JP2000015113A - Resin having active methylene group - Google Patents
Resin having active methylene groupInfo
- Publication number
- JP2000015113A JP2000015113A JP10182915A JP18291598A JP2000015113A JP 2000015113 A JP2000015113 A JP 2000015113A JP 10182915 A JP10182915 A JP 10182915A JP 18291598 A JP18291598 A JP 18291598A JP 2000015113 A JP2000015113 A JP 2000015113A
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- Prior art keywords
- group
- resin
- acid
- active methylene
- methylene group
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する分野】本発明は、ニトリル中に存在する
不純物のアルデヒドを効果的にかつ安価に除去すること
ができる樹脂に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin capable of effectively and inexpensively removing an impurity aldehyde present in a nitrile.
【０００２】[0002]
【従来の技術】ニトリル、特に、多くの脂肪族ニトリル
はオレフィンのアンモ酸化により得られ、その際、アル
デヒドが不純物として、微量に含まれる。これらアルデ
ヒドは、該ニトリルの回収工程において系内を汚染した
り、製品を着色させるという問題を引き起こす。また、
近年の化学技術の発達により、より高純度のニトリルが
必要になってきている。しかしながら、ニトリルとそれ
に不純物として含まれるアルデヒドは、比揮発度が小さ
いことが多く、単に蒸留によって分離するには多くの蒸
留段数を必要とし、且つ多くのエネルギーを消費するか
ら極めて不経済となる。そこで、ニトリルからアルデヒ
ドを効果的に除去する樹脂が切望されており、これまで
にも、いくつかの樹脂が用いられている。BACKGROUND OF THE INVENTION Nitriles, especially many aliphatic nitriles, are obtained by ammoxidation of olefins, with aldehydes being present in trace amounts as impurities. These aldehydes cause problems such as contamination of the system and coloring of the product in the nitrile recovery step. Also,
Recent advances in chemical technology have required higher purity nitriles. However, nitriles and aldehydes contained therein as impurities are often low in specific volatility, require a large number of distillation stages to simply separate by distillation, and consume a large amount of energy, which is extremely uneconomical. Therefore, a resin that effectively removes an aldehyde from a nitrile has been desired, and some resins have been used so far.
【０００３】例えば、アクリロニトリル中のアクロレイ
ンを除去する樹脂として、１級及び／又は２級アミノ基
を交換基としてもつポーラス型陰イオン交換樹脂（特公
昭５８−１１０８号）、ゲル型陰イオン交換樹脂（特開
昭５８−１３４０６３号）等、イオン交換樹脂があり、
これらイオン交換樹脂は、系内に新たな不純物を増加さ
せることなく、特異的にアルデヒドを除去することが可
能である。For example, as a resin for removing acrolein in acrylonitrile, a porous anion exchange resin having a primary and / or secondary amino group as an exchange group (Japanese Patent Publication No. 58-1108), a gel anion exchange resin (JP-A-58-134063) and the like.
These ion exchange resins can specifically remove aldehydes without increasing new impurities in the system.
【０００４】しかしながら、１級及び／又は２級アミノ
基を交換基としてもつ陰イオン交換樹脂は、アルデヒド
が樹脂のアミノ基とアミノ−カルボニル反応により共有
結合を形成するため、通常の方法では樹脂のアミノ基か
らアルデヒドを離脱することができない。そのため、イ
オン交換樹脂は再生困難で、使い捨てを前提に使用せざ
るを得ず、処理費用が増加し極めて不経済である。さら
に、アルデヒド除去レベルも不十分なものである。However, in an anion exchange resin having a primary and / or secondary amino group as an exchange group, an aldehyde forms a covalent bond with an amino group of the resin by an amino-carbonyl reaction. The aldehyde cannot be removed from the amino group. For this reason, the ion exchange resin is difficult to regenerate and must be used on the premise of disposable, which increases the processing cost and is extremely uneconomical. Furthermore, the level of aldehyde removal is also inadequate.
【０００５】また、ニトリル中の不純物であるアルデヒ
ドを除去する樹脂として、多価アミンを担持させた陽イ
オン交換樹脂があり、この樹脂は、該ニトリル中のアル
デヒドを吸着させたのち、アルデヒド除去不能となった
イオン交換樹脂を酸性水溶液に接触させて水洗させるこ
とにより再生することができる（特開平１０−７６３８
号）。本発明者らの知見によれば、この樹脂で、到達で
きるアルデヒドの除去レベルは、ゲル型陰イオン交換樹
脂の場合（特開昭５８−１３４０６３号）と同様に十分
なものではない。更に、陽イオン交換樹脂と反応吸着す
る官能基と、アルデヒドと反応する官能基とが共にアミ
ノ基で同じであり、担持させた多価アミンの利用率が低
く、そのため、貫流交換容量は０．０５モル／Ｌ−樹脂
未満であり、満足できるものではない。Further, as a resin for removing aldehyde which is an impurity in the nitrile, there is a cation exchange resin carrying a polyvalent amine, and the resin is not capable of removing the aldehyde after adsorbing the aldehyde in the nitrile. The resulting ion-exchange resin can be regenerated by bringing it into contact with an acidic aqueous solution and washing with water (Japanese Patent Laid-Open No. 10-7638).
issue). According to the findings of the present inventors, the level of aldehyde removal that can be achieved with this resin is not sufficient as in the case of a gel type anion exchange resin (Japanese Patent Application Laid-Open No. 58-14063). Furthermore, the functional group that reacts and adsorbs with the cation exchange resin and the functional group that reacts with the aldehyde are both amino groups, and the utilization rate of the polyamine supported is low. Less than 05 mol / L-resin, which is not satisfactory.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、再生が可能
で、ニトリル中の不純物アルデヒドの除去レベルが高
く、貫流交換容量が０．１５〜０．２５モル／Ｌ−樹脂
程度の十分満足できる、ニトリル精製用の樹脂を提供す
ることを課題とする。SUMMARY OF THE INVENTION The present invention can be regenerated, has a high level of removal of impurity aldehydes from nitriles, and has a satisfactory flow-through exchange capacity of about 0.15 to 0.25 mol / L-resin. It is another object of the present invention to provide a resin for purifying nitrile.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討した結果、同一分子内に活性メチ
レン基及び酸性基を有する化合物を陰イオン交換樹脂に
担持させた樹脂が極めて有効であることを見いだし本発
明に至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a resin in which a compound having an active methylene group and an acidic group in the same molecule is supported on an anion exchange resin has been developed. The present inventors have found that they are extremely effective, and have reached the present invention.
【０００８】即ち、本発明は、同一分子内に活性メチレ
ン基及び酸性基を有する化合物を陰イオン交換樹脂に担
持させてなる樹脂である。That is, the present invention is a resin comprising a compound having an active methylene group and an acidic group in the same molecule supported on an anion exchange resin.
【０００９】ここで活性メチレン基とは、例えばOrgani
c Reactions Vol.15(1967), JOHN WILEY ＆ SONS, INC.
刊行、第２２３頁に記載されているように、Ｘ−ＣＨ
2 −Ｙの一般式を有し、ＸやＹが、ＮＯ2 、ＣＮ、ＣＯ
Ｒ、ＣＯＡｒ、ＣＯＮＨＲ、ＣＯＮＨＡｒ、ＣＯ2 Ｒ、
ＣＯ2 Ｈ、ＳＯ2 、Ｓ、オルト位及び／又はパラ位に電
子吸引性基を有するＡｒ、４級ピリジニウム塩及びその
類似ヘテロ環等の官能基であり、メチレン基がこれらの
官能基と結合しているメチレン基をいう。但し、Ｒはア
ルキル基、Ａｒはアリール基を表す。Here, the active methylene group is, for example, Organi
c Reactions Vol.15 (1967), JOHN WILEY & SONS, INC.
As described on page 223 of the publication, X-CH
Has the general formula 2 -Y, X and Y are, NO 2, CN, CO
R, COAr, CONHR, CONHAr, CO 2 R,
CO 2 H, SO 2 , S, Ar having an electron-withdrawing group at the ortho-position and / or para-position, and quaternary pyridinium salts and similar functional groups such as heterocycles, and a methylene group is bonded to these functional groups. Methylene group. Here, R represents an alkyl group and Ar represents an aryl group.
【００１０】本発明の担持において用いられる化合物
は、活性メチレン基と共に酸性基を有しているが、その
酸性基としての種類は、カルボキシル基、スルホン酸
基、スルフィン酸基、ホスホン酸基、ホスフィン酸基、
などが挙げられる。The compound used in the carrier of the present invention has an acidic group together with an active methylene group. The acidic group includes carboxyl group, sulfonic group, sulfinic group, phosphonic group, phosphine group and phosphine group. Acid groups,
And the like.
【００１１】この様な酸性基の中でもカルボキシル基、
スルホン酸基は上記のＸやＹにも該当し、酸性基も兼ね
ることから、前記化合物は、ＸやＹが酸性基であれば、
必ずしもＸ、Ｙ以外に酸性基を有していなくてもよい。
このような化合物は、構造が単純であり、従って安価で
入手が容易になる等の利点があるので、好ましい。Among such acidic groups, a carboxyl group,
The sulfonic acid group also corresponds to the above-described X and Y, and also serves as an acidic group. Therefore, if X or Y is an acidic group,
It is not always necessary to have an acidic group other than X and Y.
Such a compound is preferable because it has a simple structure, and thus has advantages such as low cost and easy availability.
【００１２】このようなＸやＹが酸性基を兼ねる化合物
の例としては、マロン酸、マロン酸モノエステル、マロ
ン酸モノアミド、シアノ酢酸、アセト酢酸、アセトンジ
カルボン酸、スルホ酢酸、スルホ酢酸エステル、スルホ
酢酸アミド、アセトンスルホン酸等が挙げられる。Examples of compounds in which X or Y also serves as an acidic group include malonic acid, malonic acid monoester, malonic acid monoamide, cyanoacetic acid, acetoacetic acid, acetonedicarboxylic acid, sulfoacetic acid, sulfoacetic acid ester, sulfoacetic acid ester, and sulfoacetic acid ester. Acetamide, acetonesulfonic acid and the like can be mentioned.
【００１３】これらの中でも、酢酸のメチル基の炭素を
前述のＸ、Ｙの官能基で置換したα−置換酢酸、即ち、
マロン酸、マロン酸モノメチル、マロン酸モノエチル、
シアノ酢酸、アセト酢酸、スルホ酢酸、アセトンジカル
ボン酸が、効果並びに入手の容易さから特に好ましい。
これらのα−置換酢酸は単独で用いても、あるいは２種
以上を併用してもよい。Among them, α-substituted acetic acid in which the carbon of the methyl group of acetic acid is substituted by the above-mentioned X and Y functional groups, that is,
Malonic acid, monomethyl malonate, monoethyl malonate,
Cyanoacetic acid, acetoacetic acid, sulfoacetic acid, and acetonedicarboxylic acid are particularly preferred from the viewpoints of effectiveness and availability.
These α-substituted acetic acids may be used alone or in combination of two or more.
【００１４】本発明に使用される陰イオン交換樹脂は、
特にその種類を問わないが、ニトリルを加水分解させな
いためには、弱塩基性又は中塩基性陰イオン交換樹脂が
好ましい。具体的には、レバチットＭＰ６２（商品名、
バイエル社製）、ダイアイオンＷＡ２０（商品名、三菱
化学社製）、ダウエックスＭＷＡ−１（商品名、ダウケ
ミカル社製）等の弱塩基性樹脂、あるいは、レバチット
ＭＰ６４（商品名、バイエル社製）、アンバーライトＩ
ＲＡ６８（商品名、オルガノ社製）等の中塩基性樹脂等
が挙げられる。これらの陰イオン交換樹脂は、市販のも
のを予め、希薄なアルカリで前処理した後、十分水洗し
て使用するのが好ましい。The anion exchange resin used in the present invention comprises:
Although the type thereof is not particularly limited, a weakly basic or neutral basic anion exchange resin is preferable in order not to hydrolyze the nitrile. Specifically, Levatit MP62 (trade name,
Weak basic resins such as Bayer Corporation), Diaion WA20 (trade name, manufactured by Mitsubishi Chemical Corporation), Dowex MWA-1 (trade name, manufactured by Dow Chemical Company), or Levatit MP64 (trade name, manufactured by Bayer) ), Amberlite I
Medium-basic resins such as RA68 (trade name, manufactured by Organo Corporation) and the like. These anion exchange resins are preferably used after pre-treatment of a commercially available anion exchange resin with a dilute alkali in advance, followed by sufficient washing with water.
【００１５】本発明において使用されるニトリルとして
は、脂肪族ニトリルおよび芳香族ニトリルのいずれもが
対象となり、具体的には、例えば、アクリロニトリル、
メタクリロニトリル、アセトニトリルおよびプロピオニ
トリルなどの炭素数２〜４の脂肪族ニトリル、べンゾニ
トリルなどの芳香族ニトリルであり、これらニトリル中
に含まれるアルデヒドはアクロレイン、メタクロレイ
ン、アセトアルデヒド、プロピレンアルデヒドおよびベ
ンズアルデヒドなどである。The nitrile used in the present invention includes both aliphatic nitriles and aromatic nitriles. Specifically, for example, acrylonitrile,
C2-C4 aliphatic nitriles such as methacrylonitrile, acetonitrile and propionitrile, aromatic nitriles such as benzonitrile, and the aldehydes contained in these nitriles are acrolein, methacrolein, acetaldehyde, propylene aldehyde and benzaldehyde. And so on.
