JPS63107755A - Regeneration of ion exchange resin - Google Patents
Regeneration of ion exchange resinInfo
- Publication number
- JPS63107755A JPS63107755A JP61253624A JP25362486A JPS63107755A JP S63107755 A JPS63107755 A JP S63107755A JP 61253624 A JP61253624 A JP 61253624A JP 25362486 A JP25362486 A JP 25362486A JP S63107755 A JPS63107755 A JP S63107755A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- exchange resin
- anion exchange
- regeneration
- 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
- 239000003456 ion exchange resin Substances 0.000 title claims description 20
- 229920003303 ion-exchange polymer Polymers 0.000 title claims description 20
- 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 title claims description 18
- 238000011069 regeneration method Methods 0.000 title abstract description 22
- 230000008929 regeneration Effects 0.000 title abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000000284 extract Substances 0.000 claims description 12
- 230000001172 regenerating effect Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 7
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 8
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 abstract description 8
- 229940018557 citraconic acid Drugs 0.000 abstract description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 8
- 239000011976 maleic acid Substances 0.000 abstract description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 3
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001429 chelating resin Polymers 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- 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〕
この発明は、イオン交換樹脂の再生方法に関するもので
ある。さらに詳しくはイソブチレン、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含有ガスにより接触酸化して得ら
れるメタクリル酸に含まれるマレイン酸およびシトラコ
ン酸などの２塩基酸の除去に用いる塩基性陰イオン交換
樹脂の再生方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to a method for regenerating ion exchange resins. More specifically, removal of dibasic acids such as maleic acid and citraconic acid contained in methacrylic acid obtained by catalytic oxidation of isobutylene, tertiary butanol, methacrolein, or isobutyraldehyde with a molecular oxygen-containing gas in the presence of water vapor. The present invention relates to a method for regenerating a basic anion exchange resin used for.
本発明者らは、先にイソブチレン、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の精製法として場合により有
機溶剤で抽出したのち塩基性陰イオン交換樹脂で処理す
る方法を提案した（特願昭６Ｏ−４９２４８）。一方、
同様にして製造されたメタクリル酸含有液を有機溶剤で
抽出するにあたり、あらかじめ活性炭あるいはアミノ基
及び／又はアミンを有する弱塩基性陰イオン交換樹脂等
により処理することにより、有機溶剤で抽出する際に生
成し易いスカムの生成を防止する方法も提案されている
（特開昭５Ｏ−５２０２１）。 而て、塩基性陰イオン
交換樹脂で処理可能な被対象液としては、メタクリル酸
水溶液、メタクリル酸含有抽出液、抽出溶剤分離後のメ
タクリル酸およびメタクリル酸をエステル化したのち蒸
留分離された未反応メタクリル酸含有留分等がある。The present inventors previously discovered isobutylene, tertiary butanol,
As a purification method for methacrylic acid obtained by catalytically oxidizing methacrolein or isobutyraldehyde with molecular oxygen in the presence of water vapor in a one- or two-step reaction, it is optionally extracted with an organic solvent and then treated with a basic anion exchange resin. proposed a method of treatment (Japanese Patent Application No. 6O-49248). on the other hand,
When extracting a methacrylic acid-containing liquid produced in the same way with an organic solvent, it is possible to treat it with activated carbon or a weakly basic anion exchange resin containing amino groups and/or amines in advance. A method for preventing the formation of scum that is easily generated has also been proposed (Japanese Patent Laid-Open No. 50-52021). Therefore, target liquids that can be treated with basic anion exchange resins include aqueous methacrylic acid solutions, methacrylic acid-containing extracts, methacrylic acid after separation of the extraction solvent, and unreacted liquids separated by distillation after esterification of methacrylic acid. There are methacrylic acid-containing fractions, etc.
