JPS62106044A - Recovery of methacrylic acid - Google Patents
Recovery of methacrylic acidInfo
- Publication number
- JPS62106044A JPS62106044A JP24293285A JP24293285A JPS62106044A JP S62106044 A JPS62106044 A JP S62106044A JP 24293285 A JP24293285 A JP 24293285A JP 24293285 A JP24293285 A JP 24293285A JP S62106044 A JPS62106044 A JP S62106044A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- boiling components
- polymer
- distillation
- organic solvent
- 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
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の回収法に関する。ざら（こ詳し
くはタメクｌ）ル酸を蒸留分離した缶残液から、メック
１ノル酸を回収する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for recovering methacrylic acid. This invention relates to a method for recovering MEC 1-noric acid from the residual liquid obtained by distilling and separating Zara (more specifically, Tameclic acid) acid.
〔従来の技術及び発明が解決しようとする問題点インブ
チレン、第３級ブタノール、メタクロレインまたはイン
ブチルアルテヒトを水蒸気の存在下に分子状酸素で１段
または２段の反応で接触酸化しで得られる、メタクリル
酸は抽出および蒸留などの通常の精製手段で高純度の製
品とすることができる。しかし、最終的にメタクリル酸
を得るまでにはメタクリル酸水溶液からアルデヒド類お
よびケトン類等の軽沸点成分の除去、抽出処理復の溶剤
回収、メタクリル酸よりも低沸点の酸の分離そして高沸
点成分の分離と幾度となく加熱状態に曝される。そのた
め各工程の処理はフェノチアジン、ヘンシフエッチアジ
ン、ハイドロキノン、メトキシハイドロキノン、メチレ
ンブルーおよび分子状酸素など従来公知の重合葉止剤存
在下に遂行されではいるか、メタクリル酸等の重合を完
全に抑制することはできす工程を経る毎にメタクリル酸
等の重合物か徐々に蓄積され、＠終工程では無視てきな
い量となる。したがって、メタクリル酸を精留留去した
後の高沸点成分中には相当量の重合物が存在するため、
メタクリル酸の留出率（留出量／供給量）８高くしすぎ
ると缶部の液粘度かｔ昇し、再沸器の熱効率の悪化、更
にはメタり１ノル酸等の重合を助長する結果となる。そ
こで、必然的にメタク）ノル酸の留出率はある範囲以下
に抑えることになり、缶残液として重合物を含む高沸点
成分と共に相当量のメタクリル酸を排出することになる
。[Problems to be Solved by the Prior Art and the Invention It is not possible to catalytically oxidize inbutylene, tertiary butanol, methacrolein or inbutylartecht with molecular oxygen in the presence of water vapor in a one- or two-step reaction. The resulting methacrylic acid can be made into a highly pure product by conventional purification methods such as extraction and distillation. However, in order to finally obtain methacrylic acid, it is necessary to remove low-boiling components such as aldehydes and ketones from the methacrylic acid aqueous solution, recover the solvent after the extraction process, separate acids with lower boiling points than methacrylic acid, and then remove high-boiling components from the methacrylic acid aqueous solution. separation and repeated exposure to heating conditions. Therefore, each step of the treatment is carried out in the presence of conventionally known polymerization inhibitors such as phenothiazine, hensifetchiazine, hydroquinone, methoxyhydroquinone, methylene blue, and molecular oxygen, in order to completely inhibit the polymerization of methacrylic acid, etc. With each step, polymers such as methacrylic acid are gradually accumulated, and in the final step, the amount reaches a level that cannot be ignored. Therefore, since a considerable amount of polymer is present in the high boiling point components after rectifying methacrylic acid,
If the distillation rate (distillation amount/supply amount) of methacrylic acid is too high, the viscosity of the liquid in the can will increase, deteriorating the thermal efficiency of the reboiler, and further promoting the polymerization of methacrylic acid, etc. result. Therefore, the distillation rate of methacrylic acid must necessarily be kept below a certain range, and a considerable amount of methacrylic acid will be discharged together with high-boiling components including polymers as bottom liquid from the tank.
したがっで、本発明の目的はメタクリル酸蒸留の缶残液
からメタクリル酸を容易に、かつ効率よく回収するため
の方法を提供することにある。Therefore, an object of the present invention is to provide a method for easily and efficiently recovering methacrylic acid from the bottom liquid of methacrylic acid distillation.
（問題点を解決するための手段）
本発明者らは、この点に着目し、重合物及び高沸点成分
を含むメタクリル酸からメタクリル酸を効果的に回収す
る方法についで鋭意研究した結果、脂肪族、芳香族ある
いは脂環式の炭化水素を前記缶残液に添加するとメタク
リル酸等の重合物及び高沸点成分の一部か選択的に析出
することを見い出し、その知見に基づき本発明を完成し
た。(Means for solving the problem) The present inventors focused on this point, and as a result of intensive research into a method for effectively recovering methacrylic acid from methacrylic acid containing polymers and high-boiling components, they found that It was discovered that when a group, aromatic or alicyclic hydrocarbon is added to the bottom liquid, a part of polymers such as methacrylic acid and high boiling point components are selectively precipitated, and based on this knowledge, the present invention was completed. did.
本発明のメタクリル酸の回収法はメタクリル酸を蒸留分
離した缶残液に有機溶剤を加え、析出する重合物および
高沸点成分をか別しで除去することを特徴とするもので
ある。The method for recovering methacrylic acid of the present invention is characterized by adding an organic solvent to the bottom liquid from which methacrylic acid has been distilled off, and removing precipitated polymers and high-boiling components by filtering.
１記の缶残液は、公知の種々の方法により得られたメタ
クリル酸を基音しで得られた缶残液か使用可能である。As the can residual liquid mentioned in item 1, can residual liquid obtained by adding methacrylic acid obtained by various known methods can be used.
例えば、インブチレン、第３級ブタノール、メタクロレ
インまたはイソブチルアルデヒドを水蒸気の存在下に分
子状酸素を含有するガスによつ接触酸化し、この酸化生
成物を冷却することにより得られるメタクリル酸水溶液
から、溶媒によるメタクリル酸の抽出、溶媒の回収、メ
タクリル酸の蒸留分離をした缶残液である。For example, from an aqueous methacrylic acid solution obtained by catalytically oxidizing inbutylene, tertiary butanol, methacrolein or isobutyraldehyde with a gas containing molecular oxygen in the presence of water vapor and cooling the oxidation product. This is the bottom liquid from which methacrylic acid was extracted with a solvent, the solvent was recovered, and the methacrylic acid was separated by distillation.
缶残液の組成は過密メタクリル酸６０〜９５重量部、高
廓点物３〜３帽１部、重合物２〜１０重量部である。缶
残液中の高沸点成分はシトラコン酸、マレイン酸、テレ
フタル酸等の高；弗点の酸類、および重合葉止剤としで
添加されたハイドロキノン等であり、また重合物はメタ
クリル酸の重合物である。The composition of the remaining liquid from the can is 60 to 95 parts by weight of overcrowded methacrylic acid, 1 part by weight of 3 to 3 parts by weight of a high-temperature point substance, and 2 to 10 parts by weight of a polymer. The high boiling point components in the can residue are acids with high boiling points such as citraconic acid, maleic acid, and terephthalic acid, as well as hydroquinone added as a polymerization inhibitor, and the polymer is a polymer of methacrylic acid. It is.
本発明においで用いる有機溶剤としては、脂肪族炭化水
素のローベンクン、ローへブタン、ｎ−ヘキサンおよび
ｎ−オクタン等、脂環式炭化水素のシクロヘキサン等ま
たは芳香族炭化水素のエチルベンゼン、キシレンおよび
トルエン等を挙げることかできる。また有機溶剤の添加
量は溶剤の種類および缶残液の組成によって異なるか、
通常缶残液に対し１〜４倍量（重量）か採用される。１
倍量（重量）よつ少ない場合は重合物及び高沸点成分の
析出か充分ではなく、本来の目的を果すことかできす、
４倍量（重量）を越えで使用する場合には前工程へ返送
した際に溶剤を分離回収するためのエネルギーコストか
嵩むため好ましくない。Examples of the organic solvent used in the present invention include aliphatic hydrocarbons such as lobenkune, rhohebutane, n-hexane and n-octane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as ethylbenzene, xylene and toluene. I can list the following. Also, the amount of organic solvent added varies depending on the type of solvent and the composition of the remaining liquid in the can.
Usually, 1 to 4 times the amount (weight) of the remaining liquid in the can is used. 1
If the amount is less than double the amount (weight), the polymer and high boiling point components will not be precipitated enough, and the original purpose cannot be achieved.
If more than 4 times the amount (weight) is used, it is not preferable because the energy cost for separating and recovering the solvent increases when it is returned to the previous process.
こうして缶残液に有機溶剤を加えで析出する重合物及び
高沸点成分の〃１過に用いるｒ過器としでは特に制限は
ないか、カートリッジフィルター、加圧葉状ｒ過器など
が一般的である。In this way, there are no particular restrictions on the type of filtration device used to filter the polymers and high-boiling components that are precipitated by adding an organic solvent to the can residual liquid. Cartridge filters, pressurized leaf filtration devices, etc. are common. .
重合物及び高沸点成分を〃′別した後の有機層は前工程
であるメタクリル酸水溶液からの液々抽出工程、あるい
は抽出相からの溶剤回収工程へ返送してメタクリル酸を
回収する。また場合によっては、何機層を単独で蒸留し
て溶剤と分離しメタクリル酸を回収するとも可能である
。The organic layer after the polymer and high-boiling components have been separated is returned to the previous step of liquid-liquid extraction from an aqueous methacrylic acid solution or to the solvent recovery step from the extraction phase to recover methacrylic acid. Depending on the case, it is also possible to separately distill several layers to separate them from the solvent and recover the methacrylic acid.