【００１６】同一分子内に活性メチレン基及び酸性基を
有する化合物を陰イオン交換樹脂へ担持する方法は、例
えば、イオン交換樹脂と同一分子内に活性メチレン基及
び酸性基を有する化合物の水溶液を、固定層、移動層又
は流動層を用い、回分的または連続的に陰イオン交換樹
脂と接触させることにより行うことができるが、経済
性、操作性の面から、塔類に該イオン交換樹脂を充填し
た固定層を用いて連続的に行う方法が好ましく用いられ
る。A method for supporting a compound having an active methylene group and an acidic group in the same molecule on an anion exchange resin is described, for example, by using an aqueous solution of a compound having an active methylene group and an acidic group in the same molecule as the ion exchange resin. Using a fixed bed, moving bed or fluidized bed, it can be carried out by contacting the anion exchange resin batchwise or continuously, but from the viewpoint of economy and operability, the towers are filled with the ion exchange resin. A method of continuously using the fixed layer is preferably used.
【００１７】この場合、同一分子内に活性メチレン基及
び酸性基を有する化合物の水溶液濃度は、通常０．０１
モル／Ｌ〜飽和濃度、好ましくは、０．１〜５モル／Ｌ
である。また、流通する際の空間速度（ＳＶ）は、通常
０．１〜１０ｈｒ-1、好ましくは０．５〜５ｈｒ-1であ
る。なお、ＳＶとは、流通速度〔ｍＬ・ｈｒ-1〕を充填
量〔ｍＬ〕で除した値である。さらに、同一分子内に活
性メチレン基及び酸性基を有する化合物の流通量は、イ
オン交換樹脂のアミノ基に対して通常１〜１０当量、好
ましくは、２〜５当量である。In this case, the aqueous solution concentration of the compound having an active methylene group and an acidic group in the same molecule is usually 0.01%.
Mol / L to saturation concentration, preferably 0.1 to 5 mol / L
It is. The space velocity (SV) at the time of distribution is usually 0.1 to 10 hr -1 , preferably 0.5 to 5 hr -1 . The SV is a value obtained by dividing the flow rate [mL · hr −1 ] by the filling amount [mL]. Further, the amount of the compound having an active methylene group and an acidic group in the same molecule is usually 1 to 10 equivalents, preferably 2 to 5 equivalents to the amino group of the ion exchange resin.
【００１８】本発明の樹脂へ、精製させたいニトリルを
接触させる方法としては、固定層、移動層又は流動層を
用い、回分的又は連続的に流通させて接触させる方法で
行うことができるが、経済性、操作性の面から、塔類に
該イオン交換樹脂を充填した固定層を用い連続的に行う
方法が好ましい。The nitrile to be purified can be brought into contact with the resin of the present invention by a method of using a fixed bed, a moving bed or a fluidized bed in a batchwise or continuous flow and contacting the resin. From the viewpoints of economy and operability, a method in which the column is continuously used using a fixed bed filled with the ion exchange resin in a column is preferable.
【００１９】この方法における、ニトリルを流通させる
際のＳＶは、ニトリル中のアルデヒド濃度に依存する
が、通常０．１〜２０ｈｒ-1、好ましくは０．５〜１０
ｈｒ-1である。In this method, the SV at the time of flowing the nitrile depends on the aldehyde concentration in the nitrile, but is usually 0.1 to 20 hr -1 , preferably 0.5 to 10 hr -1 .
hr -1 .
【００２０】本発明の樹脂の中で、同一分子内に活性メ
チレン基及び酸性基を有する化合物を陰イオン交換樹脂
にイオン交換反応により担持させた樹脂は、アルデヒド
吸着後のイオン交換樹脂の再生が容易に行える。すなわ
ち、イオン交換反応により担持させた同一分子内に活性
メチレン基及び酸性基を有する化合物の活性メチレン基
と、ニトリル中のアルデヒドとが反応を起こして生成し
た結合物の樹脂からの離脱は、通常の陰イオン交換樹脂
の再生方法により極めて容易に行うことができる。例え
ば、塩基性水溶液に接触させた後、十分に水洗すればよ
い。次いで、同一分子内に活性メチレン基及び酸性基を
有する化合物を再び担持し、蒸留水による洗浄、ニトリ
ルによる水の除去を行った後、再び、アルデヒドを不純
物として含むニトリルの精製に使用することができる。Among the resins of the present invention, a resin in which a compound having an active methylene group and an acidic group in the same molecule is carried on an anion exchange resin by an ion exchange reaction can regenerate the ion exchange resin after aldehyde adsorption. Easy to do. That is, the active methylene group of the compound having an active methylene group and an acidic group in the same molecule carried by the ion exchange reaction and the aldehyde in the nitrile react with each other to release a bond from the resin. It can be carried out extremely easily by the method for regenerating an anion exchange resin. For example, after contacting with a basic aqueous solution, it may be sufficiently washed with water. Next, a compound having an active methylene group and an acidic group in the same molecule is again supported, washed with distilled water and removed with nitrile, and then used again for purification of nitrile containing aldehyde as an impurity. it can.
【００２１】[0021]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
【００２２】実施例１〜７ 弱塩基性陰イオン交換樹脂レバチットＭＰ６２（バイエ
ル社製）１５ｍＬを３本のガラスカラムに充填し、室温
下で、２Ｎ苛性ソーダ水溶液を４５ｍＬ／ｈｒの速度で
４時間通液し、蒸留水１Ｌで十分に洗浄した。カラム上
部より１モル／Ｌの表１に示す同一分子内に活性メチレ
ン基及び酸性基を有する化合物を１５ｍＬ／ｈｒの速度
で４時間通液して該同一分子内に活性メチレン基及び酸
性基を有する化合物をイオン交換樹脂に担持させた。こ
れを蒸留水１Ｌで十分に洗浄後、ニトリルで水を除去し
た。次いで、それぞれカラム上部よりアクリロニトリル
（アクロレイン３ｐｐｍを含む）、メタクリロニトリル
（メタクロレイン３ｐｐｍを含む）、アセトニトリル
（アセトアルデヒド３ｐｐｍを含む）を４５ｍＬ／ｈｒ
の速度で通液させた。通液２日後、カラム下部から流出
してきたニトリルをサンプリングし、不純物として含ま
れるアルデヒドの濃度をガスクロマトグラム装置で測定
した。Examples 1 to 7 15 mL of weakly basic anion exchange resin Levatit MP62 (manufactured by Bayer) was packed in three glass columns, and a 2N aqueous sodium hydroxide solution was passed at room temperature for 4 hours at a rate of 45 mL / hr. The solution was washed with 1 L of distilled water. 1 mol / L of a compound having an active methylene group and an acidic group in the same molecule shown in Table 1 was passed from the top of the column at a rate of 15 mL / hr for 4 hours to allow the active methylene group and the acidic group to flow in the same molecule. The compound was carried on an ion exchange resin. After sufficiently washing this with 1 L of distilled water, water was removed with nitrile. Then, acrylonitrile (containing 3 ppm of acrolein), methacrylonitrile (containing 3 ppm of methacrolein), and acetonitrile (containing 3 ppm of acetaldehyde) at 45 mL / hr from the top of the column.
The liquid was passed at the speed shown in FIG. Two days after the passage, the nitrile flowing out from the lower part of the column was sampled, and the concentration of aldehyde contained as an impurity was measured with a gas chromatogram device.
【００２３】比較例１ 弱塩基性陰イオン交換樹脂レバチットＭＰ６２（バイエ
ル社製）を強酸性陽イオン交換樹脂アンバーリスト１５
（オルガノ社製）に、２Ｎ苛性ソーダを１Ｎ硫酸に、ま
た、同一分子内に活性メチレン基及び酸性基を有する化
合物をエチレンジアミンに変えた以外は、実施例１〜７
と同様に操作を実施した。COMPARATIVE EXAMPLE 1 A weakly basic anion exchange resin Levatit MP62 (manufactured by Bayer) was replaced with a strongly acidic cation exchange resin Amberlyst 15
Examples 1 to 7 except that 2N caustic soda was changed to 1N sulfuric acid and a compound having an active methylene group and an acidic group in the same molecule was changed to ethylenediamine.
The operation was performed in the same manner as described above.
【００２４】比較例２ 同一分子内に活性メチレン基及び酸性基を有する化合物
を担持させないこと以外は、実施例１〜７と同様に操作
を実施した。実施例１〜７及び、比較例１、２の結果を
表１、２、３に示す。Comparative Example 2 The same operation as in Examples 1 to 7 was carried out except that a compound having an active methylene group and an acidic group in the same molecule was not carried. Tables 1, 2, and 3 show the results of Examples 1 to 7 and Comparative Examples 1 and 2.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】実施例８ アルデヒドを不純物として含むニトリルを、アクリロニ
トリル（アクロレイン３ｐｐｍを含む）のみにし、通液
日数を４０日とした以外は、実施例１と同様に操作を実
施した。Example 8 The same operation as in Example 1 was carried out except that the nitrile containing an aldehyde as an impurity was only acrylonitrile (containing 3 ppm of acrolein) and the number of passing days was 40 days.
【００２９】比較例３ アルデヒドを不純物として含むニトリルを、アクリロニ
トリル（アクロレイン３ｐｐｍを含む）のみにし、通液
日数を４０日とした以外は、比較例１と同様に操作を実
施した。実施例８、比較例３の結果を表４に示す。Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that the nitrile containing an aldehyde as an impurity was only acrylonitrile (containing 3 ppm of acrolein) and the number of passing days was 40 days. Table 4 shows the results of Example 8 and Comparative Example 3.
【００３０】[0030]
【表４】 [Table 4]
【００３１】実施例９および比較例４ 弱塩基性陰イオン交換樹脂レバチットＭＰ６２（バイエ
ル社製）１５ｍＬをガラスカラムに充填し、室温下で、
２Ｎ苛性ソーダ水溶液を４５ｍＬ／ｈｒの速度で４時間
通液し、蒸留水１Ｌで十分に洗浄した。カラム上部より
１モル／Ｌマロン酸を１５ｍＬ／ｈｒの速度で４時間通
液してマロン酸をイオン交換樹脂に担持させた。この樹
脂をビーカーに取り、蒸留水１Ｌで十分に洗浄後、アク
リロニトリルで水を除去した。ここに、アクロレイン５
％を含むアクリロニトリル５０ｍＬを加え、室温下、５
時間攪拌し、さらに一晩放置して樹脂に担持されたマロ
ン酸とアクロレインとの反応を完了させた。この樹脂を
再びガラスカラムに充填し、カラム上部よりアクリロニ
トリル（アクロレイン３ｐｐｍを含む）を、１５ｍＬ／
ｈｒの速度で３日通液させ、カラム下部から流出してき
たアクリロニトリルをサンプリングし、不純物として含
まれるアクロレインの濃度が３ｐｐｍであることを確認
した（比較例４）。このイオン交換樹脂を、蒸留水１Ｌ
で十分に洗浄し、２Ｎ苛性ソーダ水溶液を１５ｍＬ／ｈ
ｒの速度で４時間通液して再生して、さらに蒸留水１Ｌ
で洗浄した。マロン酸の担持およびアクリロニトリル
（アクロレイン３ｐｐｍを含む）の通液を比較例４と同
様に行い、通液２日後、カラム下部から流出してきたア
クリロニトリルをサンプリングし、不純物として含まれ
るアクロレインの濃度を実施例１〜７と同様に測定し
た。結果を表５に示す。Example 9 and Comparative Example 4 A glass column was filled with 15 mL of weakly basic anion exchange resin Levatit MP62 (manufactured by Bayer AG), and the mixture was heated at room temperature.
A 2N aqueous solution of caustic soda was passed at a rate of 45 mL / hr for 4 hours, and sufficiently washed with 1 L of distilled water. 1 mol / L malonic acid was passed from the top of the column at a rate of 15 mL / hr for 4 hours to carry the malonic acid on the ion exchange resin. This resin was placed in a beaker, washed sufficiently with 1 L of distilled water, and then water was removed with acrylonitrile. Here, Acrolein 5
% Of acrylonitrile containing
The mixture was stirred for an hour and left overnight to complete the reaction between malonic acid supported on the resin and acrolein. This resin was filled again into a glass column, and acrylonitrile (containing 3 ppm of acrolein) was added from the top of the column to 15 mL /
The solution was allowed to pass for 3 days at a rate of hr, and acrylonitrile flowing out from the lower part of the column was sampled, and it was confirmed that the concentration of acrolein contained as an impurity was 3 ppm (Comparative Example 4). This ion exchange resin is mixed with 1 L of distilled water.
And wash with 2N aqueous sodium hydroxide solution at 15 mL / h
r for 4 hours to regenerate, and further add 1 L of distilled water
And washed. The carrying of malonic acid and the passage of acrylonitrile (containing 3 ppm of acrolein) were carried out in the same manner as in Comparative Example 4. Two days after the passage, acrylonitrile flowing out from the lower part of the column was sampled, and the concentration of acrolein contained as an impurity was measured. It measured similarly to 1-7. Table 5 shows the results.
【００３２】[0032]
【表５】 [Table 5]
【００３３】実施例１０〜１３ ダイアイオンＷＡ２０、ダウエックスＭＷＡ−１、レバ
チットＭＰ６４、アンバーライトＩＲＡ６８各々１５ｍ
Ｌをガラスカラムに充填し、室温下で、２Ｎ苛性ソーダ
水溶液を４５ｍＬ／ｈｒの速度で４時間通液し、蒸留水
１Ｌで十分に洗浄した。カラム上部より１モル／Ｌのマ
ロン酸を１５ｍＬ／ｈｒの速度で４時間通液してイオン
交換樹脂に担持させた。これを蒸留水１Ｌで十分に洗浄
後、アクリロニトリルで水を除去した。次いで、それぞ
れカラム上部よりアクリロニトリル（アクロレイン３ｐ
ｐｍを含む）を４５ｍＬ／ｈｒの速度で通液させた。通
液２日後、カラム下部から流出してきたアクリロニトリ
ルをサンプリングし、不純物として含まれるアクロレイ
ンの濃度を実施例１〜７と同様に測定した。結果を表６
に示す。Examples 10 to 13 Diaion WA20, Dowex MWA-1, Levatit MP64, Amberlite IRA68 each 15 m
L was packed in a glass column, and a 2N aqueous solution of sodium hydroxide was passed through the column at a rate of 45 mL / hr for 4 hours at room temperature, and sufficiently washed with 1 L of distilled water. 1 mol / L malonic acid was passed from the top of the column at a rate of 15 mL / hr for 4 hours to be supported on the ion exchange resin. After sufficiently washing this with 1 L of distilled water, water was removed with acrylonitrile. Next, acrylonitrile (acrolein 3p
pm) was passed at a rate of 45 mL / hr. Two days after the passage, acrylonitrile flowing out from the lower part of the column was sampled, and the concentration of acrolein contained as an impurity was measured in the same manner as in Examples 1 to 7. Table 6 shows the results
Shown in
【００３４】[0034]
【表６】 [Table 6]
【００３５】[0035]
【発明の効果】本発明の、同一分子内に活性メチレン基
及び酸性基を有する化合物を陰イオン交換樹脂に担持さ
せてなる樹脂は、活性メチレン基がアルデヒドと迅速に
反応するため、アルデヒドの除去レベルが高く、また、
陰イオン交換樹脂に反応吸着する官能基は担持化合物中
の酸性基であり、アルデヒドと反応する官能基は担持化
合物中の活性メチレン基であるので、貫流交換容量が十
分大きく、効果的にニトリル中の不純物アルデヒドを除
去することができる。さらに、不純物と反応させた後、
不純物と結合している、同一分子内に活性メチレン基及
び酸性基を有する化合物は、通常のイオン交換樹脂再生
法により容易にイオン交換樹脂から離脱させることがで
きるため、不純物の除去能力を失った樹脂の再生を行う
ことが可能である。According to the resin of the present invention in which a compound having an active methylene group and an acidic group in the same molecule is supported on an anion exchange resin, the active methylene group reacts quickly with the aldehyde to remove the aldehyde. The level is high,
The functional group adsorbing and reacting with the anion exchange resin is an acidic group in the loaded compound, and the functional group reacting with the aldehyde is an active methylene group in the loaded compound. Impurity aldehyde can be removed. Furthermore, after reacting with impurities,
Compounds having an active methylene group and an acidic group in the same molecule, which are bonded to impurities, can be easily separated from the ion-exchange resin by a normal ion-exchange resin regeneration method, and thus have lost the ability to remove impurities. It is possible to regenerate the resin.
【００３６】従って、ニトリル中のアルデヒドを効率的
に精製することができ、工業的に極めて価値が高い。Therefore, the aldehyde in the nitrile can be efficiently purified, which is extremely valuable industrially.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｃ 253/34 Ｃ０７Ｃ 253/34 (72)発明者 上原 与志一 大阪府高石市高砂１丁目６番地 三井化学 株式会社内 Ｆターム(参考） 4H006 AA01 AB80 AD17 4J002 AA031 AA071 EF036 EF066 ET006 EV236 FB231 GD01──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07C 253/34 C07C 253/34 (72) Inventor Yoshikazu Uehara 1-6 Takasago, Takaishi-shi, Osaka Address Mitsui Chemicals, Inc. F term (reference) 4H006 AA01 AB80 AD17 4J002 AA031 AA071 EF036 EF066 ET006 EV236 FB231 GD01
Claims (7)
有する化合物を陰イオン交換樹脂に担持させてなる樹
脂。1. A resin comprising a compound having an active methylene group and an acidic group in the same molecule supported on an anion exchange resin.
るメチレン基である請求項１記載の樹脂。 【化１】 Ｘ−ＣＨ2 −Ｙ ・・・・・〔１〕 （式中、Ｘ及びＹは、ＮＯ2 、ＣＮ、ＣＯＲ、ＣＯＡ
ｒ、ＣＯＮＨＲ、ＣＯＮＨＡｒ、ＣＯ2 Ｒ、ＣＯ2 Ｈ、
ＳＯ2 、Ｓ、オルト位及び／又はパラ位に電子吸引基を
有するＡｒ、４級ピリジニウム塩及びその類似ヘテロ環
からなる官能基のうちのいずれかである。但し、Ｒはア
ルキル基、Ａｒはアリール基を表す。）2. The resin according to claim 1, wherein the active methylene group is a methylene group represented by the following general formula. Embedded image X—CH 2 —Y (1) (wherein X and Y are NO 2 , CN, COR, COA
r, CONHR, CONHAr, CO 2 R, CO 2 H,
SO 2 , S, Ar having an electron-withdrawing group at the ortho-position and / or the para-position, and any one of functional groups comprising a quaternary pyridinium salt and a heterocycle similar thereto. Here, R represents an alkyl group and Ar represents an aryl group. )
基、スルフィン酸基、ホスホン酸基又はホスフィン酸基
である請求項１記載の樹脂。3. The resin according to claim 1, wherein the acidic group is a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group or a phosphinic acid group.
有する化合物が、α−置換酢酸である請求項１記載の樹
脂。4. The resin according to claim 1, wherein the compound having an active methylene group and an acidic group in the same molecule is α-substituted acetic acid.
チル、マロン酸モノエチル、シアノ酢酸、アセト酢酸、
スルホ酢酸又はアセトンジカルボン酸である請求項４記
載の樹脂。5. The method of claim 1, wherein the α-substituted acetic acid is malonic acid, monomethyl malonate, monoethyl malonate, cyanoacetic acid, acetoacetic acid,
The resin according to claim 4, which is sulfoacetic acid or acetone dicarboxylic acid.
有する化合物の担持量が、陰イオン交換樹脂のアミノ基
に対して０．５０〜１．０当量である請求項１記載の樹
脂。6. The resin according to claim 1, wherein the amount of the compound having an active methylene group and an acidic group in the same molecule is 0.50 to 1.0 equivalent relative to the amino group of the anion exchange resin.
去するために使用される、請求項１記載の樹脂。7. The resin according to claim 1, which is used for removing an aldehyde which is an impurity in the nitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18291598A JP4252128B2 (en) | 1998-06-29 | 1998-06-29 | Method for removing aldehyde from crude nitrile containing aldehyde as impurity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18291598A JP4252128B2 (en) | 1998-06-29 | 1998-06-29 | Method for removing aldehyde from crude nitrile containing aldehyde as impurity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000015113A true JP2000015113A (en) | 2000-01-18 |
| JP4252128B2 JP4252128B2 (en) | 2009-04-08 |
Family
ID=16126619
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18291598A Expired - Fee Related JP4252128B2 (en) | 1998-06-29 | 1998-06-29 | Method for removing aldehyde from crude nitrile containing aldehyde as impurity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116824A1 (en) * | 2006-04-06 | 2007-10-18 | Mitsui Chemicals, Inc. | Method of producing acrylamide |
| WO2007116781A1 (en) | 2006-04-06 | 2007-10-18 | Mitsui Chemicals, Inc. | Process for production of acrylamide |
-
1998
- 1998-06-29 JP JP18291598A patent/JP4252128B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116824A1 (en) * | 2006-04-06 | 2007-10-18 | Mitsui Chemicals, Inc. | Method of producing acrylamide |
| WO2007116781A1 (en) | 2006-04-06 | 2007-10-18 | Mitsui Chemicals, Inc. | Process for production of acrylamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4252128B2 (en) | 2009-04-08 |
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