上記した被対象液のうち、メタクリル酸自身は水溶性で
あるため、メタクリル酸水溶液、抽出溶剤分［１ｔのメ
タクリル酸、およびメタクリル酸をエステル化したのち
蒸留分離された未反応メタクリル酸含存留分等の処理に
用いる塩基性陰イオン交換樹脂の再生方法は、通常のイ
オン交換網ｍの再生方法と、同様の方法、即ち、処理原
液を通液した後、水洗浄し次いで再生液で再生したのち
水洗浄し、再び処理原液を通液する操作で充分目的を達
成することができる。Among the above-mentioned target liquids, methacrylic acid itself is water-soluble. The method for regenerating the basic anion exchange resin used for the treatment is the same as the method for regenerating the normal ion exchange network m, that is, after passing the treatment stock solution through, washing with water and then regenerating with the regeneration solution. The purpose can be sufficiently achieved by washing with water and passing the treatment stock solution through again.
しかしながら、有機溶剤を抽出溶剤として得られるメタ
クリル酸含有抽出液について同様に処理した場合、即ち
イオン交換樹脂層を水洗したのち直接処理原液を通液す
る場合、抽出溶剤が疎水性で且つ水より比重が軽いため
水との置換が充分に行なわれず、従ってイオン交換樹脂
によるイオン交換率が低く目標の性能を得ることはでき
ない。However, when a methacrylic acid-containing extract obtained by using an organic solvent as an extraction solvent is treated in the same way, that is, when the ion exchange resin layer is washed with water and then the treated solution is directly passed through the ion exchange resin layer, the extraction solvent is hydrophobic and has a higher specific gravity than water. Since the ion exchange resin is light, sufficient replacement with water is not carried out, and therefore the ion exchange rate by the ion exchange resin is low, making it impossible to achieve the target performance.
またイオン交換樹脂の再生の際に処理原液を水洗浄置換
する場合は、抽出溶剤がイオン交換樹脂粒を包み込むた
め充分に洗浄できず、従って続いて行なわれる再生処理
において再生効率が上らないばかりかイオン交換樹脂粒
が浮上する問題も発生ずる。Furthermore, when the treated solution is replaced by water washing during the regeneration of ion exchange resins, the extraction solvent envelops the ion exchange resin particles, making it impossible to wash them thoroughly, and therefore the regeneration efficiency in the subsequent regeneration process is not increased. Also, a problem arises in which ion exchange resin particles float to the surface.
本発明の目的はかかる問題の解決方法を提供することに
ある。An object of the present invention is to provide a method for solving such problems.
Ｃ問題点を解決するための手段）
上記目的を達成する本発明は、メタクリル酸含有水溶液
から有機溶剤で抽出したメタクリル酸含有抽出液を塩基
性陰イオン交換樹脂処理してメタクリル酸を精製する方
法におけるイオン交換樹脂の再生方法において、イオン
交換樹脂層をメタクリル酸抽出用有機溶剤で置換した後
、親水性の溶剤で置換洗浄し、更に水洗した後、アルカ
リ再生することを特徴とするイオン交換樹脂の再生方法
である。Means for Solving Problem C) The present invention that achieves the above object is a method of purifying methacrylic acid by treating a methacrylic acid-containing extract extracted with an organic solvent from a methacrylic acid-containing aqueous solution with a basic anion exchange resin. In the method for regenerating an ion exchange resin, the ion exchange resin layer is replaced with an organic solvent for extracting methacrylic acid, followed by replacement washing with a hydrophilic solvent, further washing with water, and then alkali regeneration. This is the reproduction method.
本発明における親水性の溶剤としては、アセトン、メタ
ノール、エタノールが適しており、特にメタノールの使
用が好ましい。Suitable hydrophilic solvents in the present invention include acetone, methanol, and ethanol, with methanol being particularly preferred.
本発明において対象となるメタクリル酸含有抽出液は、
塩基性陰イオン交換樹脂で精製可能なマレイン酸および
シトラコン酸等の二塩基酸を含むものであれば特に有用
であり、メタクリル酸の合成方法自体は特に限定されな
い。しかし乍ら、対象となるメタクリル酸含有水溶液は
５通常、イソブチレン、第３級ブタノール、メタクロレ
インあるい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て得られる
ものである。The methacrylic acid-containing extract targeted in the present invention is
It is particularly useful if it contains dibasic acids such as maleic acid and citraconic acid that can be purified with a basic anion exchange resin, and the method for synthesizing methacrylic acid itself is not particularly limited. However, the target aqueous solution containing methacrylic acid is usually obtained by catalytic oxidation of isobutylene, tertiary butanol, methacrolein, or isobutyraldehyde with a gas containing molecular oxygen in the presence of water vapor. .
メタクリル酸抽出用有機溶剤としては、水不溶性乃至は
水に難溶性であることが一般的であり、広く使用されて
いる例えばローペンタン、ローヘキサン、ｎ−へブタン
、ｎ−オタタン、シクロ、ヘキサン、エチルベンゼン、
キシレン、トルエン、シクロヘキサノン、アセトフェノ
ン、イソホロン、メチルエチルケトン、ジイソブチレン
等の有機溶剤を単独あるいは２種以上の混合溶媒として
用いることができ、なかでもキシレン、トルエン、ｎ−
ヘキサン、ｎ−へブタン等のイＴＲ溶剤が多用される。Organic solvents for extracting methacrylic acid are generally insoluble or poorly soluble in water, and widely used examples include rhopentane, rhohexane, n-hebutane, n-otatane, cyclo, hexane, ethylbenzene,
Organic solvents such as xylene, toluene, cyclohexanone, acetophenone, isophorone, methyl ethyl ketone, and diisobutylene can be used alone or as a mixed solvent of two or more, and among them, xylene, toluene, n-
TR solvents such as hexane and n-hebutane are often used.
本発明で使用しつる塩基性陰イオン交換樹脂としては、
表される強塩基性のもの、 −Ｎ（Ｃ）１３ｈおよびポ
リアミンに代表される弱塩基性のもの、および−ＣＯＮ
Ｉ＋（（：Ｈ２）ｎ Ｎ （Ｃ１１３） ２に代表され
る中塩基性のものの何れでもよく、また樹脂の形成とし
ても多孔質型およびゲル型共に使用可能である。特にメ
タクリル酸水溶液以外の形で処理する場合は非水溶液用
の樹脂の使用が好ましい。The basic anion exchange resins used in the present invention include strong basic ones as shown below, weak basic ones typified by -N(C)13h and polyamines, and -CON
Any medium basic type represented by I+((:H2)n N (C113) 2 can be used, and both porous type and gel type can be used to form a resin. In particular, forms other than methacrylic acid aqueous solution can be used. In the case of treatment with a non-aqueous solution, it is preferable to use a resin for non-aqueous solutions.
上記した塩基性陰イオン交換樹脂としては、例えば弱塩
基性陰イオン交換樹脂アンバーリストＡ−２１、弱塩基
性陰イオン交換樹脂レバチットＭＰ−６２、強塩基性陰
イオン交換樹脂アンバーリスト２８、同Ａ−２６、強塩
基性陰イオン交換樹脂アンバーライトｒＲ＾−４００等
を挙げることができる。Examples of the above-mentioned basic anion exchange resins include weakly basic anion exchange resin Amberlyst A-21, weakly basic anion exchange resin Revatit MP-62, strong basic anion exchange resin Amberlyst 28, and Amberlyst A-21. -26, strongly basic anion exchange resin Amberlite rR^-400, and the like.
塩基性陰イオン交換樹脂による処理及び再生方法として
は、回分式でも連続式でも差支えないが、工業的には連
続式が有利である。連続的に処理再生する場合には、塩
基性陰イオン交換樹脂を充填したカラムに所定の温度に
保った前記メタクリル酸含有抽出液を一定の流速で通過
させることにより、検出限界のｌ ｐｐｍ以下のマレイ
ン酸およびシトラコン酸を実質上台まないメタクリル酸
を１ｉＩることができる。この場合のイオン交換処理温
度は、通常、１０〜６０℃、液空間速度は０．２〜２０
！／ｊ−ｈｒの範囲で行なわれる。The treatment and regeneration method using the basic anion exchange resin may be either a batch method or a continuous method, but the continuous method is industrially advantageous. In the case of continuous processing and regeneration, the methacrylic acid-containing extract kept at a predetermined temperature is passed through a column packed with a basic anion exchange resin at a constant flow rate, so that the detection limit is 1 ppm or less. Methacrylic acid substantially free of maleic acid and citraconic acid can be used. In this case, the ion exchange treatment temperature is usually 10 to 60°C, and the liquid hourly space velocity is 0.2 to 20°C.
