JP4582641B2 - Polymerization inhibitor and method for inhibiting polymerization of acrylonitrile - Google Patents
Polymerization inhibitor and method for inhibiting polymerization of acrylonitrile Download PDFInfo
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Description
本発明は、アクリロニトリルの製造時、精製時におけるアクリロニトリルの重合を抑制し、さらに重合によって生じる汚れの発生を効果的に抑制するアクリロニトリルの重合抑制剤および重合抑制方法に関するものである。 The present invention relates to an acrylonitrile polymerization inhibitor and a polymerization inhibition method that inhibits the polymerization of acrylonitrile during the production and purification of acrylonitrile, and further effectively suppresses the generation of dirt caused by the polymerization.
アクリロニトリルは、熱、光、その他の要因により極めて重合しやすく、製造、精製工程において、しばしば重合により関連設備内でファウリング（汚れ）が発生しトラブルを起こすことが知られている。汚れが、アクリロニトリルの製造工程、精製工程の製造タンク、蒸留塔（精留塔）、液送配管に付着すると、アクリロニトリルの製造・精製が制御できなくなり、操業に支障を来す。さらに製品品質の低下の原因ともなる。また、関連設備内に付着した重合反応物（汚れ）の除去は、人力による作業で行なわざるを得ないために、作業効率が悪く、その結果、長期間の運転停止を余儀なくされ、経済的損失が大きい。また、そこで、アクリロニトリル関連設備内での汚れを抑制する重合抑制剤および重合抑制方法が数多く提案・実施されてきた。 It is known that acrylonitrile is very easily polymerized due to heat, light, and other factors, and fouling (contamination) often occurs in related equipment during the production and purification processes, causing trouble. If dirt adheres to the acrylonitrile production process, the purification process production tank, the distillation tower (rectification tower), and the liquid feed pipe, the production and purification of acrylonitrile cannot be controlled, which hinders operations. In addition, it may cause a reduction in product quality. In addition, removal of the polymerization reaction product (dirt) adhering to the related equipment is unavoidable due to work by human power, resulting in poor work efficiency. As a result, it is necessary to stop the operation for a long time, resulting in economic loss. Is big. Accordingly, a number of polymerization inhibitors and polymerization suppression methods that suppress contamination in acrylonitrile-related facilities have been proposed and implemented.
一般に重合抑制剤としては、従来、ハイドロキノンやピロガロール（例えば、特許文献１参照）が用いられてきたが、十分な効果を示さず、これに替わる重合抑制剤としてヒドロキシアミン、フェニレンジアミン（例えば、特許文献２参照）、ニトロシルラジカル（例えば、特許文献３参照）の利用が提案されてきた。しかし、依然として十分な重合抑制効果を得るには至っていない。そのため、より優れたアクリロニトリルの重合抑制剤および効果的な重合抑制方法が強く望まれている。 In general, hydroquinone or pyrogallol (for example, see Patent Document 1) has been used as a polymerization inhibitor, but it does not show a sufficient effect, and hydroxyamine and phenylenediamine (for example, patents) as alternative polymerization inhibitors. The use of nitrosyl radicals (see, for example, Patent Document 3) has been proposed. However, a sufficient polymerization inhibitory effect has not yet been obtained. Therefore, a more excellent acrylonitrile polymerization inhibitor and an effective polymerization suppression method are strongly desired.
本発明は、アクリロニトリルの製造時、精製時におけるアクリロニトリルの重合を抑制し、さらに重合によって生じる汚れの発生を効果的に抑制するアクリロニトリルの重合抑制剤および重合抑制方法を提供することにある。 An object of the present invention is to provide an acrylonitrile polymerization inhibitor and a polymerization inhibition method that inhibits the polymerization of acrylonitrile during the production and purification of acrylonitrile, and further effectively suppresses the generation of dirt caused by the polymerization.
本発明者らは、アクリロニトリルの重合特性を詳細に検討した結果、特定のグリシン誘導体と、ハイドロキノンおよび／又はニトロキシルラジカル化合物の併用がアクリロニトリルの重合抑制に有効であることを見出し、本発明を完成するに至った。 As a result of detailed investigation of the polymerization characteristics of acrylonitrile, the present inventors have found that the combined use of a specific glycine derivative and hydroquinone and / or nitroxyl radical compound is effective in inhibiting the polymerization of acrylonitrile, and completed the present invention. It came to do.
すなわち、請求項１に係る発明は、（Ａ）エチレン−Ｎ、Ｎ´−ビスカルボキシメチル−Ｎ、Ｎ´−ジグリシン（エチレンジアミン四酢酸）、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、及びそれらのナトリウム塩、カリウム塩の完全中和塩または部分中和塩から選ばれた少なくとも１種であるグリシン誘導体と、（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物である４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルを有効成分として含むことを特徴とするアクリロニトリル重合抑制剤組成物である。
That is, the invention according to claim 1 includes (A) ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid), diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, and their A glycine derivative that is at least one selected from a completely neutralized salt or a partially neutralized salt of a sodium salt, a potassium salt, and (B) 4-hydroxy-2,2,6 , which is a hydroquinone and / or nitroxyl radical compound , 6-Tetramethylpiperidine-1-oxyl as an active ingredient is an acrylonitrile polymerization inhibitor composition.
請求項２に係る発明は、アクリロニトリルの製造時、精製時において、（Ａ）エチレン−Ｎ、Ｎ´−ビスカルボキシメチル−Ｎ、Ｎ´−ジグリシン（エチレンジアミン四酢酸）、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、及びそれらのナトリウム塩、カリウム塩の完全中和塩または部分中和塩から選ばれた少なくとも１種であるグリシン誘導体と、（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物である４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルを、アクリロニトリルを含む工程液に同時に用いることを特徴とするアクリロニトリル重合抑制方法である。
According to the second aspect of the present invention, during the production and purification of acrylonitrile, (A) ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid), diethylenetriaminepentaacetic acid, triethylenetetra amine hexaacetic acid, and sodium salts thereof, and glycine derivative is at least one selected from the complete neutralization salts or partial neutralization salts of potassium salt, a (B) hydroquinone and / or nitroxyl radical compound 4- A method for inhibiting acrylonitrile polymerization, wherein hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is simultaneously used in a process liquid containing acrylonitrile.
請求項３に係る発明は、請求項２記載のアクリロニトリル重合抑制方法であり、アクリロニトリルを含む工程液に、前記（Ａ）グリシン誘導体と、前記（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物を重量比０．１：９９．９〜９０：１０で用いることを特徴としている。
The invention according to claim 3, a polyacrylonitrile suppression method according to claim 2, in step solution containing acrylonitrile, weight ratio wherein (A) a glycine derivative, the (B) hydroquinone and / or nitroxyl radical compound It is used by 0.1: 99.9-90: 10.
請求項４に係る発明は、請求項２又は３記載のアクリロニトリル重合抑制方法であり、アクリロニトリルを含む工程液に、前記（Ａ）グリシン誘導体と、前記（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物を合計でアクリロニトリルに対して０．０５〜１０００ｐｐｍ添加することを特徴としている。
The invention according to claim 4, a claim 2 or 3 polyacrylonitrile suppression method described in Step solution containing acrylonitrile, the (A) a glycine derivative, the (B) hydroquinone and / or nitroxyl radical compound It is characterized by adding 0.05 to 1000 ppm in total with respect to acrylonitrile.
本発明のアクリロニトリルの重合抑制剤およびアクリロニトリルの重合抑制方法により、アクリロニトリルの製造、精製時におけるアクリロニトリルの重合を効果的に抑制することができ、特にアクリロニトリル製造・精製時の操業の安定化、アクリロニトリルの品質の向上に大きく寄与することができる。 The acrylonitrile polymerization inhibitor and the acrylonitrile polymerization suppression method of the present invention can effectively suppress the polymerization of acrylonitrile during the production and purification of acrylonitrile, and in particular, stabilize the operation during the production and purification of acrylonitrile. It can greatly contribute to quality improvement.
本発明は、アクリロニトリルの製造時、精製時において、特定の（Ａ）グリシン誘導体と、特定の（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物を含むアクリロニトリル重合抑制剤、および、アクリロニトリルを含む工程に特定の（Ａ）グリシン誘導体と、特定の（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物を同時に用いることによって、アクリロニトリルの重合を抑制し、さらにアクリロニトリルの重合によって生じる汚れの発生抑制を効果的に達成し得るアクリロニトリル重合抑制方法である。 The present invention is specific to a process including an acrylonitrile polymerization inhibitor containing a specific (A) glycine derivative, a specific (B) hydroquinone and / or nitroxyl radical compound, and an acrylonitrile at the time of production and purification of acrylonitrile. By simultaneously using (A) the glycine derivative of (A) and the specific (B) hydroquinone and / or nitroxyl radical compound, the polymerization of acrylonitrile is suppressed, and the generation of dirt caused by the polymerization of acrylonitrile is effectively achieved. This is a method for inhibiting acrylonitrile polymerization.
本発明において重合抑制の対象となるアクリロニトリルは、特に限定されるものではなく、通常のアクリロニトリルの製造方法により得られるアクリロニトリルであり、具体的には次の方法により得られるアクリロニトリルである。
（１）プロピレンをアンモ酸化してアクリロニトリルを製造する方法（例えばソハイオ法、ＳＮＡＭ法）、
（２）エチレンクロロヒドリンにシアン化ナトリウムを作用させ、エチレンシアンヒドリンとして脱水してアクリロニトリルを得る方法、
（３）エチレンオキサイドを原料としてシアン化水素をアルカリ性触媒下で液相反応させてエチレンシアンヒドリンとし、これを脱水してアクリロニトリルを得る方法、
（４）アセトアルデヒドとシアン化水素を触媒の存在下で反応させラクトニトリルを得、これを脱水してアクリロニトリルを製造する方法（ラクトニトリル法）
等があげられる。
In the present invention, the acrylonitrile to be subjected to polymerization inhibition is not particularly limited, and is acrylonitrile obtained by an ordinary method for producing acrylonitrile, specifically, acrylonitrile obtained by the following method.
(1) A method for producing acrylonitrile by ammoxidation of propylene (for example, Sohio method, SNA method),
(2) A method of obtaining acrylonitrile by allowing sodium cyanide to act on ethylene chlorohydrin and dehydrating it as ethylene cyanohydrin,
(3) A method in which ethylene cyanide is used as a raw material and hydrogen cyanide is subjected to a liquid phase reaction in the presence of an alkaline catalyst to form ethylene cyanohydrin, which is dehydrated to obtain acrylonitrile.
(4) A method in which acetaldehyde and hydrogen cyanide are reacted in the presence of a catalyst to obtain lactonitrile, which is dehydrated to produce acrylonitrile (lactononitrile method).
Etc.
本発明における（Ａ）グリシン誘導体（以下「（Ａ）成分」とする）は、エチレン−Ｎ、Ｎ´−ビスカルボキシメチル−Ｎ、Ｎ´−ジグリシン（エチレンジアミン四酢酸）、ジエチレントリアミン五酢酸、トリエチレンテトラアミン六酢酸、及びそれらのナトリウム塩、カリウム塩の完全中和塩または部分中和塩から選ばれた少なくとも１種である。
In the present invention, (A) glycine derivative (hereinafter referred to as “component (A)”) is ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid), diethylenetriaminepentaacetic acid, triethylene. It is at least one selected from tetraamine hexaacetic acid, and a completely or partially neutralized salt of a sodium salt or potassium salt thereof.
本発明で用いる（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物（以下「（Ｂ）成分」とする）におけるハイドロキノンは、特に限定されるものではなく通常、工業的に入手できるハイドロキノンが用いられる。 The hydroquinone in (B) hydroquinone and / or nitroxyl radical compound (hereinafter referred to as “component (B)”) used in the present invention is not particularly limited, and industrially available hydroquinone is usually used.
また、（Ｂ）成分のニトロキシルラジカル化合物は、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルである。
Moreover, the nitroxyl radical compound of the (B) component is 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl .
本発明のアクリロニトリルの重合抑制剤は、（Ａ）成分と（Ｂ）成分を含む重合抑制剤であり、通常、両成分を溶剤に溶解させて用いられる。用いる溶剤は、（Ａ）成分と（Ｂ）成分を溶解し、適用するアクリロニトリルの工程の状況を考慮して適宜選択されれば良く、特に限定されるものではないが、通常、水、低級アルコール類のメタノール、エタノール、エチレングリコール、セルソルブ類のメチルセルソルブ、ブチルセルソルブ等が挙げられる。これらの中でも水が好適である。 The polymerization inhibitor for acrylonitrile of the present invention is a polymerization inhibitor containing a component (A) and a component (B), and is usually used by dissolving both components in a solvent. The solvent to be used may be appropriately selected in consideration of the state of the acrylonitrile process in which the component (A) and the component (B) are dissolved, and is not particularly limited, but usually water, lower alcohol Methanol, ethanol, ethylene glycol, and cell solves such as methyl cell solve and butyl cell solve. Of these, water is preferred.
アクリロニトリルの重合抑制剤における（Ａ）成分と（Ｂ）成分の濃度は、特に限定されるものではなく、使用状況を考慮して適宜選択されれば良く、通常、両者の合計で１〜８０重量％である。（Ａ）成分と（Ｂ）成分の濃度が１重量％未満では、本発明の効果を十分に発揮できない場合がある。また、（Ａ）成分と（Ｂ）成分の濃度が８０重量％を超えると、溶液の粘度が高くなり、取扱性の低下や当該重合抑制剤中の（Ａ）成分と（Ｂ）成分の析出が生じて製品安定性が損なわれる場合があり、好ましくない。 The concentration of the component (A) and the component (B) in the polymerization inhibitor of acrylonitrile is not particularly limited and may be appropriately selected in consideration of the use situation. %. When the concentrations of the component (A) and the component (B) are less than 1% by weight, the effects of the present invention may not be sufficiently exhibited. Moreover, when the density | concentration of (A) component and (B) component exceeds 80 weight%, the viscosity of a solution will become high, the handleability fall or precipitation of the (A) component and (B) component in the said polymerization inhibitor. May occur, which may impair product stability.
本発明のアクリロニトリル重合抑制剤の製造は、特に限定されるものではなく、撹拌下、溶剤に（Ａ）成分と（Ｂ）成分を添加して均一溶液として調製して得られる。 The production of the acrylonitrile polymerization inhibitor of the present invention is not particularly limited, and can be obtained by adding the components (A) and (B) to a solvent under stirring and preparing a uniform solution.
本発明のアクリロニトリル重合抑制方法は、アクリロニトリルの製造時、精製時において、（Ａ）グリシン誘導体と、（Ｂ）ハイドロキノンおよび／又はニトロキシルラジカル化合物を、アクリロニトリルを含む工程液に同時に用いることによって、アクリロニトリルの重合抑制および重合によって生じる汚れの発生を効果的に抑制し得るアクリロニトリル重合抑制方法である。 The method for inhibiting acrylonitrile polymerization according to the present invention comprises using acrylonitrile by simultaneously using (A) a glycine derivative and (B) a hydroquinone and / or nitroxyl radical compound in a process liquid containing acrylonitrile during the production and purification of acrylonitrile. This is a method for inhibiting polymerization of acrylonitrile, which can effectively inhibit the occurrence of contamination caused by polymerization.
本発明のアクリロニトリル重合抑制方法は、（Ａ）成分、（Ｂ）成分を同時に用いることにより優れた重合抑制効果を発揮するものであり、その効果は（Ａ）成分と（Ｂ）成分の合計量に対して低比率の（Ａ）成分を（Ｂ）成分と同時に用いることによっても優れた重合抑制効果を発揮する。（Ａ）成分と（Ｂ）成分の添加比率は、通常、０．１：９９．９〜９０：１０を目安として添加され、好ましくは０．５：９９．５〜８０：２０、より好ましくは１：９９〜７０：３０である。（Ａ）成分と（Ｂ）成分の添加比率の範囲は、本発明を実施した結果から見出されたものであり、この範囲外では本発明の充分な効果を得ることができない場合がある。 The acrylonitrile polymerization inhibition method of the present invention exhibits an excellent polymerization inhibition effect by simultaneously using the component (A) and the component (B), and the effect is the total amount of the component (A) and the component (B). On the other hand, an excellent polymerization inhibitory effect is exhibited by using the component (A) at a low ratio simultaneously with the component (B). The addition ratio of the component (A) and the component (B) is usually 0.1: 99.9 to 90:10, preferably 0.5: 99.5 to 80:20, more preferably 1: 99-70: 30. The range of the addition ratio of the component (A) and the component (B) is found from the results of carrying out the present invention, and if it is outside this range, the sufficient effect of the present invention may not be obtained.
