の重合防止剤が精製塔１１から排出されることがあり、Ｈ１≦Ｈ２を満たす位置（すなわち、易重合性物質導入部２５と同じ高さの位置またはそれより低い位置）に、重合防止剤導入部２７を設けた場合には、精製塔１１内の塔頂部１５近傍における重合防止剤の量が不足し、易重合性物質が重合することがある。
易重合性物質とは、重合性の官能基を有する物質のことである。易重合性物質としては、蒸留により精製できる易重合性物質であれば特に制限されないが、（メタ）アクリル酸または（メタ）アクリル酸エステルが好ましく、それらの中でも、（メタ）アクリル酸または（メタ）アクリル酸のメチルエステル、エチルエステル、ｎ−プロピルエステル、イソプロピルエステル、ｎ−ブチルエステル、イソブチルエステル、ｔ−ブチルエステル、２−エチルヘキシルエステル、シクロヘキシルエステル、Ｎ，Ｎ’−ジメチルアミノエチルエステルがさらに好ましい。
精製塔１１内に供給される第１の重合防止剤としては、公知の重合防止剤などを任意に使用することができ、易重合性物質の種類、精製塔１１の運転条件などにより適宜選択される。第１の重合防止剤の具体例としては、例えば、ハイドロキノン、ベンゾキノン、ハイドロキノンモノメチルエーテル、カテコール、２，４−ジメチル−６−ターシャリーブチルフェノール、２，６−ジターシャリーブチル−４−メチルフェノール等のフェノール類、Ｎ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミン、Ｎ，Ｎ−ジフェニル−パラ−フェニレンジアミン、Ｎ，Ｎ’−ジ−２−ナフチル−パラ−フェニレンジアミン等のアミン類、４−ヒドロキシ−２，２，４，４−テトラメチルピペリジン−Ｎ−オキシル等のＮ−オキシル型化合物、フェノチアジン等を挙げることができる。これらは、必要に応じて２種類以上組み合わせて使用することもできる。
上述した易重合性物質の精製装置では、第１の重合防止剤を導入する重合防止剤導入部２７が、精製塔の中間部２６に設けられており、第１の重合防止剤を、重合防止剤導入部２７から精製塔１１内に導入するので、精製塔１１内の殆どの部分に重合防止剤を存在させることができ、易重合性物質の重合を防止できる。それとともに、重合防止剤導入部２７は、塔頂部１５にはないので、塔頂部導出管１６から第１の重合防止剤が必要以上に留出することを抑制できる。そのため、重合防止剤が原因となって易重合性物質の製品を着色させることを防止できる。また、精製装置１０から留出した易重合性物質に新たに重合防止剤を添加することで、易重合性物質製品中の重合防止剤濃度を容易に一定にできるので、品質を向上させることができる。
また、重合防止剤導入部２７が、上記式（１）を満たす位置に設けられていれば、精製塔１１内での重合を防止できるとともに、導出管１６から離れているので、第１の重合防止剤が精製塔１１から必要以上に留出することをより確実に防止できる。
また、易重合性物質が（メタ）アクリル酸または（メタ）アクリル酸エステルの場合には、生産量が多いため、精製塔１１内での重合抑制効果および品質向上効果が絶大となる。
次に、本発明の易重合性物質の精製方法の一例について説明する。この易重合性物質の精製方法では、上述した易重合性物質の精製装置１０が使用されており、まず、未精製の易重合性物質を易重合性物質供給管１２によって、精製塔１１の易重合性物質導入部２５に導入する。それとともに、第１の重合防止剤を重合防止剤供給管１３によって、精製塔１１の重合防止剤導入部２７に導入する。その際、第１の重合防止剤を易重合性物質の溶液とすることが好ましい。第１の重合防止剤を易重合性物質の溶液とすると、精製塔１１内に容易に導入できる。
導入された液状の易重合性物質は、精製塔１１の底部１８へと流下し、底部１８に達した易重合性物質の一部は底部導出管１９を介してリボイラ２０に導入され、加熱されて蒸気化される。次いで、リボイラ２０によって蒸気化した易重合性物質は、再導入管２１を介して再び精製塔１１内に導入され、精製塔１１内を上昇する。このような、液状易重合性物質の流下および蒸気状易重合性物質の上昇に伴って、気液が接触し、気液での物質移動と熱移動とが繰り返されることで、塔頂部１５に低沸点成分である易重合性物質が濃縮される。
次いで、塔頂部１５に達した蒸気状の易重合性物質を、塔頂部導出管１６を介して凝縮器１４内に導入し、冷却し、凝縮して液化する。次いで、凝縮器１４で液化された易重合性物質の一部を、還流管１７を介して塔頂部１５に還流させて精製塔１１内を流下させるとともに、凝縮器１４で液化された易重合性物質の残りの一部を、製品とするために、次工程送液管２３によって次工程に送液する。
一方、精製塔１１の底部１８には、高沸点成分である不純物が濃縮されおり、この不純物は一部の易重合性物質とともに、底部導出管１８および不純物排出管２２を介して精製装置１０外に排出される。
さらに、精製装置１０から排出された易重合性物質に、輸送中あるいは貯蔵中の重合を防止させることを目的として、第２の重合防止剤を添加することがある。その場合、上述した精製方法では、精製塔１１内に導入する第１の重合防止剤に、第２の重合防止剤と異なるものを用いることができる。第１の重合防止剤と第２の重合防止剤とが異なるものであれば、目的に応じた重合防止剤を適切に使用することができる。例えば、易重合性物質の製品に添加される第２の重合防止剤では精製塔１１内の重合を抑制する効果が不十分なことがあるので、第１の重合防止剤として、重合抑制効果の高いものを使用することができる。また、重合抑制効果の高い第１の重合防止剤は着色の原因となるものが多く、第２の重合防止剤として、易重合性物質の製品を着色させにくいものを使用することができる。
なお、精製塔１１内の重合を抑制できれば、第１の重合防止剤に第２の重合防止剤と同じ種類のものを使用してもよいが、第１の重合防止剤が精製塔１１から排出されると、製品中の重合防止剤濃度を一定とするのが困難になり、製品の品質が低下するおそれがあるので、第１の重合防止剤と第２の重合防止剤が同じものであっても第１の重合防止剤を精製塔から必要以上に留出することは好ましくない。
上述した易重合性物質の精製方法では、精製装置１０を用いるので、精製塔１１内での易重合性物質の重合を防止できる。また、第１の重合防止剤は精製塔１１から必要以上に留出しないので、着色の原因となる重合防止剤の易重合性物質製品への混入を抑制できる。また、精製した易重合性物質に新たに第２の重合防止剤を添加することができるので、易重合性物質の製品中の重合防止剤濃度を容易に一定にできる。したがって、易重合性物質の製品の品質を向上させることができる。
実施例：
以下、実施例および比較例により本発明をより具体的に説明する。ただし、実施例は本発明の一態様を示すものであって、本発明を何ら制限するものではない。
なお、以下の実施例および比較例において、図１の易重合性物質の精製装置を使用した。また、重合防止剤の量は、液体クロマトグラフィ（定量限界０．５ｐｐｍ）により測定した。
（実施例１）
塔径１８００ｍｍで３０段の棚段を持つ精製塔１１（理論段数１０段）を用いて、易重合性物質であるメタクリル酸メチル（ＭＭＡ）の精製を行った。なお、精製に供した未精製ＭＭＡは、触媒とハイドロキノンの共存下、メタクリル酸とメタノールより合成し、あらかじめ未反応のメタクリル酸と過剰のメタノール、および水を取り除いたものである。