! /j-hr.
このようにして所定の時間通液すると、採用したイオン
交換樹脂が破過点に到達するので、本発明方法によって
特徴的な次のような再生方法が適用される。When the ion exchange resin is passed through the resin for a predetermined period of time in this way, the employed ion exchange resin reaches its breakthrough point, so the following regeneration method, which is characteristic of the method of the present invention, is applied.
即ち、メタクリル酸含有抽出液の通液を停止し、カラム
内残留液を前記メタクリル酸抽出用有機溶剤で洗浄置換
する。この場合の液空間速度は通常２〜Ｉｏｎ／７ｈｒ
、好ましくは４〜８１／Ｉｈｒの範囲であり、通液量は
通液時間として通常０．３〜１時間の範囲で充分である
。この場合に用いる該有機溶剤としては、メタクリル酸
の抽出に用いる溶剤と同じである方が、後工程における
分離口′収の面から好ましい。That is, the flow of the methacrylic acid-containing extract solution is stopped, and the remaining solution in the column is washed and replaced with the organic solvent for methacrylic acid extraction. In this case, the liquid hourly space velocity is usually 2-Ion/7hr.
, preferably in the range of 4 to 81/Ihr, and the amount of liquid to be passed is usually sufficient in the range of 0.3 to 1 hour as the time for passing the liquid. The organic solvent used in this case is preferably the same as the solvent used for extracting methacrylic acid from the standpoint of separation yield in the subsequent step.
次いで圧縮空気で該置換溶剤を押出した後か、あるいは
直接前記親水性の溶剤で、通常、液空間速度２〜＋０７
／Ａｈｒ、好ましくは４〜８１／Ｉｈｒの範囲で押出し
置換する。この場合の通液１ｔｔは通液時間として通常
０．３〜１時間の範囲である。The displacement solvent is then extruded with compressed air or directly with the hydrophilic solvent, usually at a liquid hourly space velocity of 2 to +0.7
/Ahr, preferably in the range of 4 to 81/Ihr. In this case, 1 tt of liquid passing is usually in the range of 0.3 to 1 hour as the liquid passing time.
次いで該親水性の溶剤を圧縮空気で押出した後か、ある
いは直接蒸留水などの水で押出して置換し、更に水で充
分に洗浄する。この水洗工程は一般的に採用される通液
速度、通液量で充分である。またこの工程およびその前
工程より排出されるメタクリル酸抽出用有機溶剤および
適宜の濃度の親水性の溶媒は適宜の方法により回収され
再使用されることは特に詳述する迄もない。Next, the hydrophilic solvent is replaced by extrusion with compressed air or directly with water such as distilled water, and then thoroughly washed with water. In this water washing step, generally employed liquid passing rates and amounts are sufficient. It is needless to mention in detail that the organic solvent for extracting methacrylic acid and the hydrophilic solvent of appropriate concentration discharged from this step and the preceding step are recovered and reused by an appropriate method.
次いで塩基性陰イオン交換樹脂等の再生方法として用い
られるアルカリ再生法が採用され、例えば５重量％程度
の苛性ソーダ水溶液を液空間速度１〜５ｊ／ｊｈｒの範
囲で所定時間再生処理する方法が採用される。再生処理
後は水で充分に洗浄処理した後、再び圧縮空気で水を押
出し、斯くして得られる再生塩基性陰イオン交換樹脂は
メタクリル酸含有水溶液から有機溶剤で抽出したメタク
リル酸含有抽出液と接触処理するメタクリル酸の積装法
に有効に再使用される。Next, an alkali regeneration method used as a method for regenerating basic anion exchange resins and the like is adopted, for example, a method in which a caustic soda aqueous solution of about 5% by weight is regenerated at a liquid hourly space velocity of 1 to 5 j/jhr for a predetermined period of time is adopted. Ru. After the regeneration treatment, the water is thoroughly washed with water, and then the water is extruded with compressed air again, and the regenerated basic anion exchange resin thus obtained is mixed with a methacrylic acid-containing extract extracted from the methacrylic acid-containing aqueous solution with an organic solvent. It can be effectively reused in the loading method of contact-treated methacrylic acid.
（作用と効果）
本発明のイオン交換樹脂の再生方法は、マレイン酸およ
びシトラコン酸等の２塩基酸を不純物として含むメタク
リル酸含有抽出液を直接塩基性陰イオン交換樹脂で処理
する方法により、実質上マレイン酸およびシトラコン酸
等の２塩基酸を含まないメタクリル酸を得るのに有効に
利用される。而て本発明の再生方法においては、イオン
交換樹脂層をメタクリル酸抽出用有機溶剤、好ましくは
水不溶性乃至は難溶性有機溶剤で置換し次いで親水性の
溶剤で置換洗浄しているので、最初の置換液からメタク
リル酸を回収することによりメタクリル酸の精製ロスを
少なくし、次いで行なわれる親水性の溶剤との置換によ
り更に行なわれる水との置換を容易にし、これによって
例えばイオン交換樹脂粒が水不溶性打機溶剤等によって
被覆される量を低下せしめ、更に行なわれる陰イオン交
換樹脂のアルカリ再生効率を著しく向上させることがで
きる。また本発明の方法による場合は各工程における洗
浄効率も向上しまたイオン交換樹脂の浮上もない。斯く
してメタクリル酸の精製に有効な、メタクリル酸含有抽
出液と塩基性陰イオン交換樹脂とを接触させる積装方法
が円滑に実施できる。(Functions and Effects) The method for regenerating an ion exchange resin of the present invention involves directly treating a methacrylic acid-containing extract containing dibasic acids such as maleic acid and citraconic acid as impurities with a basic anion exchange resin. It is effectively used to obtain methacrylic acid that does not contain dibasic acids such as upper maleic acid and citraconic acid. In the regeneration method of the present invention, the ion exchange resin layer is replaced with an organic solvent for extracting methacrylic acid, preferably a water-insoluble or poorly soluble organic solvent, and then replaced and washed with a hydrophilic solvent. By recovering methacrylic acid from the replacement liquid, the purification loss of methacrylic acid is reduced, and the subsequent replacement with a hydrophilic solvent facilitates the subsequent replacement with water. It is possible to reduce the amount of coating with an insoluble battering machine solvent and the like, and to significantly improve the efficiency of alkali regeneration of the anion exchange resin. Furthermore, in the case of the method of the present invention, the cleaning efficiency in each step is improved and there is no floating of the ion exchange resin. In this way, the loading method of bringing the methacrylic acid-containing extract into contact with the basic anion exchange resin, which is effective for purifying methacrylic acid, can be carried out smoothly.
（実施例）
以下、実施例をあげて本発明をさらに具体的に説明する
。(Examples) Hereinafter, the present invention will be explained in more detail by giving examples.
実施例１
イソブチレンを出発原料として気相接触酸化して、その
反応生成ガスを冷却凝縮してＩＦ＃られるメタクリル酸
の水溶液から、キシレンを油剤として得られたメタクリ
ル酸含有抽出液を、弱塩基性陰イオン交換樹脂アンバー
リストＡ−２１を５０ｃｃ充填したカラム（２０ｍ／ｍ
φＸ ３０ｃｍ）に空間速度４１／Ｉｈｒの流速で通液
し、得られる処理液中のマレイン酸およびシトラコン酸
の濃度を高速液体クロマトグラフィ（ＩＩＰＬｃ）で分
析したところ入口で各々２８４ｐｐｍ、 ２５１ｐｐｍ
であったマレイン酸、シトラコン酸は検出されなかった
。約４時間通液処理した後、処理原液をキシレンに切換
え同じく空間速度４！／１ｈ「で３０分間カラム内の置
換を行った。次いでキシレンをアセトンに切換え、同じ
く空間速度４１１／ｊｈｒで１時間キシレンの置換及び
イオン交換樹脂（以下、樹脂と略称する）の洗浄を行っ
た。次に水を空間速度７１／Ａｈｒで４０分間通水し十
分に樹脂を洗浄した後、４％苛性ソーダ水溶液を空間速
度３ｊ／ｊｈｒで１時間通液して樹脂の再生を行い、そ
の復水で十分に洗浄した。斯くして再生された樹脂を用
いてメタクリル酸含有抽出液と再接触させた結果、再生
率は当初９８％であり、充分に利用しつることがわかっ
た。Example 1 A methacrylic acid-containing extract obtained by using xylene as an oil agent was obtained from an aqueous solution of methacrylic acid obtained by gas-phase catalytic oxidation using isobutylene as a starting material, cooling and condensing the reaction product gas, and using xylene as an oil agent. A column packed with 50 cc of anion exchange resin Amberlyst A-21 (20 m/m
The concentration of maleic acid and citraconic acid in the resulting treated solution was analyzed by high performance liquid chromatography (IIPLc) and found to be 284 ppm and 251 ppm, respectively, at the inlet.
Maleic acid and citraconic acid were not detected. After about 4 hours of liquid flow treatment, the treatment stock solution was switched to xylene and the space velocity was also 4! /1h'' for 30 minutes. Next, xylene was replaced with acetone, and the xylene was replaced and the ion exchange resin (hereinafter referred to as resin) was washed for 1 hour at the same space velocity of 411/jhr. Next, water was passed for 40 minutes at a space velocity of 71/Ahr to thoroughly wash the resin, and then a 4% caustic soda aqueous solution was passed for 1 hour at a space velocity of 3J/Jhr to regenerate the resin. When the thus regenerated resin was brought into contact with the methacrylic acid-containing extract, the regeneration rate was initially 98%, indicating that it could be fully utilized.
比較例
アセトンによる置換洗浄操作を除いた以外は実施例１と
同じ操作を行った結果、再生中に樹脂が浮き上る現象が
みられ樹脂の再生率も７０％と低かった。Comparative Example The same operation as in Example 1 was carried out except for the replacement washing operation with acetone. As a result, a phenomenon in which the resin floated up during regeneration was observed, and the regeneration rate of the resin was as low as 70%.
実施例２
親水性溶剤としてメタノールを用いた他は実施例１と同
様の方法で実験した結果、樹脂のＩＩＴ生率は９７％で
あった。Example 2 An experiment was carried out in the same manner as in Example 1 except that methanol was used as the hydrophilic solvent, and as a result, the IIT yield of the resin was 97%.
実施例３
メタクリル酸の抽出溶剤としてｎ−へブタンを用いた他
は実施例１と同様の方法で実験した結果樹脂の再生率は
９７％であった。Example 3 An experiment was conducted in the same manner as in Example 1 except that n-hebutane was used as the extraction solvent for methacrylic acid. As a result, the resin regeneration rate was 97%.
実施例４
実施例１と同様の方法で、樹脂を強塩基性陰イオン交換
樹脂アンバーリスト２８に変えて実施したところ、樹脂
の再生率は９８％であった。Example 4 A test was carried out in the same manner as in Example 1 except that the resin was replaced with a strongly basic anion exchange resin Amberlyst 28, and the regeneration rate of the resin was 98%.
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Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Kyowa Gas Chemical Industry Co., Ltd.
Claims (1)
メタクリル酸含有抽出液を塩基性陰イオン交換樹脂処理
してメタクリル酸を精製する方法におけるイオン交換樹
脂の再生方法において、イオン交換樹脂層をメタクリル
酸抽出用有機溶剤で置換した後、親水性の溶剤で置換洗
浄し、更に水洗した後、アルカリ再生することを特徴と
するイオン交換樹脂の再生方法。(1) In a method for regenerating ion exchange resin in a method for purifying methacrylic acid by treating a methacrylic acid-containing extract extracted with an organic solvent from a methacrylic acid-containing aqueous solution with a basic anion exchange resin, the ion exchange resin layer is replaced with methacrylic acid. A method for regenerating an ion exchange resin, which comprises replacing with an organic solvent for extraction, followed by replacement washing with a hydrophilic solvent, further washing with water, and then regenerating with an alkali.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253624A JPH0722714B2 (en) | 1986-10-27 | 1986-10-27 | Regeneration method of ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253624A JPH0722714B2 (en) | 1986-10-27 | 1986-10-27 | Regeneration method of ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63107755A true JPS63107755A (en) | 1988-05-12 |
| JPH0722714B2 JPH0722714B2 (en) | 1995-03-15 |
Family
ID=17253939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61253624A Expired - Fee Related JPH0722714B2 (en) | 1986-10-27 | 1986-10-27 | Regeneration method of ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722714B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012521867A (en) * | 2009-03-27 | 2012-09-20 | ルーサイト インターナショナル ユーケー リミテッド | Treatment method of ion exchange resin |
| CN106489001A (en) * | 2014-07-09 | 2017-03-08 | 夏普株式会社 | Washing machine |
-
1986
- 1986-10-27 JP JP61253624A patent/JPH0722714B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012521867A (en) * | 2009-03-27 | 2012-09-20 | ルーサイト インターナショナル ユーケー リミテッド | Treatment method of ion exchange resin |
| US8835518B2 (en) | 2009-03-27 | 2014-09-16 | Lucite International Uk Limited | Process for the treatment of an ion exchange resin |
| US9821304B2 (en) | 2009-03-27 | 2017-11-21 | Lucite International Uk Limited | Process for the treatment of an ion exchange resin |
| CN106489001A (en) * | 2014-07-09 | 2017-03-08 | 夏普株式会社 | Washing machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0722714B2 (en) | 1995-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2118204C1 (en) | Method of removing corrosive metal impurities from liquid compositions and method of producing carboxylic acid and/or its anhydride | |
| EP1843997B1 (en) | Treatment of an aqueous mixture containing an alkylene oxide with an ion exchange resin | |
| US6242655B1 (en) | Glycol purification | |
| US3959382A (en) | Method for reactivating palladium catalysts | |
| KR100422598B1 (en) | Nitrile Refining Method | |
| US2624699A (en) | Purification of crude acetone | |
| US6187973B1 (en) | Glycol purification | |
| EP0194867B1 (en) | Process for purifying methacrylic acid | |
| JP2752602B2 (en) | Separation method of oxidation catalyst for trimellitic acid production | |
| US6525229B2 (en) | Process for separating ethylene glycol | |
| JPS63107755A (en) | Regeneration of ion exchange resin | |
| US2813130A (en) | Recovery of osmium compounds by adsorption on alumina | |
| US2792344A (en) | Methanol purification | |
| JP2013129613A (en) | Method of producing trialkylene glycol | |
| RU2226429C2 (en) | Selective separation of iron by treatment with ion- exchange resin containing groups of diphosphonic acids | |
| JPS60149558A (en) | Purification of tertiary butylhydro peroxide containing primary and secondary alkylhydro peroxide polutants | |
| US5770777A (en) | Method reducing UV absorption in ethylene glycols, water, and mixtures | |
| JPS6312460B2 (en) | ||
| US3725459A (en) | Process for purifying adiponitrile | |
| JP5438974B2 (en) | Process for treating aqueous mixtures containing dipolar aprotic compounds | |
| JPS647064B2 (en) | ||
| JPS62126151A (en) | Production of methacrylic acid ester | |
| JPH11279095A (en) | Manufacture of bisphenol-a | |
| JPS5830384A (en) | Method for recovering amines in waste water in high concentration | |
| JPS5925361A (en) | Separation of amino acid and mandelic acid form compounded substance of amino acid and mandelic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |