JPH0193559A - Treatment of distillation bottom residue of methacrylic acid - Google Patents
Treatment of distillation bottom residue of methacrylic acidInfo
- Publication number
- JPH0193559A JPH0193559A JP2971687A JP2971687A JPH0193559A JP H0193559 A JPH0193559 A JP H0193559A JP 2971687 A JP2971687 A JP 2971687A JP 2971687 A JP2971687 A JP 2971687A JP H0193559 A JPH0193559 A JP H0193559A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- distillation
- bottom residue
- solvent
- methanol
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004821 distillation Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 37
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 230000032050 esterification Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PGIGZWJIJSINOD-UHFFFAOYSA-N 12h-benzo[a]phenothiazine Chemical compound C1=CC=CC2=C3NC4=CC=CC=C4SC3=CC=C21 PGIGZWJIJSINOD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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蒸留残液の処理方法１′−関する
。さらに詳しくはメタクリル酸を主成分として含有する
蒸留缶残液からメタクリル酸をメタクリル酸メチルとし
て有効に回収するためのメタクリル酸蒸留缶残液の処理
方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method 1' for treating methacrylic acid distillation residue. More specifically, the present invention relates to a method for treating methacrylic acid distillation bottom liquid for effectively recovering methacrylic acid as methyl methacrylate from distillation bottom liquid containing methacrylic acid as a main component.
〔従来の技術及び発明が解決しようとする問題点〕イソ
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で
１段または２段の反応で接触酸化して得られるメタクリ
ル酸は、抽出及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。[Prior art and problems to be solved by the invention] Isobutylene, tertiary butanol, methacrolein or isobutyraldehyde is catalytically oxidized with molecular oxygen in the presence of water vapor in one or two steps. The methacrylic acid obtained can be made into a highly pure product by conventional purification methods such as extraction and distillation.
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
脇息成分の除去、抽出処理後の溶剤回収、メタクリル酸
より低沸点の酸の分離、そして高沸点成分の分離工程等
、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、ベンゾフェノチアジン、ハイド
ロキノン、ハイドロキノンモノメチルエーテル、メチレ
ンブルーおよび分子状酸素などの従来公知の重合禁止剤
の存在下に遂行されれてはいるが、メタクリル酸等の重
合を完全に抑制することはできず、工程を経るごとに高
沸点成分、メタクリル酸等の重合物および重合禁止剤等
が徐々に蓄積され、最終工程では無視できない量となっ
ている。However, in order to finally obtain methacrylic acid, it is necessary to remove light-boiling side effects such as aldehydes and ketones from an aqueous methacrylic acid solution, recover the solvent after the extraction process, separate acids with a lower boiling point than methacrylic acid, and It is exposed to heating conditions many times, such as in the process of separating boiling point components. Therefore, although each process is carried out in the presence of conventionally known polymerization inhibitors such as phenothiazine, benzophenothiazine, hydroquinone, hydroquinone monomethyl ether, methylene blue, and molecular oxygen, the polymerization of methacrylic acid, etc. is completely inhibited. High-boiling components, polymers such as methacrylic acid, polymerization inhibitors, etc. gradually accumulate with each step, and in the final step they reach a non-negligible amount.
このような缶残液中の高沸点成分としては、マレイン酸
、シトラコン酸、安息香酸、トルイル酸、トリメリット
酸等の酸類、ベンズアルデヒド、トルアルデヒド等のア
ルデヒド類が含まれ、また重合物としてはメタクリル酸
やメタクロレインの重合物が含まれる。メタクリル酸を
精留留去した後の缶残液中にはこれらの高沸点成分、重
合物、重合禁止剤等が相当燵存在するため、メタクリル
酸の留出率、すなわち、留出量／供給量の割合を高くし
すぎると、メタクリル酸の純度が低下し、同時に缶部の
液粘度が上昇し、塔底リボイラーの熱効率の悪化、さら
にはメタクリル酸等の重合を助長する結果となる。特に
高沸点酸類は缶部で結晶化して析出し易く安定な操業を
妨げる結果となる。High boiling point components in such bottom liquid include acids such as maleic acid, citraconic acid, benzoic acid, toluic acid, and trimellitic acid, and aldehydes such as benzaldehyde and tolualdehyde. Contains polymers of methacrylic acid and methacrolein. Since a considerable amount of these high-boiling components, polymers, polymerization inhibitors, etc. are present in the bottom liquid after rectifying methacrylic acid, the distillation rate of methacrylic acid, that is, the distillation amount/supply If the ratio is too high, the purity of methacrylic acid will decrease, and at the same time, the liquid viscosity in the can will increase, resulting in deterioration of the thermal efficiency of the bottom reboiler and further promoting the polymerization of methacrylic acid and the like. In particular, high boiling point acids tend to crystallize and precipitate in the can, which hinders stable operation.
そこで、必然的にメタクリル酸の留出率をある範囲以下
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
。したがって、該缶残液を廃棄または焼却することはメ
タクリル酸の損失をまねき、ひいては原単位の悪化およ
びコスト増につながるために、何等かの方法でこれらの
メタクリル酸の回収を計らなければならなかった。Therefore, it is inevitable that the distillation rate of methacrylic acid is kept below a certain range, and a considerable amount of methacrylic acid is discharged as bottom liquid together with high-boiling components including polymers. Therefore, discarding or incinerating the residual liquid from the can will lead to a loss of methacrylic acid, which will lead to a worsening of the basic unit and an increase in costs, so some method must be taken to recover this methacrylic acid. Ta.
従来、一般的な方法と１．て、蒸発缶等による缶残液の
再蒸発によりメタクリル酸を回収するか、または有機溶
剤抽出によりメタクリル酸を回収する方法が考えられて
きた。しかし、前者は回収率の悪さやメタクリル酸の重
合に起因する操業上の問題などがあり、また後者は抽出
溶剤により多量の浮滓が生成し、エマルジョン化や抽出
塔のフラッディングが発生するなど、いずれも有効な方
法とは言えない。Conventionally, common methods and 1. Therefore, methods have been considered in which methacrylic acid is recovered by re-evaporation of the residual liquid in an evaporator or the like, or by extraction with an organic solvent. However, the former has operational problems such as poor recovery and polymerization of methacrylic acid, while the latter produces a large amount of dregs due to the extraction solvent, causing emulsification and flooding of the extraction tower. Neither method can be said to be effective.
本発明者らは上記した問題点に着目し、メタクリル酸を
蒸留分離した後の重合物および高沸点成分を含む缶残液
からメタクリル酸を効果的に回収する方法について鋭意
検討した結果１本発明に係る特有の不純物を含む缶残液
に対しては、メタクリル酸メチルとして回収する方法が
優れていることを見出し本発明を完成した。The present inventors focused on the above-mentioned problems and conducted intensive studies on a method for effectively recovering methacrylic acid from the polymer after distillation and separation of methacrylic acid and from the bottom liquid containing high-boiling components.1 The present invention was made as a result of the present invention. The present invention has been completed based on the discovery that a method of recovering methyl methacrylate from the remaining liquid containing specific impurities is superior.
すなわち、本発明はイソブチレン、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り接触酸化し、
この酸化生成物を冷却することによって得られるメタク
リル酸水溶液から溶媒によりメタクリル酸を抽出し、該
溶媒を分離回収したのち軽佛点成分を次いでメタクリル
酸を蒸留分離し、なほ缶残液に残存するメタクリル酸を
回収するに当り、該缶残液を強酸性陽イオン交換・樹脂
の存在下にメタクリル酸に対して２〜５倍モル１１のメ
タノールにより８５〜９５℃でエステル化し、生成した
メタクリル酸メチルを蒸留回収することを特徴とするメ
タクリル酸蒸留缶残液の処理方法である。That is, the present invention uses isobutylene, tertiary butanol,
Catalytic oxidation of methacrolein or isobutyraldehyde with a gas containing molecular oxygen in the presence of water vapor,
The methacrylic acid is extracted with a solvent from the methacrylic acid aqueous solution obtained by cooling this oxidation product, and after the solvent is separated and recovered, the light point component is then separated by distillation, and the methacrylic acid remains in the Naho can residual liquid. To recover methacrylic acid, the remaining liquid from the tank is esterified at 85 to 95°C with methanol in an amount of 2 to 5 times the mole of methacrylic acid in the presence of a strongly acidic cation exchange resin at 85 to 95°C. This is a method for treating methacrylic acid distillation can residual liquid, which is characterized by recovering methyl by distillation.
本発明の方法が対象とする缶残液は、イソブチレン、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
により常法により接触酸化し、この酸化成生成物を冷却
することによって得られるメタクリル酸水溶液を、溶媒
によるメタクリル酸の抽出、溶媒の回収、軽沸脇息成分
の除去等を行った粗メタクリル酸から常法によってメタ
クリル酸を蒸留分離した缶残液である。The bottom liquid targeted by the method of the present invention is obtained by catalytically oxidizing isobutylene, tertiary butanol, methacrolein, or isobutyraldehyde with a gas containing molecular oxygen in the presence of water vapor, and then producing the oxidized product. The methacrylic acid aqueous solution obtained by cooling the product is extracted from the methacrylic acid using a solvent, the solvent is recovered, the light-boiling side gas components are removed, and the methacrylic acid is distilled off from the crude methacrylic acid using a conventional method. It is a liquid.
本発明の方法においては缶残液の組成は、通常、メタク
リル酸６０〜９５重量部、高沸点物３〜３０重量部およ
び重合物１〜１０重量部の範囲の全体として１００重量
部となる割合いのものであることが好ましい。In the method of the present invention, the composition of the bottom liquid is usually 60 to 95 parts by weight of methacrylic acid, 3 to 30 parts by weight of a high boiling point substance, and 1 to 10 parts by weight of a polymer, in a proportion that makes a total of 100 parts by weight. It is preferable that it be of good quality.
本発明の方法は少量の缶残液を回分処理する際にも適用
できるが、一般には工業的に大量規模で行なわれるメタ
クリル酸製造プロセスにおいて排出される缶残液を、連
続処理する方法として特に優れている。Although the method of the present invention can be applied to the batch treatment of small amounts of can residual liquid, it is especially suitable as a method for continuous treatment of can residual liquid discharged in the methacrylic acid manufacturing process, which is generally carried out on an industrial scale. Are better.
本発明の目的は、缶残液中のメタクリル酸を有官軍鈍物
を含むことなくワンパスで効率よく回収することであり
、さらには高沸点ないし非揮発性残査を、例えば缶出液
として排出する際の工程トラブルを起すことなく高濃度
に排出させることにある。そのためには缶残液中のカル
ボン酸類を高い転化率でメチルエステル化することが必
要である。本発明の方法によれば有害不純物をほとんど
含まないメタクリル酸メチルが高収率で蒸留回収できる
と同時に缶残液の性状が改良されトラブルなく安定操業
が可能となる。The purpose of the present invention is to efficiently recover methacrylic acid in the bottom liquid in one pass without containing military obsolete substances, and furthermore, to discharge high boiling point or non-volatile residues as, for example, bottom liquid. The goal is to discharge high concentrations without causing any process troubles. For this purpose, it is necessary to convert the carboxylic acids in the bottom liquid into methyl esters at a high conversion rate. According to the method of the present invention, methyl methacrylate containing almost no harmful impurities can be recovered by distillation at a high yield, and at the same time, the properties of the bottom liquid are improved, allowing stable operation without trouble.
本発明において使用する強酸性陽イオン交換樹脂はスル
ホン酸基を有するイオン交換樹脂であり、母体構造はス
チレン系で、マクロポーラス型であることが好ましく、
例えばダイヤイオンＰＫ２２８ 、ＰＫ２１２．ＰＫ−
２１６（三菱化成（株）、レバチット５Ｐ−１２０，５
Ｐ−１１２（バイエル社）、アンバーライト２５２（ロ
ームアンドハース社）等の商品名を挙げることができる
。そしてこれらの樹脂は通常、空間速度として０．５〜
２．Ｏｈｒ−１の速１の反応液と接触させてエステル化
反応させることができる。The strongly acidic cation exchange resin used in the present invention is an ion exchange resin having a sulfonic acid group, and preferably has a styrene-based matrix structure and a macroporous type.
For example, Diaion PK228, PK212. PK-
216 (Mitsubishi Kasei Corporation, Revachit 5P-120,5
Product names include P-112 (Bayer) and Amberlite 252 (Rohm and Haas). These resins usually have a space velocity of 0.5 to
2. The esterification reaction can be carried out by contacting Ohr-1 with a reaction solution of speed 1.
エステル化反応におけるメタノールの使用量は、 。The amount of methanol used in the esterification reaction is:
缶残液の組成にもよるが通常１缶残液中のメタクリル酸
に対して２〜５倍モル量の範囲で使用する０反応温度は
８５〜９５℃で行う必要があり、８５℃以下では転化率
が低くまた９５℃以上では強酸性陽イオン交換樹脂の劣
化を早めるため採用できない、したがって反応は通常２
．５〜３゜５ＫＧ／ｃｍ″の加圧下に液状で行なわれる
。Although it depends on the composition of the residual liquid in the can, the amount used is usually 2 to 5 times the molar amount of methacrylic acid in the residual liquid in one can.The reaction temperature must be 85 to 95°C, and if it is below 85°C, The conversion rate is low and temperatures above 95°C accelerate the deterioration of the strongly acidic cation exchange resin, so it cannot be used. Therefore, the reaction is usually
．． It is carried out in liquid form under pressure of 5 to 3.5 KG/cm''.
即ち、本発明においては上記エステル化反応によって該
缶残液中に存在する前記高沸点成分である酸類も同様に
エステル化されるが１周知の通り通常のエステル化反応
の平衡恒数は余り大きな撒ではなく、本発明におけるメ
タクリル酸および高沸点の酸類のエステル化も略同様で
ある０本発明者らの検討では、メタノールによるメチル
エステル化の場合には、メタクリル酸をメチルエステル
化する為の通常の反応条件において、メタクリル酸のエ
ステル化率より高沸点の酸類のエステル化率の方が大で
あることが見出されている。したかってメタクリル酸の
エステル化率を高めるために前記反応温度が特に設定さ
れる。この条件においては高沸点成分の酸類はよりエス
テル化率が進み缶残液はエステル生成物が主成分となる
ため、液性が改善されその後の取扱いも容易となる。−
方、イオン交換樹脂を高温域で使うことは一般に好まし
くないが、本発明の如き挟雑物の多い缶残液を処理する
場合は、該樹脂の触媒活性点が著しく阻害されるため特
に本発明の温度設定が重要となる。That is, in the present invention, the acids, which are the high-boiling components present in the bottom liquid of the tank, are also esterified by the esterification reaction, but as is well known, the equilibrium constant of a normal esterification reaction is too large. In the present invention, the esterification of methacrylic acid and high-boiling acids is almost the same as in the case of methyl esterification with methanol. It has been found that under normal reaction conditions, the esterification rate of high boiling point acids is greater than the esterification rate of methacrylic acid. Therefore, the reaction temperature is specifically set in order to increase the esterification rate of methacrylic acid. Under these conditions, the esterification rate of the high-boiling point components of acids increases, and the ester product becomes the main component of the remaining liquid in the tank, so that the liquid properties are improved and subsequent handling becomes easier. −
On the other hand, it is generally not preferable to use ion exchange resins in high temperature ranges, but when treating can residue with a lot of impurities as in the present invention, the catalytic active sites of the resin are significantly inhibited, so the use of ion exchange resins in high temperature ranges is particularly undesirable. The temperature setting is important.
エステル化反応した缶残益は、常法に従って蒸留するこ
とによりメタクリル酸メチル、メタノールおよび水を主
成分とする流出液として回収することができる。この蒸
留液中にはメタクリル酸メチルとの分離が困難な物質は
ほとんど留出しない、エステル化反応後蒸留によって回
収したメタクリル酸メチルを主成分とする流出液は、メ
タクリル酸からメタクリル酸メチルを生産する工程の適
所、たとえばエステル化塔（槽）から排出される流れに
供給することによりメタクリル酸メチル、メタノール、
および水を分離し精製することができる。またメタクリ
ル酸メチルを蒸留回収したあとの缶残液は適度の流動性
を有するので容易に排出することができる。The residue from the can after the esterification reaction can be recovered as an effluent containing methyl methacrylate, methanol, and water as main components by distillation according to a conventional method. Almost no substances that are difficult to separate from methyl methacrylate are distilled out in this distillate.The effluent mainly composed of methyl methacrylate recovered by distillation after the esterification reaction produces methyl methacrylate from methacrylic acid. Methyl methacrylate, methanol,
and water can be separated and purified. Further, the remaining liquid after distilling and recovering methyl methacrylate has appropriate fluidity and can be easily discharged.
本発明の処理方法によれば、従来缶残液として高沸点成
分および重合物とともに廃棄または焼却されていたメタ
クリル酸をメタクリル酸メチルとして容易に、かつ効率
良く回収することができる。さらに、缶残液中のメタク
リル酸は有害不純物をほとんど含むことなく回収でき、
また最終的に得られる缶出液は配管閉塞等のトラブルを
起すことなく、液状で安定して排出することができる。According to the treatment method of the present invention, methacrylic acid, which has conventionally been discarded or incinerated together with high-boiling components and polymers as can residual liquid, can be easily and efficiently recovered as methyl methacrylate. Furthermore, the methacrylic acid in the remaining liquid from the can can be recovered with almost no harmful impurities.
Further, the finally obtained bottoms can be stably discharged in liquid form without causing troubles such as pipe clogging.
強酸性陽イオン交換樹脂（三菱化成工業■製、ダイヤイ
オンＰＫ−２２８）を常法により塩融を用いて水素型に
イオン交換したのちエステル化反応器に２ｆＬ充填した
。A strongly acidic cation exchange resin (manufactured by Mitsubishi Kasei Corporation, Diaion PK-228) was ion-exchanged into a hydrogen form using salt melting in a conventional manner, and then 2 fL was charged into an esterification reactor.
イソブチレンの接触酸化反応によって得られた粗メタク
リル酸を、精密蒸留した缶残液（メタクリル酸８８．８
４％、安息香酸２．０１％ 、パラトルイル酸ｏ、８ｅ
’ｉ、 、 ソノ他揮発成分０．７１％ 、重合禁止剤
４．８８２、非揮発成分２．８９％ 、各重量％）に、
該缶残液中のメタクリル酸に対して３倍モル量のメタノ
ールを混合した第１表のフィード原液をエステル化反応
器へ空間速度１．Ｑｈｒ’で供給し、９０℃でエステル
化反応を行い、同じく第１表に示す組成のエステル化反
応生成物を得た。Crude methacrylic acid obtained by the catalytic oxidation reaction of isobutylene is distilled to distill the bottom liquid (methacrylic acid 88.8
4%, benzoic acid 2.01%, paratoluic acid o, 8e
'i, , 0.71% of other volatile components, 4.882% of polymerization inhibitor, 2.89% of non-volatile components, each weight%),
The feed stock solution shown in Table 1, in which methanol is mixed in an amount three times the molar amount of methacrylic acid in the bottom liquid of the tank, is fed to the esterification reactor at a space velocity of 1. The esterification reaction was carried out at 90° C. to obtain an esterification reaction product having the same composition as shown in Table 1.
第１表
エステル化反応器からとり出された反応生成物を塔径２
５ｍｍ 、段数２０段のガラス製オールグーショウ型蒸
留塔に供給し、メタクリル酸メチルを回収し第２表に示
す組成の留出液を得た。Table 1 The reaction product taken out from the esterification reactor was
Methyl methacrylate was recovered by supplying it to a glass all-gourmet distillation column with a diameter of 5 mm and 20 plates to obtain a distillate having the composition shown in Table 2.
比較例１
温度を種々変えた以外は実施例１と同様の方法でエステ
ル化を行い、同じく第３表に示す組成のエステル化反応
物を得た。Comparative Example 1 Esterification was carried out in the same manner as in Example 1, except that the temperature was variously changed, to obtain an esterification reaction product having the same composition as shown in Table 3.
第 ３ 表 特許出願人 三井東圧化学株式会社 協和ガス化学工業株式会社Table 3 Patent applicant Mitsui Toatsu Chemical Co., Ltd. Kyowa Gas Chemical Industry Co., Ltd.
Claims (1)
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り接触酸化し、この酸化生成
物を冷却することによって得られるメタクリル酸水溶液
から溶媒によりメタクリル酸を抽出し該溶媒を分離回収
したのち軽沸点成分を次いでメタクリル酸を蒸留分離し
、なほ缶残液に残存するメタクリル酸を回収するに当り
、該缶残液を強酸性陽イオン交換樹脂の存在下にメタク
リル酸に対して２〜５倍モル量のメタノールにより８５
〜９５℃でエステル化し、生成したメタクリル酸メチル
を蒸留回収することを特徴とするメタクリル酸蒸留缶残
液の処理方法。(1) Using a solvent from an aqueous methacrylic acid solution obtained by catalytically oxidizing isobutylene, tertiary butanol, methacrolein, or isobutyraldehyde with a gas containing molecular oxygen in the presence of water vapor and cooling the oxidation product. After extracting methacrylic acid and separating and recovering the solvent, the light boiling point components are then separated by distillation, and in order to recover the methacrylic acid remaining in the Naho can residual liquid, the can residual liquid is treated with a strongly acidic cation exchange resin. 85 with methanol in a molar amount 2 to 5 times that of methacrylic acid in the presence of
A method for treating methacrylic acid distillation bottom liquid, which comprises performing esterification at ~95°C and recovering the produced methyl methacrylate by distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62029716A JPH0761981B2 (en) | 1987-02-13 | 1987-02-13 | Method for processing residual liquid of methacrylic acid distillation still |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62029716A JPH0761981B2 (en) | 1987-02-13 | 1987-02-13 | Method for processing residual liquid of methacrylic acid distillation still |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0193559A true JPH0193559A (en) | 1989-04-12 |
| JPH0761981B2 JPH0761981B2 (en) | 1995-07-05 |
Family
ID=12283834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62029716A Expired - Fee Related JPH0761981B2 (en) | 1987-02-13 | 1987-02-13 | Method for processing residual liquid of methacrylic acid distillation still |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761981B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1043302A3 (en) * | 1999-04-05 | 2003-01-02 | Nippon Shokubai Co., Ltd. | Method for handling waste oil |
| US6965243B2 (en) | 2003-03-21 | 2005-11-15 | Junichi Yamagishi | Capacitance sensor |
| WO2006085540A1 (en) * | 2005-02-09 | 2006-08-17 | Mitsubishi Rayon Co., Ltd. | PROCESS FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID |
| JP2013121946A (en) * | 2011-11-07 | 2013-06-20 | Mitsubishi Rayon Co Ltd | Method and apparatus for producing methacrolein and methacrylic acid from isobutanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945020A (en) * | 1972-09-08 | 1974-04-27 |
-
1987
- 1987-02-13 JP JP62029716A patent/JPH0761981B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945020A (en) * | 1972-09-08 | 1974-04-27 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1043302A3 (en) * | 1999-04-05 | 2003-01-02 | Nippon Shokubai Co., Ltd. | Method for handling waste oil |
| US6965243B2 (en) | 2003-03-21 | 2005-11-15 | Junichi Yamagishi | Capacitance sensor |
| WO2006085540A1 (en) * | 2005-02-09 | 2006-08-17 | Mitsubishi Rayon Co., Ltd. | PROCESS FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID |
| US7820856B2 (en) | 2005-02-09 | 2010-10-26 | Mitsubishi Rayon Co., Ltd. | Process for producing α,β-unsaturated carboxylic acid |
| JP4922917B2 (en) * | 2005-02-09 | 2012-04-25 | 三菱レイヨン株式会社 | Process for producing α, β-unsaturated carboxylic acid |
| JP2013121946A (en) * | 2011-11-07 | 2013-06-20 | Mitsubishi Rayon Co Ltd | Method and apparatus for producing methacrolein and methacrylic acid from isobutanol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761981B2 (en) | 1995-07-05 |
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