このＭＭＡの精製では、まず、塔頂部１５の圧力が２００ｈＰａの減圧条件下、上から数えて２０段目の棚段（易重合性物質導入部２５）に未精製ＭＭＡを毎時８２５０Ｌで導入した。それとともに、第１の重合防止剤であるＮ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミンを３．８質量％含有するＭＭＡを上から数えて１０段目の棚段（重合防止剤導入部２７）に毎時６．２Ｌで導入した。そして、ＭＭＡを流下させ、精製塔１１の底部１８からＭＭＡをリボイラ２０に送り、リボイラ２０でＭＭＡの蒸気を発生させ、その蒸気を精製塔１１内に再導入した。このようにして、気液間で物質移動と熱移動とを繰り返させて、塔頂部１５に低沸点成分であるＭＭＡを濃縮させた。
次いで、塔頂部導出管１６を介して導出されたＭＭＡ蒸気を、冷媒として４℃の水を用いた凝縮器１４に導入して凝縮した。次いで、凝縮されたＭＭＡの内、毎時１００００Ｌを還流管１７によって還流液として精製塔１１の塔頂部１５に戻し、残りの液を、次工程送液管２３を介して精製装置１０外に留出させた。
その結果、精製装置１０から留出液としてＭＭＡを毎時７９５０Ｌで得ることができた。留出したＭＭＡ中にはハイドロキノンは検出されなかった。また、ＭＭＡ製品を日光に４時間暴露したが、外観に変化はなく、Ｎ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミンは混入していなかった。
（実施例２）
塔径７００ｍｍで２０段の棚段を持つ精製塔１１（理論段数５．５段）を用いて、メタクリル酸ブチル（ＢＭＡ）の精製を行った。なお精製に供した未精製ＢＭＡは、触媒とＮ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミンの共存下、ＭＭＡとブタノールより合成し、あらかじめ過剰のＭＭＡとブタノールを取り除いたものである。
このＢＭＡの精製では、塔頂部１５の圧力が８０ｈＰａの減圧条件下、上から数えて１８段目の棚段（易重合性物質導入部２５）に未精製ＢＭＡを毎時１２００Ｌで導入した。それとともに、第１の重合防止剤である２，４−ジメチル−６−ターシャリーブチルフェノールを０．３重量％含むＢＭＡを、上から数えて５段目の棚段（重合防止剤導入部２７）に、毎時５Ｌで導入した。そして、ＢＭＡを流下させ、精製塔１１の底部１８からＢＭＡをリボイラ２０に送り、リボイラ２０でＢＭＡの蒸気を発生させ、その蒸気を精製塔１１内に再導入した。このようにして、気液間で物質移動と熱移動とを繰り返させて、塔頂部１５に低沸点成分であるＢＭＡを濃縮させた。
次いで、塔頂部導出管１６を介して導出させたＢＭＡ蒸気を、冷媒として４℃の水を用いた凝縮器１４に導入して凝縮した。次いで、凝縮されたＢＭＡの内、毎時１５０Ｌを還流管１７によって還流液として精製塔１１の塔頂部１５に戻し、残りの液を、次工程送液管２３を介して精製装置１０外に留出させた。
その結果、精製装置１０から留出液としてＢＭＡを毎時９５０Ｌで得ることができた。留出したＢＭＡ製品中には２，４−ジメチル−６−ターシャリーブチルフェノールは検出されなかった。また、製品を日光に４時間暴露したが、外観に変化はなかった。
（比較例１）
第１の重合防止剤としてＮ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミンを３．８重量％含有するＭＭＡを、凝縮器１４から精製塔１１の塔頂部１５に戻す還流管１７の還流液の中に毎時６．２Ｌで導入した以外は、実施例１と同じ方法でＭＭＡを精製した。
その結果、精製装置１０から留出液としてＭＭＡを毎時７４８０Ｌで得ることができた。留出したＭＭＡ中にはハイドロキノンは検出されなかった。しかし、ＭＭＡ製品を日光に１時間暴露したところ、無色透明の液が赤く着色し、留出したＭＭＡ中にＮ−イソプロピル−Ｎ’−フェニル−パラ−フェニレンジアミンが混入したことが判明した。
産業上の利用可能性
本発明によれば、第１の重合防止剤を導入する重合防止剤導入部が、精製塔の中間部に設けられており、その重合防止剤導入部から精製塔内に第１の重合防止剤を導入するので、精製塔内の殆どの部分に第１の重合防止剤を存在させることができ、精製塔内での易重合性物質の重合を防止できる。それとともに、重合防止剤導入部は、塔頂部にはないので、第１の重合防止剤を精製塔から必要以上に留出することを抑制でき、着色の原因となる重合防止剤の易重合性物質製品への混入を防止できる。また、新たに重合防止剤を添加することで、易重合性物質製品中の重合防止剤濃度を容易に一定にできるので、品質を向上させることができる。
【図面の簡単な説明】
図１は本発明の易重合性物質の精製装置の一例を示す模式図である。TECHNICAL FIELD The present invention relates to a purification apparatus and a purification method for easily polymerizable substances such as vinyl type polymerizable monomers.
This application is based on Japanese Patent Application No. 2002-79369, the contents of which are incorporated herein.
Background Art Since easily polymerizable substances such as vinyl-type polymerizable monomers are very easily polymerized in a purification tower when purified by distillation using a purification tower, various kinds of substances have been conventionally used in the purification tower. A method of purifying by distillation by introducing a polymerization inhibitor has been proposed. For example, a method of introducing a polymerization inhibitor such as hydroquinone, phenols, amines, phenothiazine, N-oxyl type compound into a purification tower is known, and a method using a combination of several polymerization inhibitors described above. Has been proposed.
Proposals for introducing the polymerization inhibitor include a condenser that condenses the vapor of the easily polymerizable substance discharged from the purification tower, a pipe for refluxing the condensed easily polymerizable substance to the purification tower, and the top of the purification tower. Has been. These methods were very effective for preventing polymerization in the purification tower.
However, at any of the above-described polymerization inhibitor introduction positions, a part of the polymerization inhibitor is distilled off from the purification tower together with the easily polymerizable substance, and the polymerization inhibitor may be mixed into the product of the easily polymerizable substance. As a result, the polymerization inhibitor may cause coloring, and the product of the easily polymerizable substance may be colored. In addition, since a polymerization inhibitor is mixed, it is difficult to obtain a stable polymer due to a change in the polymerizability of the easily polymerizable substance when the product of the easily polymerizable substance is polymerized into a polymer. It was.
As a method for introducing a polymerization inhibitor, a method of adding a polymerization inhibitor to an unpurified easily polymerizable substance introduced into a purification tower has been proposed. However, this method can prevent distillation of the polymerization inhibitor, but it has been observed that a polymer is formed in the vicinity of the top of the purification tower, and the polymerization in the purification tower cannot be sufficiently suppressed. . In addition, a method of simultaneously introducing a polymerization inhibitor at a position where an unpurified easily polymerizable substance is introduced into a purification tower is also conceivable, but this method involves adding a polymerization inhibitor to an unpurified easily polymerizable substance. The polymerization in the purification tower could not be sufficiently suppressed.
DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is necessary to prevent polymerization in the purification tower and to provide a polymerization inhibitor from the purification tower when purifying the easily polymerizable substance by distillation. It aims at providing the refinement | purification apparatus and purification method of an easily polymerizable substance which can suppress the above distillation and can obtain a high quality product.
An apparatus for purifying an easily polymerizable substance according to the present invention is an apparatus for purifying an easily polymerizable substance comprising a purification tower for continuously distilling and purifying an easily polymerizable substance. Apart from this, a polymerization inhibitor introduction part for introducing the first polymerization inhibitor into the purification tower is provided in the intermediate part of the purification tower.
Here, the intermediate part of the purification tower is a part from the easily polymerizable substance introduction part to the top of the tower. The easily polymerizable substance introduction part is a part for introducing an unpurified easily polymerizable substance into the purification tower.
In the apparatus for purifying an easily polymerizable substance of the present invention, the relationship between the theoretical plate number H1 from the top of the purification tower to the introduction of the easily polymerizable substance and the theoretical plate number H2 from the top of the purification tower to the introduction of the polymerization inhibitor is expressed by the following formula. It is preferable that an easily polymerizable substance introduction part and a polymerization inhibitor introduction part are provided at a position satisfying (1).
0.1 × H1 ≦ H2 <H1 (1)
Moreover, in the refiner | purifier of the easily polymerizable substance of this invention, it is preferable that the said easily polymerizable substance is (meth) acrylic acid or (meth) acrylic acid ester.
Further, in the purification method of the easily polymerizable substance of the present invention, the easily polymerizable substance introduction part is provided in the purification tower, and separately from this, the polymerization inhibitor introduction part is provided in the intermediate part of the purification tower. A method for purifying an easily polymerizable substance using a tower, wherein the easily polymerizable substance is continuously introduced from the easily polymerizable substance introduction part, and the first polymerization inhibitor is introduced into the purification tower from the polymerization inhibitor introduction part. Having a stage of introduction.
In the purification method of the easily polymerizable substance of the present invention, the purification tower has a theoretical plate number H1 from the top of the purification tower to the introduction of the easily polymerizable substance and a theoretical plate number H2 from the top of the purification tower to the introduction of the polymerization inhibitor. It is preferable that the purification tower is provided with an easily polymerizable substance introduction part and a polymerization inhibitor introduction part at a position where the relationship satisfies the following formula (1).
0.1 × H1 ≦ H2 <H1 (1)
Moreover, in the purification method of the easily polymerizable substance of the present invention, the easily polymerizable substance is preferably (meth) acrylic acid or (meth) acrylic acid ester.
The purification method of the easily polymerizable substance of the present invention may further include a step of adding a second polymerization inhibitor different from the first polymerization inhibitor to the purified easily polymerizable substance obtained from the tower top.
BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The apparatus for purifying an easily polymerizable substance of the present invention will be described with reference to FIG. This easily polymerizable substance purification apparatus 10 includes a purification column 11 that continuously distills and purifies easily polymerizable substances, and an easily polymerizable substance supply pipe 12 that supplies unpurified easily polymerizable substances to the purification tower 11. And a polymerization inhibitor supply pipe 13 that supplies the first polymerization inhibitor to the purification tower 11 and a condenser 14 that condenses the easily polymerizable substance vapor discharged from the purification tower 11. .
Further, the purification tower 11 includes a tower top outlet pipe 16 for leading the vaporized easily polymerizable substance from the tower top 15, a reflux pipe 17 for refluxing from the condenser 14 to the tower top 15, and a bottom 18 of the purification tower 11. A bottom outlet pipe 19 for deriving the easily polymerizable substance from the bottom, a reboiler 20 for heating a part of the easily polymerizable substance sent via the bottom outlet pipe 19, and a vapor of the easily polymerizable substance generated in the reboiler 20 A reintroduction pipe 21 that is reintroduced into the purification tower 11 and an impurity discharge pipe 22 that discharges the remaining part of the easily polymerizable substance that has been sent via the bottom outlet pipe 18 are attached.
Further, the condenser 14 is provided with a next-process liquid feeding pipe 23 for feeding the liquid to the next process.
The purification tower 11 is not particularly limited as long as it can purify an easily polymerizable substance by distillation. For example, a plate tower type purification tower, a packed tower type purification tower, or the like is used. Further, the purification tower 11 can be decompressed.
An easily polymerizable substance introduction unit 25 to which the easily polymerizable substance supply pipe 12 is connected is provided at an appropriate position of the purification tower 11. The position of the easily polymerizable substance introducing unit 25 can be determined by obtaining the theoretical plate number H1 from the easily polymerizable substance introducing unit 25 to the top 15 of the tower according to the type and amount of impurities to be separated in the easily polymerizable substance. That is, the purification column 11 is provided with a shelf or packed bed having the theoretical plate number H1 necessary for separating impurities between the easily polymerizable substance introduction unit 25 and the column top 15.
For the purpose of preventing the polymerization of the easily polymerizable substance in the purification tower 11, a polymerization inhibitor supply pipe 13 is connected to the intermediate column 26 of the purification tower 11, and the first polymerization inhibitor is added to the purification tower 11. A polymerization inhibitor introduction unit 27 for introduction into the purification tower 11 is provided. The position at which the polymerization inhibitor introduction unit 27 is provided depends on the performance of the purification column 11, the liquid physical properties of the easily polymerizable substance to be processed, the balance of the polymerization inhibitor distribution in the vertical direction of the purification column 11, and the like. Although it is appropriately determined within the range of 26, it is preferable that the theoretical plate number H2 from the polymerization inhibitor introduction part 27 to the tower top part 15 satisfies the following formula (1).
0.1 × H1 ≦ H2 <H1 (1)
(Here, H1 represents the number of theoretical plates from the easily polymerizable substance introduction part 25 to the top 15 of the purification tower 11).
In particular, the polymerization inhibitor introduction part 27 is preferably provided at a position where the theoretical plate number H2 from the polymerization inhibitor introduction part 27 to the purification tower top 15 satisfies the following formula (2).
0.2 × H1 ≦ H2 ≦ 0.7 × H1 (2)
In addition, when the polymerization inhibitor introduction part 27 is provided at a position satisfying 0.1 × H1> H2, the number of theoretical plates from the polymerization inhibitor introduction part 27 to the tower top part 15 is small, and the first polymerization inhibitor May be discharged from the purification tower 11, and a polymerization inhibitor introduction part 27 is provided at a position satisfying H1 ≦ H2 (that is, a position having the same height as or lower than the easily polymerizable substance introduction part 25). In this case, the amount of the polymerization inhibitor in the vicinity of the column top 15 in the purification column 11 may be insufficient, and the easily polymerizable substance may be polymerized.
An easily polymerizable substance is a substance having a polymerizable functional group. The easily polymerizable substance is not particularly limited as long as it is an easily polymerizable substance that can be purified by distillation, but (meth) acrylic acid or (meth) acrylic acid ester is preferable, and among these, (meth) acrylic acid or (meta ) Acrylic acid methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, t-butyl ester, 2-ethylhexyl ester, cyclohexyl ester, N, N'-dimethylaminoethyl ester preferable.
As the first polymerization inhibitor supplied into the purification column 11, a known polymerization inhibitor or the like can be arbitrarily used, and is appropriately selected depending on the kind of the easily polymerizable substance, the operating conditions of the purification column 11, and the like. The Specific examples of the first polymerization inhibitor include hydroquinone, benzoquinone, hydroquinone monomethyl ether, catechol, 2,4-dimethyl-6-tertiary butylphenol, 2,6-ditertiary butyl-4-methylphenol, and the like. Amines such as phenols, N-isopropyl-N′-phenyl-para-phenylenediamine, N, N-diphenyl-para-phenylenediamine, N, N′-di-2-naphthyl-para-phenylenediamine, 4- Examples thereof include N-oxyl type compounds such as hydroxy-2,2,4,4-tetramethylpiperidine-N-oxyl, phenothiazine and the like. These may be used in combination of two or more as required.
In the purification apparatus for the easily polymerizable substance described above, the polymerization inhibitor introduction part 27 for introducing the first polymerization inhibitor is provided in the intermediate part 26 of the purification tower, and the first polymerization inhibitor is used as the polymerization inhibitor. Since it introduce | transduces in the refinement | purification tower 11 from the agent introduction part 27, a polymerization inhibitor can be made to exist in most parts in the refinement | purification tower 11, and superposition | polymerization of an easily polymerizable substance can be prevented. At the same time, since the polymerization inhibitor introduction part 27 is not provided in the tower top part 15, it is possible to suppress the first polymerization inhibitor from being distilled more than necessary from the tower top outlet pipe 16. Therefore, it is possible to prevent the product of the easily polymerizable substance from being colored due to the polymerization inhibitor. Also, by adding a new polymerization inhibitor to the easily polymerizable substance distilled from the purification apparatus 10, the concentration of the polymerization inhibitor in the easily polymerizable substance product can be easily made constant, so that the quality can be improved. it can.
Further, if the polymerization inhibitor introduction part 27 is provided at a position satisfying the above formula (1), the polymerization in the purification tower 11 can be prevented and the separation from the outlet pipe 16 is made. It can prevent more reliably that an inhibitor distills from the purification tower 11 more than necessary.
Further, when the easily polymerizable substance is (meth) acrylic acid or (meth) acrylic acid ester, since the production amount is large, the polymerization suppression effect and the quality improvement effect in the purification tower 11 become enormous.
Next, an example of the purification method of the easily polymerizable substance of the present invention will be described. In the purification method of the easily polymerizable substance, the above-described purification apparatus 10 for the easily polymerizable substance is used. First, the unpurified easily polymerizable substance is easily removed from the purification column 11 by the easily polymerizable substance supply pipe 12. It introduces into the polymerizable substance introduction part 25. At the same time, the first polymerization inhibitor is introduced into the polymerization inhibitor introduction section 27 of the purification tower 11 through the polymerization inhibitor supply pipe 13. At that time, it is preferable that the first polymerization inhibitor is a solution of an easily polymerizable substance. If the first polymerization inhibitor is a solution of an easily polymerizable substance, it can be easily introduced into the purification tower 11.
The introduced liquid easily polymerizable substance flows down to the bottom 18 of the purification tower 11, and a part of the easily polymerizable substance reaching the bottom 18 is introduced into the reboiler 20 through the bottom outlet pipe 19 and heated. Vaporized. Next, the easily polymerizable substance vaporized by the reboiler 20 is again introduced into the purification tower 11 through the reintroduction pipe 21 and rises in the purification tower 11. As the liquid easily polymerizable substance flows down and the vaporized easily polymerizable substance rises, the gas and liquid come into contact with each other, and the mass transfer and heat transfer in the gas and liquid are repeated. The easily polymerizable substance which is a low boiling point component is concentrated.
Next, the vapor-like easily polymerizable substance that has reached the tower top 15 is introduced into the condenser 14 via the tower top outlet pipe 16, cooled, condensed and liquefied. Next, a part of the easily polymerizable substance liquefied by the condenser 14 is refluxed to the tower top 15 via the reflux pipe 17 to flow down in the purification tower 11, and the easily polymerizable substance liquefied by the condenser 14 is circulated. In order to make the remaining part of the substance into a product, it is fed to the next process through the next process feed pipe 23.
On the other hand, impurities that are high-boiling components are concentrated in the bottom 18 of the purification tower 11, and these impurities together with some easily polymerizable substances are added to the outside of the purification apparatus 10 via the bottom outlet pipe 18 and the impurity discharge pipe 22. To be discharged.
Furthermore, a second polymerization inhibitor may be added to the easily polymerizable substance discharged from the purification apparatus 10 for the purpose of preventing polymerization during transportation or storage. In that case, in the purification method described above, the first polymerization inhibitor introduced into the purification tower 11 can be different from the second polymerization inhibitor. If the first polymerization inhibitor and the second polymerization inhibitor are different, a polymerization inhibitor according to the purpose can be appropriately used. For example, the second polymerization inhibitor added to the product of the easily polymerizable substance may have an insufficient effect of suppressing the polymerization in the purification tower 11. Higher ones can be used. Moreover, the 1st polymerization inhibitor with a high polymerization inhibitory effect has many which causes coloring, and what can hardly color the product of an easily polymerizable substance can be used as a 2nd polymerization inhibitor.
If the polymerization in the purification tower 11 can be suppressed, the same kind of the second polymerization inhibitor as the first polymerization inhibitor may be used, but the first polymerization inhibitor is discharged from the purification tower 11. If this is done, it will be difficult to keep the concentration of the polymerization inhibitor in the product constant, and the quality of the product may be reduced. Therefore, the first polymerization inhibitor and the second polymerization inhibitor are the same. However, it is not preferable to distill the first polymerization inhibitor from the purification tower more than necessary.
In the purification method of the easily polymerizable substance described above, since the purification apparatus 10 is used, the polymerization of the easily polymerizable substance in the purification tower 11 can be prevented. In addition, since the first polymerization inhibitor does not distill from the purification tower 11 more than necessary, mixing of the polymerization inhibitor that causes coloring into the easily polymerizable substance product can be suppressed. Moreover, since a 2nd polymerization inhibitor can be newly added to the refine | purified easily polymerizable substance, the polymerization inhibitor density | concentration in the product of a easily polymerizable substance can be made constant easily. Therefore, the quality of products of easily polymerizable substances can be improved.
Example:
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, an Example shows one aspect | mode of this invention and does not restrict | limit this invention at all.
In the following Examples and Comparative Examples, the easily polymerizable substance purification apparatus of FIG. 1 was used. The amount of the polymerization inhibitor was measured by liquid chromatography (quantitative limit 0.5 ppm).
(Example 1)
Purification of methyl methacrylate (MMA), which is an easily polymerizable substance, was performed using a purification tower 11 (10 theoretical plates) having a tower diameter of 1800 mm and 30 stages. The unpurified MMA subjected to purification was synthesized from methacrylic acid and methanol in the presence of a catalyst and hydroquinone, and unreacted methacrylic acid, excess methanol and water were removed in advance.
In the purification of MMA, unpurified MMA was first introduced at a rate of 8250 L per hour into the 20th shelf (easily polymerizable substance introduction part 25) counted from above under the reduced pressure condition where the pressure at the top 15 of the column was 200 hPa. At the same time, MMA containing 3.8% by mass of N-isopropyl-N′-phenyl-para-phenylenediamine as the first polymerization inhibitor was counted from the top to the 10th shelf (polymerization inhibitor introduction part). 27) was introduced at 6.2 L per hour. Then, MMA was caused to flow down, MMA was sent from the bottom 18 of the purification tower 11 to the reboiler 20, MMA vapor was generated by the reboiler 20, and the vapor was reintroduced into the purification tower 11. In this way, mass transfer and heat transfer were repeated between the gas and liquid, and MMA, which is a low boiling point component, was concentrated at the tower top 15.
Next, the MMA vapor led out through the tower top outlet pipe 16 was introduced into the condenser 14 using water at 4 ° C. as a refrigerant and condensed. Next, 10000 L / hour of the condensed MMA is returned to the top 15 of the purification tower 11 through the reflux pipe 17 as a reflux liquid, and the remaining liquid is distilled out of the purification apparatus 10 through the next-stage liquid feeding pipe 23. I let you.
As a result, MMA was obtained as a distillate from the purification apparatus 10 at 7950 L / hour. Hydroquinone was not detected in the distilled MMA. Moreover, although the MMA product was exposed to sunlight for 4 hours, the appearance did not change, and N-isopropyl-N′-phenyl-para-phenylenediamine was not mixed.
(Example 2)
Purification of butyl methacrylate (BMA) was performed using a purification column 11 (theoretical plate number 5.5 plate) having a tower diameter of 700 mm and 20 plates. The unpurified BMA subjected to purification was synthesized from MMA and butanol in the presence of a catalyst and N-isopropyl-N′-phenyl-para-phenylenediamine, and excess MMA and butanol were removed in advance.
In this purification of BMA, unpurified BMA was introduced into the 18th shelf (easily polymerizable substance introduction part 25) at 1200 L / hr under the reduced pressure condition where the pressure at the column top 15 was 80 hPa. At the same time, BMA containing 0.3% by weight of 2,4-dimethyl-6-tertiary butylphenol which is the first polymerization inhibitor is counted from the top as the fifth shelf (polymerization inhibitor introduction part 27). Introduced at 5 liters per hour. Then, BMA was caused to flow down, BMA was sent from the bottom 18 of the purification tower 11 to the reboiler 20, BMA vapor was generated by the reboiler 20, and the vapor was reintroduced into the purification tower 11. In this way, mass transfer and heat transfer were repeated between the gas and liquid, and BMA, which is a low boiling point component, was concentrated at the tower top 15.
Next, the BMA vapor led out through the tower top outlet pipe 16 was introduced into the condenser 14 using water at 4 ° C. as a refrigerant and condensed. Next, 150 L / hour of the condensed BMA is returned to the top 15 of the purification tower 11 as a reflux liquid through the reflux pipe 17, and the remaining liquid is distilled out of the purification apparatus 10 through the next-stage liquid feed pipe 23. I let you.
As a result, BMA could be obtained from the purification apparatus 10 as a distillate at 950 L / hour. 2,4-Dimethyl-6-tertiary butylphenol was not detected in the distilled BMA product. The product was exposed to sunlight for 4 hours, but the appearance did not change.
(Comparative Example 1)
Refluxed liquid in the reflux pipe 17 returns MMA containing 3.8% by weight of N-isopropyl-N′-phenyl-para-phenylenediamine as the first polymerization inhibitor from the condenser 14 to the top 15 of the purification column 11. MMA was purified in the same manner as in Example 1 except that it was introduced into the flask at 6.2 L / hour.
As a result, MMA was obtained as a distillate from the purification apparatus 10 at 7480 L / hour. Hydroquinone was not detected in the distilled MMA. However, when the MMA product was exposed to sunlight for 1 hour, the colorless and transparent liquid turned red and it was found that N-isopropyl-N′-phenyl-para-phenylenediamine was mixed in the distilled MMA.
Industrial Applicability According to the present invention, the polymerization inhibitor introduction part for introducing the first polymerization inhibitor is provided in the intermediate part of the purification tower, and the polymerization inhibitor introduction part is provided in the purification tower. Since the first polymerization inhibitor is introduced, the first polymerization inhibitor can be present in most parts of the purification tower, and the polymerization of the easily polymerizable substance in the purification tower can be prevented. At the same time, since the polymerization inhibitor introduction part is not at the top of the column, it is possible to suppress the first polymerization inhibitor from being distilled more than necessary from the purification tower, and the easy polymerization of the polymerization inhibitor that causes coloring. Mixing into a substance product can be prevented. Further, by newly adding a polymerization inhibitor, the concentration of the polymerization inhibitor in the easily polymerizable substance product can be easily made constant, so that the quality can be improved.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of a purification apparatus for easily polymerizable substances of the present invention.

Claims (7)

易重合性物質を連続的に蒸留して精製する精製塔を具備する易重合性物質の精製装置において、易重合性物質導入部が精製塔に設けられており、これとは別に第１の重合防止剤を精製塔内に導入する重合防止剤導入部が精製塔の中間部に設けられている易重合性物質の精製装置。In a purification apparatus for easily polymerizable substances comprising a purification tower for continuously purifying easily polymerizable substances by distillation, an easily polymerizable substance introduction part is provided in the purification tower. An apparatus for purifying an easily polymerizable substance, wherein a polymerization inhibitor introduction part for introducing an inhibitor into the purification tower is provided in an intermediate part of the purification tower. 請求項１に記載の易重合性物質の精製装置であって、精製塔塔頂部から易重合性物質導入部までの理論段数Ｈ１と精製塔塔頂部から重合防止剤導入部までの理論段数Ｈ２との関係が下記式（１）を満たす位置に易重合性物質導入部と重合防止剤導入部が設けられている易重合性物質の精製装置。
０．１×Ｈ１≦Ｈ２＜Ｈ１ （１）The apparatus for purifying an easily polymerizable substance according to claim 1, wherein the theoretical plate number H1 from the top of the purification tower to the introduction of the easily polymerizable substance and the theoretical plate number H2 from the top of the purification tower to the introduction of the polymerization inhibitor are An easily polymerizable substance purification apparatus in which an easily polymerizable substance introduction part and a polymerization inhibitor introduction part are provided at a position where the relationship satisfies the following formula (1).
0.1 × H1 ≦ H2 <H1 (1) 請求項１または２に記載の易重合性物質の精製装置であって、前記易重合性物質が、（メタ）アクリル酸または（メタ）アクリル酸エステルである易重合性物質の精製装置。The apparatus for purifying easily polymerizable substances according to claim 1 or 2, wherein the easily polymerizable substance is (meth) acrylic acid or (meth) acrylic acid ester. 易重合性物質導入部が精製塔に設けられており、これとは別に重合防止剤導入部が精製塔の中間部に設けられている精製塔を使用する易重合性物質の精製方法であって、易重合性物質導入部から易重合性物質を連続的に導入し、重合防止剤導入部から第１の重合防止剤を精製塔内に導入する段階を有する易重合性物質の精製方法。A method for purifying an easily polymerizable substance using a purification tower in which an easily polymerizable substance introduction part is provided in a purification tower and a polymerization inhibitor introduction part is provided in an intermediate part of the purification tower. A method for purifying an easily polymerizable substance, comprising the steps of continuously introducing an easily polymerizable substance from the easily polymerizable substance introducing section and introducing a first polymerization inhibitor into the purification tower from the polymerization inhibitor introducing section. 請求項４に記載の易重合性物質の精製方法であって、精製塔が、精製塔塔頂部から易重合性物質導入部までの理論段数Ｈ１と精製塔塔頂部から重合防止剤導入部までの理論段数Ｈ２との関係が下記式（１）を満たす位置に易重合性物質導入部と重合防止剤導入部が設けられている精製塔である易重合性物質の精製方法。
０．１×Ｈ１≦Ｈ２＜Ｈ１ （１）5. The method for purifying an easily polymerizable substance according to claim 4, wherein the purifying tower includes a theoretical plate number H1 from the top of the purifying tower to the easily polymerizable substance introducing part and from the top of the purifying tower to the polymerization inhibitor introducing part. A method for purifying a readily polymerizable substance, which is a purification tower in which a readily polymerizable substance introducing part and a polymerization inhibitor introducing part are provided at a position where the relationship with the theoretical plate number H2 satisfies the following formula (1).
0.1 × H1 ≦ H2 <H1 (1) 請求項４または５に記載の易重合性物質の精製方法であって、前記易重合性物質が、（メタ）アクリル酸または（メタ）アクリル酸エステルである易重合性物質の精製方法。The method for purifying an easily polymerizable substance according to claim 4 or 5, wherein the easily polymerizable substance is (meth) acrylic acid or (meth) acrylic acid ester. 請求項４〜６に記載の易重合性物質の精製方法であって、塔頂から取得した精製された易重合性物質に第１の重合防止剤と異なる第２の重合防止剤を添加する段階を更に有する易重合性物質の精製方法。It is a purification method of the easily polymerizable substance of Claims 4-6, Comprising: The step which adds the 2nd polymerization inhibitor different from a 1st polymerization inhibitor to the purified easily polymerizable substance acquired from the tower top A method for purifying an easily polymerizable substance further comprising:
JP2003576066A 2002-03-20 2003-03-19 Purification device and purification method for easily polymerizable substances Withdrawn JPWO2003078015A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002079369 2002-03-20
JP2002079369 2002-03-20
PCT/JP2003/003319 WO2003078015A1 (en) 2002-03-20 2003-03-19 Apparatus and method for purifying easily polymerizable substance

Publications (1)

Publication Number Publication Date
JPWO2003078015A1 true JPWO2003078015A1 (en) 2005-07-14

Family

ID=28035651

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2003576066A Withdrawn JPWO2003078015A1 (en) 2002-03-20 2003-03-19 Purification device and purification method for easily polymerizable substances

Country Status (2)

Country Link
JP (1) JPWO2003078015A1 (en)
WO (1) WO2003078015A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3787261B2 (en) * 1999-04-16 2006-06-21 株式会社日本触媒 Method for preventing polymerization of easily polymerizable compounds
JP2001131116A (en) * 1999-11-08 2001-05-15 Nippon Shokubai Co Ltd Method of distillation for liquid including material liable to polymerize
JP2002053871A (en) * 2000-08-07 2002-02-19 Nippon Zeon Co Ltd Method for separating and purifying conjugated dienes and apparatus for separating and purification
JP4848112B2 (en) * 2001-09-28 2011-12-28 住友化学株式会社 Distillation method of easily polymerizable substances

Also Published As

Publication number Publication date
WO2003078015A1 (en) 2003-09-25

Similar Documents

Publication Publication Date Title
JP5892729B2 (en) Method for producing high purity methacrylic acid
JP6064014B2 (en) Polymerization and soil control methods in acrylic acid and acrylate processes
CN101337888A (en) Method for preparing butanediol dimethylacrylate
RU2374221C2 (en) Method of continuous production of alkylamino(meth)acrylamides
EP1749812A1 (en) Polymerization inhibitor, composition containing the same and process for producing easily polymerizable compound with the polymerization inhibitor
SK21497A3 (en) Process for preparing refined acrylic acid esters
KR20100093031A (en) Method and plant for purifying unsaturated compounds
SA08290304B1 (en) Method for producing (meth)acrylic acid
TWI778001B (en) Process for isolating pure 2-ethylhexyl acrylate or pure 2-propylheptyl acrylate from the corresponding crude alkyl acrylate by distillation
TWI764965B (en) Process for isolating pure butyl acrylate from crude butyl acrylate by distillation, where butyl is n-butyl or isobutyl
JP2907043B2 (en) Method for decomposing Michael adduct of acrylic acid or methacrylic acid ester
TW201043598A (en) Composition stabilized for a purification and process for purifying and for preparing hydroxyalkyl(meth)acrylates
JP3551621B2 (en) Method for producing (meth) acrylic acid ester
JPWO2003078015A1 (en) Purification device and purification method for easily polymerizable substances
TWI771353B (en) Process for isolating pure tert-butyl (meth)acrylate from crude tert-butyl (meth)acrylate by distillation
JP2024506199A (en) Improved method for producing high purity alkyl acrylates
WO2009084320A1 (en) Α-hydroxymethyl acrylate compounds and method of producing the same
JP2022533439A (en) Improved method for producing high purity alkyl acrylates
US20080128263A1 (en) Process for producing acrylic acid
JP6844106B2 (en) Distillation method of unsaturated carboxylic acid silyl ester
JP2534323B2 (en) Method for stabilizing methyl methacrylate
JP4687843B2 (en) Method for purifying methacrylic acid
US11261150B2 (en) Method for purifying (meth)acrylic esters
JP3312638B2 (en) (Meth) acrylic acid polymerization inhibitor composition and method for preventing (meth) acrylic acid polymerization using the composition
JP2002155021A (en) Polymerization inhibitor composition for vinyl monomer and method for producing high-purity (meth)acrylic acid

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 20060606