（Ａ）成分、（Ｂ）成分の添加量は、適用するアクリロニトリルの工程と必要とする重合抑制の程度を考慮して決定され、通常は（Ａ）成分、（Ｂ）成分のそれぞれが、工程液中に含まれるアクリロニトリルに対して０．０５〜１０００ｐｐｍ、好ましくは、０．１〜５００ｐｐｍ、より好ましくは０．５〜１００ｐｐｍである。また、（Ａ）成分、（Ｂ）成分の合計添加量として、０．１〜２０００ｐｐｍ、好ましくは、０．２〜１０００ｐｐｍ、より好ましくは１〜２００ｐｐｍである。（Ａ）成分、（Ｂ）成分のそれぞれの添加量が０．０５ｐｐｍ未満では、本発明の効果を発揮することができない場合がある。（Ａ）成分、（Ｂ）成分のそれぞれの添加量が１０００ｐｐｍを超えて用いることは、なんら妨げるものではないが、添加量に見合った効果の向上がみられず、経済的な見地から不利なことがある。 The amount of component (A) and component (B) added is determined in consideration of the acrylonitrile step to be applied and the degree of polymerization inhibition required, and usually each of component (A) and component (B) is a step. It is 0.05-1000 ppm with respect to the acrylonitrile contained in a liquid, Preferably, it is 0.1-500 ppm, More preferably, it is 0.5-100 ppm. Moreover, as total addition amount of (A) component and (B) component, it is 0.1-2000 ppm, Preferably, it is 0.2-1000 ppm, More preferably, it is 1-200 ppm. If the addition amount of each of the component (A) and the component (B) is less than 0.05 ppm, the effects of the present invention may not be exhibited. The use of each component (A) and component (B) in excess of 1000 ppm does not hinder the effect, but there is no improvement in the effect corresponding to the amount added, which is disadvantageous from an economic standpoint. Sometimes.
（Ａ）成分、（Ｂ）成分の添加は、（Ａ）成分、（Ｂ）成分をそのまま添加する方法と、それぞれを溶剤に溶解して添加する方法があり、いずれを用いても良い。使用される溶剤は、適用するアクリロニトリルの工程の状況および各成分の溶解性を考慮して適宜選択されれば良く、特に限定されるものではないが、通常、水、低級アルコール類のメタノール、エタノール、エチレングリコール、セルソルブ類のメチルセルソルブ、ブチルセルソルブ等が挙げられ、これらの中でも水が好適である。溶剤に溶解して使用する場合の各成分の濃度は、適用するアクリロニトリルの工程の状況および各成分の溶解性を考慮して適宜選択されれば良く、特に限定されるものではないが、通常、１〜６０重量％である。 There are two methods for adding the component (A) and the component (B). The component (A) and the component (B) can be added as they are, and the method of adding each component dissolved in a solvent can be used. The solvent to be used may be appropriately selected in consideration of the state of the acrylonitrile process to be applied and the solubility of each component, and is not particularly limited, but usually water, methanol of lower alcohols, ethanol , Ethylene glycol, and cell solves such as methyl cell solve and butyl cell solve. Among these, water is preferable. The concentration of each component when used by dissolving in a solvent is not particularly limited as long as it is appropriately selected in consideration of the state of the acrylonitrile process to be applied and the solubility of each component. 1 to 60% by weight.
（Ａ）成分、（Ｂ）成分の添加箇所は、アクリロニトリルの製造工程内においては、アクリロニトリルを含む工程液の一部が重合し、その重合物が付着し汚れとなる箇所の手前であり、具体的にはプロピレンをアンモ酸化してアクリロニトリルを製造するソハイオ法、ＳＮＡＭ法、エチレンシアンヒドリンとして脱水してアクリロニトリルを得る方法、エチレンシアンヒドリンを脱水してアクリロニトリルを得る方法、ラクトニトリルを脱水してアクリロニトリルを製造するラクトニトリル法等の脱水塔あるいはそのフィード液、アクリロニトリル精製塔あるいはそのフィード液、およびその周辺の工程に添加される。また、貯蔵時や輸送時には保管タンク、貯蔵タンク、移送タンク等の貯蔵設備に添加される。 In the acrylonitrile production process, the (A) component and the (B) component are added before the location where a part of the process liquid containing acrylonitrile is polymerized and the polymer adheres and becomes dirty. Specifically, the Sohio method for ammoxidizing propylene to produce acrylonitrile, the SNA method, the method for dehydrating ethylene cyanohydrin to obtain acrylonitrile, the method for dehydrating ethylene cyanohydrin to obtain acrylonitrile, the dehydrating lactonitrile Thus, it is added to a dehydration tower such as a lactonitrile method for producing acrylonitrile or a feed liquid thereof, an acrylonitrile purification tower or a feed liquid thereof, and a process in the vicinity thereof. In addition, it is added to storage facilities such as storage tanks, storage tanks, and transfer tanks during storage and transportation.
（Ａ）成分、（Ｂ）成分の添加方法は、特に限定されるものではなく、通常の薬液注入ポンプを用いて、連続添加方法あるいは間歇添加方法によって添加される。 The addition method of (A) component and (B) component is not specifically limited, It adds by the continuous addition method or the intermittent addition method using a normal chemical solution injection pump.
本発明を実施例により更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（グリシン誘導体）
Ｇ−１：エチレン−Ｎ，Ｎ’−ビスカルボキシメチル−Ｎ，Ｎ’−ジグリシン（エチレンジアミン四酢酸）４Ｎａ塩
Ｇ−２：ジエチレントリアミン五酢酸・５Ｎａ塩
Ｇ−３：トリエチレンテトラアミン六酢酸・６Ｎａ塩
(Glycine derivative)
G-1: Ethylene-N, N′-biscarboxymethyl-N, N′-diglycine (ethylenediaminetetraacetic acid) 4Na salt
G-2: Diethylenetriaminepentaacetic acid / 5Na salt
G-3: Triethylenetetraamine hexaacetic acid, 6Na salt
（ハイドロキノン）
ＨＱ：ハイドロキノン
(Hydroquinone)
HQ: Hydroquinone
（ニトロキシラジカル化合物）
Ｈ−ＴＥＭＰＯ：４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル
(Nitroxy radical compound)
H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
（その他）
ＤＥＨＡ：Ｎ，Ｎ−ジエチルヒドロキシルアミン
ＰＤＡ：Ｎ，Ｎ’−ジ−第二−ブチル−ｐ−フェニレンジアミン
(Other)
DEHA: N, N-diethylhydroxylamine PDA: N, N′-di-secondary-butyl-p-phenylenediamine
（重合抑制試験）
窒素ガス導入バルブとサンプル抜き出しバルブを備えた１００ｍＬのステンレス製オートクレーブにアクリロニトリル１００ｇと表１記載の所定量の（Ａ）グリシン誘導体と（Ｂ）ハイドロキノンあるいは／又はニトロキシラジカル化合物を添加し、窒素ガスを５０ｍＬ／分の割合で導入しながら、系内の酸素を除去した後、窒素ガスで０．１ＭＰａに加圧して両方のバルブを閉じ、１００℃のオイルバスに浸漬し、２時間加熱した。２時間後、反応液約５ｇを採取し、正確に秤量した後、１μｍガラス繊維瀘紙〔ミリポア社（Ｍｉｌｌｉｐｏｒｅ Ｃｏｒｐ．）製〕にて瀘別し、生成したポリマーを分離した。分離したポリマーを５０℃で６時間乾燥した後、秤量し、反応液中の生成ポリマー量（重量ｐｐｍ）を算出した。生成ポリマー量が少ないほど、アクリロニトリルの重合抑制効果が高く、好ましい。結果を表１に示した。
(Polymerization inhibition test)
Add 100 g of acrylonitrile and a predetermined amount of (A) glycine derivative and (B) hydroquinone and / or nitroxy radical compound described in Table 1 to a 100 mL stainless steel autoclave equipped with a nitrogen gas introduction valve and a sample extraction valve, and then add nitrogen gas Was introduced at a rate of 50 mL / min, the oxygen in the system was removed, and the pressure was increased to 0.1 MPa with nitrogen gas, both valves were closed, immersed in an oil bath at 100 ° C., and heated for 2 hours. After 2 hours, about 5 g of the reaction solution was collected and weighed accurately, and then separated by 1 μm glass fiber paper (Millipore Corp.) to separate the produced polymer. The separated polymer was dried at 50 ° C. for 6 hours and then weighed to calculate the amount of polymer produced (weight ppm) in the reaction solution. The smaller the amount of polymer produced, the higher the polymerization inhibitory effect of acrylonitrile, which is preferable. The results are shown in Table 1.
Claims (4)
The process solution containing acrylonitrile, the (A) and glycine derivative, wherein (B) acrylonitrile polymerization of hydroquinone and / or 0.05~1000ppm claim 2 or 3 wherein added to acrylonitrile in the total nitroxyl radical compound Suppression method.
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| US12098070B2 (en) | 2019-04-02 | 2024-09-24 | Ecolab Usa Inc. | Pure chlorine dioxide generation system with reduced acid usage |
| US12304980B2 (en) | 2022-04-01 | 2025-05-20 | Ecolab Usa Inc. | Antifoulant compositions for vapor-space applications |
| US12344581B2 (en) | 2022-04-01 | 2025-07-01 | Ecolab Usa Inc. | Antifoulant compositions for high-severity processing of vinylic monomer streams |
| US12428360B2 (en) | 2022-04-01 | 2025-09-30 | Ecolab Usa Inc. | Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers |
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| JP6138087B2 (en) * | 2014-06-04 | 2017-05-31 | 伯東株式会社 | Piperidine-1-oxyls-containing polymerization inhibitor composition with improved long-term stability of polymerization inhibition effect and polymerization inhibition method using the same |
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| JPS4834824A (en) * | 1971-09-14 | 1973-05-22 | ||
| JPS60190406A (en) * | 1982-05-03 | 1985-09-27 | モンサント コンパニ− | Improved stopping and reopening method for radical group polymerization |
| EP0140519A1 (en) * | 1983-09-02 | 1985-05-08 | Pfizer Inc. | Use of chelating agents in water desalination |
| JPS60220345A (en) * | 1984-04-17 | 1985-11-05 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photosensitive material |
| US4711735A (en) * | 1986-09-12 | 1987-12-08 | Gulley Harold J | Coolant additive with corrosion inhibitive and scale preventative properties |
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| JP3566380B2 (en) * | 1995-02-20 | 2004-09-15 | 三新化学工業株式会社 | Method for producing 3- [2- (benzothiazolyl) thio] propionic acid |
| JPH0967311A (en) * | 1995-08-31 | 1997-03-11 | Nippon Shokubai Co Ltd | Prevention of polymerization of acrylic esters |
| US5550272A (en) * | 1995-10-02 | 1996-08-27 | General Electric Company | Method for hydrosilating unsaturated monomers |
| WO1997016464A1 (en) * | 1995-10-27 | 1997-05-09 | Basf Aktiengesellschaft | Use of polycarboxylic acid semi-amides as scale inhibitors |
| JP3586503B2 (en) * | 1995-10-30 | 2004-11-10 | 三菱レイヨン株式会社 | Method for producing tertiary butyl acrylamide |
| JPH101660A (en) * | 1995-12-22 | 1998-01-06 | Nitto Chem Ind Co Ltd | Chelating agent and cleaning agent using the same |
| JP2000026391A (en) * | 1998-07-08 | 2000-01-25 | Hakuto Co Ltd | Method for controlling contamination in acrylonitrile manufacturing process |
| JP2000034267A (en) * | 1998-07-16 | 2000-02-02 | Asahi Chem Ind Co Ltd | Prevention of polymerizing nitriles |
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| US12098070B2 (en) | 2019-04-02 | 2024-09-24 | Ecolab Usa Inc. | Pure chlorine dioxide generation system with reduced acid usage |
| US12304980B2 (en) | 2022-04-01 | 2025-05-20 | Ecolab Usa Inc. | Antifoulant compositions for vapor-space applications |
| US12344581B2 (en) | 2022-04-01 | 2025-07-01 | Ecolab Usa Inc. | Antifoulant compositions for high-severity processing of vinylic monomer streams |
| US12428360B2 (en) | 2022-04-01 | 2025-09-30 | Ecolab Usa Inc. | Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers |
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