（発明の効果）
本発明の方法によれば従来缶残液として高沸点成分およ
び重合物と共に排棄または焼却されでいたメタクリル酸
を容易に、かつ、９力率的に回収することかできる。(Effects of the Invention) According to the method of the present invention, methacrylic acid, which has conventionally been discarded or incinerated together with high-boiling components and polymers as a residual liquid in a can, can be easily recovered with a power factor of 9.
以下に実施例をあげて本発明をざらに具体的に説明する
。EXAMPLES The present invention will be explained in detail below with reference to Examples.
実施例１
、メタクリル酸８４．５重量部、高沸点成分１０．３重
１部、重合物５．２重量部からなる、メタクリル酸精留
塔の缶残液１０に９にｎ−ヘキサン２０に９を加えて充
分に撹拌し、重合物か完全に析出したところで、０．１
ｍ′のカートリッジフィルターを通して処理を行った。Example 1 The residue of a methacrylic acid rectification column, consisting of 84.5 parts by weight of methacrylic acid, 1 part by weight of high-boiling components, and 5.2 parts by weight of polymer, was mixed into 10 parts by weight and 9 parts by weight of n-hexane by 20 parts by weight. 9 was added and stirred thoroughly, and when the polymer was completely precipitated, 0.1
The treatment was carried out through a cartridge filter of m'.
得られた叶へキサン溶液中のメタクリル酸は２８．８重
量部、高沸点成分２．２重量部、重合物０．１重量部で
メタクリル酸の回収率は９８．０％、重合物の除去率は
９４．２％、高沸点成分の除去率は６０．１％であった
。The obtained Kanohexane solution contained 28.8 parts by weight of methacrylic acid, 2.2 parts by weight of high-boiling components, and 0.1 part by weight of polymer, and the recovery rate of methacrylic acid was 98.0%, and the polymer was removed. The removal rate was 94.2%, and the removal rate of high boiling point components was 60.1%.
実施例２および３
表−１に示した組成の缶残液をｎ−へキサンによつ実施
例１と同様に処理を行った。結果を表−１に示した。Examples 2 and 3 The bottom liquid having the composition shown in Table 1 was treated with n-hexane in the same manner as in Example 1. The results are shown in Table-1.
実施例４および６
缶残液に対する溶剤の添加量を変えて実施例］と同様の
処理を行った結果を表−２に示した。Examples 4 and 6 Table 2 shows the results of carrying out the same treatment as in Example 4 and 6 by changing the amount of solvent added to the can residual liquid.
Claims (1)
え、析出する重合物および高沸点成分を濾別して除去す
ることを特徴とするメタクリル酸の回収法。 ２、上記有機溶剤がｎ−ペンタン、ｎ−ヘキサン、ｎ−
ヘプタン、ｎ−オクタン、シクロヘキサン、トルエン、
エチルベンゼンまたはキシレンである特許請求の範囲第
１項記載の方法。[Scope of Claims] 1. A method for recovering methacrylic acid, which comprises adding an organic solvent to the bottom liquid from which methacrylic acid has been separated by distillation, and filtering and removing precipitated polymers and high-boiling components. 2. The above organic solvent is n-pentane, n-hexane, n-
heptane, n-octane, cyclohexane, toluene,
The method according to claim 1, wherein ethylbenzene or xylene is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60242932A JPH0739367B2 (en) | 1985-10-31 | 1985-10-31 | Methacrylic acid recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60242932A JPH0739367B2 (en) | 1985-10-31 | 1985-10-31 | Methacrylic acid recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62106044A true JPS62106044A (en) | 1987-05-16 |
| JPH0739367B2 JPH0739367B2 (en) | 1995-05-01 |
Family
ID=17096359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60242932A Expired - Fee Related JPH0739367B2 (en) | 1985-10-31 | 1985-10-31 | Methacrylic acid recovery method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0739367B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6069053A (en) * | 1984-08-02 | 1985-04-19 | Mitsubishi Rayon Co Ltd | Extraction and separation of methacrylic acid |
| JPS60104034A (en) * | 1983-11-11 | 1985-06-08 | Nippon Kayaku Co Ltd | Recovery of methacrylic acid |
-
1985
- 1985-10-31 JP JP60242932A patent/JPH0739367B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104034A (en) * | 1983-11-11 | 1985-06-08 | Nippon Kayaku Co Ltd | Recovery of methacrylic acid |
| JPS6069053A (en) * | 1984-08-02 | 1985-04-19 | Mitsubishi Rayon Co Ltd | Extraction and separation of methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0739367B2 (en) | 1995-05-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |