JP2012056856A - Production method of n-vinyl formamide - Google Patents
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本発明は、Ｎ−ビニルホルムアミドの製造方法に関し、詳しくは、Ｎ−（α−置換−エチル）ホルムアミドの熱分解によるＮ−ビニルホルムアミドの製造方法に関する。 The present invention relates to a method for producing N-vinylformamide, and more particularly to a method for producing N-vinylformamide by thermal decomposition of N- (α-substituted-ethyl) formamide.
Ｎ−ビニルホルムアミドは、凝集剤、製紙用薬剤、繊維処理剤、塗料添加剤などとして広く利用されているポリビニルアミン及びポリアミジンの原料として有用な物質であり、Ｎ−（α−置換−エチル）ホルムアミドの熱分解によって製造される。 N-vinylformamide is a substance useful as a raw material for polyvinylamine and polyamidine, which are widely used as flocculants, papermaking agents, fiber treatment agents, paint additives, and the like. N- (α-substituted-ethyl) formamide Manufactured by thermal decomposition.
上記の熱分解は、減圧下、蒸発器でＮ−（α−置換−エチル）ホルムアミドを蒸発させ、得られた蒸気を加熱した反応管に導いて熱分解し、得られたガスを凝縮させる方法によって行われるが、この際、蒸発器や反応管が生成するハルツによって汚染され易いため、製造を中断して洗浄しなければならないという問題がある。 The above pyrolysis is a method in which N- (α-substituted-ethyl) formamide is evaporated with an evaporator under reduced pressure, the resulting vapor is led to a heated reaction tube, and pyrolyzed, and the resulting gas is condensed. However, at this time, since it is easily contaminated by Harz produced by the evaporator and the reaction tube, there is a problem that the production must be interrupted and cleaned.
従来、反応管の汚染を回避する技術については幾つかの提案がなされているが（特許文献１及び２）、蒸発器の汚染を回避する技術については未だ提案されていない。 Conventionally, some proposals have been made on techniques for avoiding contamination of the reaction tube (Patent Documents 1 and 2), but techniques for avoiding contamination of the evaporator have not yet been proposed.
本発明は、上記実情に鑑みなされたものであり、その目的は、Ｎ−（α−置換−エチル）ホルムアミドの熱分解によるＮ−ビニルホルムアミドの製造方法において、原料の蒸発器の汚染を少なくして洗浄回数を減らすことにより、生産性を向上させることにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to reduce contamination of a raw material evaporator in a method for producing N-vinylformamide by thermal decomposition of N- (α-substituted-ethyl) formamide. The purpose of this is to improve productivity by reducing the number of washings.
本発明者らは、鋭意検討した結果、原料のＮ−（α−置換−エチル）ホルムアミドに少量のホルムアミドを混合することにより、蒸発器の伝熱面の汚染を抑えることが出来ることを見出し本発明に到達した。 As a result of intensive studies, the present inventors have found that contamination of the heat transfer surface of the evaporator can be suppressed by mixing a small amount of formamide with the raw material N- (α-substituted-ethyl) formamide. The invention has been reached.
すなわち、本発明の要旨は、減圧下、蒸発器でＮ−（α−置換−エチル）ホルムアミドを蒸発させ、得られた蒸気を加熱した反応管に導いて熱分解するＮ−ビニルホルムアミドの製造方法において、Ｎ−（α−置換−エチル）ホルムアミドにホルムアミドを混合して蒸発器で蒸発させることを特徴とするＮ−ビニルホルムアミドの製造方法に存する。 That is, the gist of the present invention is to produce N-vinylformamide by evaporating N- (α-substituted-ethyl) formamide with an evaporator under reduced pressure, and introducing the resulting vapor into a heated reaction tube to thermally decompose. In N- (α-substituted-ethyl) formamide mixed with formamide and evaporated in an evaporator.
本発明によれば原料の蒸発器の汚染を抑えることが可能になる。 According to the present invention, contamination of the raw material evaporator can be suppressed.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において、出発原料として使用されるＮ−（α−置換−エチル）ホルムアミドのエチル基のα−置換基としては、例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基などの低級アルコキシ基又はシアノ基などが挙げられる。これらの中では、メトキシ基またはシアノ基が好ましい、すなわち、出発原料としては、Ｎ−（α−メトキシエチル）ホルムアミド又はＮ−（α−シアノエチル）ホルムアミドが好ましい。特に、Ｎ−（α−メトキシエチル）ホルムアミドが好ましい。 In the present invention, examples of the α-substituent of the ethyl group of N- (α-substituted-ethyl) formamide used as a starting material include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Examples thereof include lower alkoxy groups such as butoxy group, s-butoxy group and t-butoxy group, or cyano group. Among these, a methoxy group or a cyano group is preferable, that is, N- (α-methoxyethyl) formamide or N- (α-cyanoethyl) formamide is preferable as a starting material. In particular, N- (α-methoxyethyl) formamide is preferable.
熱分解は、公知の方法に従って、減圧下、蒸発器でＮ−（α−置換−エチル）ホルムアミドを蒸発させ、得られた蒸気を加熱した反応管に導いて熱分解し、得られたガスを凝縮させる方法によって行われる。 In the thermal decomposition, N- (α-substituted-ethyl) formamide is evaporated in an evaporator under a reduced pressure according to a known method, and the resulting vapor is led to a heated reaction tube to be thermally decomposed. This is done by the method of condensation.
蒸発器としては、濡れ壁式蒸発器、回転式薄膜蒸発器、蒸発釜、内部にコイル等を有する蒸発釜、シェル＆チューブ対応の熱交換器などが例示される。これらの中では、蒸発率が高く、滞留時間の短い形式のものが好ましく、流下式の濡れ壁式蒸発器や回転式薄膜蒸発器が好ましい。蒸発器の運転圧力は、通常３〜６００ｍｍＨｇ、好ましくは５０〜５００ｍｍＨｇ、運転温度（内壁温度）は、通常８０〜２１０℃、好ましくは１００〜２００℃である。 Examples of the evaporator include a wet wall evaporator, a rotary thin film evaporator, an evaporator, an evaporator having a coil and the like, a shell and tube compatible heat exchanger, and the like. Among these, a type having a high evaporation rate and a short residence time is preferable, and a flow-down type wet wall evaporator and a rotary thin film evaporator are preferable. The operating pressure of the evaporator is usually 3 to 600 mmHg, preferably 50 to 500 mmHg, and the operating temperature (inner wall temperature) is usually 80 to 210 ° C, preferably 100 to 200 ° C.
反応管としては、例えば、加熱手段を備えた空塔または充填塔が使用される。反応器の温度（内壁温度）は、通常２００〜６００℃、好ましくは３００〜５００℃である。また、滞留時間は通常０．０１〜２０秒、好ましくは０．１〜４秒である。 As the reaction tube, for example, an empty tower or a packed tower equipped with heating means is used. The temperature (inner wall temperature) of the reactor is usually 200 to 600 ° C, preferably 300 to 500 ° C. The residence time is usually 0.01 to 20 seconds, preferably 0.1 to 4 seconds.
本発明の最大の特徴は、Ｎ−（α−置換−エチル）ホルムアミドにホルムアミドを混合して蒸発器で蒸発させる点にある。 The greatest feature of the present invention is that N- (α-substituted-ethyl) formamide is mixed with formamide and evaporated in an evaporator.
Ｎ−（α−置換−エチル）ホルムアミドに混合するホルムアミドの量は、通常０．１重量％以上、好ましくは０．５重量％以上、更に好ましくは１重量％以上である。ホルムアミドの量が０．１重量％未満の場合は蒸発器の伝熱面の汚染を抑える効果が小さい。ホルムアミドの混合量の上限は、特に制限されないが、余りにも多い場合は、蒸発器でホルムアミドも蒸発させることに伴ってＮ−ビニルホルムアミドの生産性が低下し、熱分解後のＮ−ビニルホルムアミドの純度が低下し、Ｎ−ビニルホルムアミドの精製の負荷が増大するため、通常３０重量％である。 The amount of formamide to be mixed with N- (α-substituted-ethyl) formamide is usually 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more. When the amount of formamide is less than 0.1% by weight, the effect of suppressing contamination of the heat transfer surface of the evaporator is small. The upper limit of the mixing amount of formamide is not particularly limited, but if it is too large, the productivity of N-vinylformamide decreases as the formamide is evaporated in the evaporator, and the N-vinylformamide after pyrolysis is reduced. The purity is usually 30% by weight because the purity decreases and the purification load of N-vinylformamide increases.
Ｎ−（α−置換−エチル）ホルムアミドにホルムアミドを混合することにより、蒸発器の伝熱面の汚染が抑制される理由は、必ずしも明確ではないが、汚染物質（ハルツ）の溶解度がホルムアミド存在により向上するためであろうと考えられる。 The reason why contamination of the heat transfer surface of the evaporator is suppressed by mixing formamide with N- (α-substituted-ethyl) formamide is not necessarily clear, but the solubility of the contaminant (Hartz) is due to the presence of formamide. It is thought to be for improvement.
また、Ｎ−（α−置換−エチル）ホルムアミドとしてＮ−（α−メトキシエチル）ホルムアミドを使用した場合、ホルムアミドはＮ−（α−メトキシエチル）ホルムアミドと沸点が近く蒸発挙動が近いため伝熱面の下端でも洗浄効果があるメリットがある。この場合、伝熱面の蒸発率をあまり高くしすぎると、ホルムアミドを添加しても伝熱面下端に汚染が生ずる。従って、蒸発率（フィード量に対する蒸発量の比率）は、通常９９％以下、好ましくは９５％以下に抑えるのがよい。なお、Ｎ−（α−置換−エチル）ホルムアミドに混合されたホルムアミドは、熱分解後にＮ−ビニルホルムアミドから容易に分離することが出来る。なお、上記の蒸発率は、以下の式で求められる。 In addition, when N- (α-methoxyethyl) formamide is used as N- (α-substituted-ethyl) formamide, the formamide has a boiling point close to that of N- (α-methoxyethyl) formamide, so that the heat transfer surface is close. There is an advantage that there is a cleaning effect even at the lower end of. In this case, if the evaporation rate of the heat transfer surface is too high, contamination occurs at the lower end of the heat transfer surface even if formamide is added. Therefore, the evaporation rate (ratio of the evaporation amount to the feed amount) is usually 99% or less, preferably 95% or less. The formamide mixed with N- (α-substituted-ethyl) formamide can be easily separated from N-vinylformamide after thermal decomposition. In addition, said evaporation rate is calculated | required with the following formula | equation.
［数１］
蒸発率（％）＝（１−未蒸発量／フィード量）×１００
[Equation 1]
Evaporation rate (%) = (1−non-evaporated amount / feed amount) × 100
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
（蒸発器および反応管）
蒸発器は、３本の垂直管（内径２５ｍｍ、長さ１ｍ）の外部に１６０〜１９０℃のシリコンオイルが循環して加熱する垂直濡れ壁式蒸発器を使用した。反応管は、外部に電気ヒーターを備えた空塔（内径５０ｍｍ、長さ１．５ｍ）を使用した。蒸発器の出口と反応管の入口とは、外部に電気ヒーターを備えた連結管（内径５０ｍｍ）により接続した。
(Evaporator and reaction tube)
The evaporator used was a vertical wet wall evaporator in which silicon oil of 160 to 190 ° C. was circulated and heated outside three vertical tubes (inner diameter 25 mm, length 1 m). As the reaction tube, an empty column (inner diameter: 50 mm, length: 1.5 m) equipped with an electric heater was used. The outlet of the evaporator and the inlet of the reaction tube were connected to each other by a connecting tube (inner diameter: 50 mm) equipped with an electric heater.
（成分分析）
Ｎ−（α−メトキシエチル）ホルムアミド、Ｎ−ビニルホルムアミド、ホルムアミドは液体クロマトグラフィーで絶対検量線法にて定量した。条件は以下の通りである。
(Component analysis)
N- (α-methoxyethyl) formamide, N-vinylformamide, and formamide were quantified by an absolute calibration curve method using liquid chromatography. The conditions are as follows.
カラム：「ＭＣＩＧＥＬ ＯＤＳ」（１ＨＵ ５μ）（４．６ｍｍφ×１５０ｍｍ）
溶離液：０．０１Ｍ−Ｎａ２ＨＰＯ４水溶液（脱気して使用）
検出器：ＵＶ２００ｎｍ及び２２０ｎｍ
Column: “MCIGEL ODS” (1HU 5 μ) (4.6 mmφ × 150 mm)
Eluent: 0.01M-Na 2 HPO 4 aqueous solution (degassed by using)
Detector: UV 200nm and 220nm
実施例１：
蒸発器の運転温度（内壁温度）は１６０〜１９０℃、反応管の温度（内壁温度）は４５０℃、連結管の温度（内壁温度）は２２０℃とした。液状のＮ−（α−メトキシエチル）ホルムアミドに１．５重量％のホルムアミドを添加し、蒸発器の上部から２Ｋｇ／ｈｒの供給速度で供給し、蒸発器の内壁を流下させて蒸発させ、反応管へ導いて熱分解させ、生成した熱分解ガスを急冷液化し、熱分解液を取得した。蒸発器から反応管の全体は反応管で１２０ｍｍＨｇとなるように内部を減圧にし、２週間の連続運転を行った。蒸発器でのワンパスの蒸発率は９０％であった。２週間の連続運転の後、蒸発器を解体してチェックした結果、３本の垂直管の内部はきれいなままで付着物はみられなかった。
Example 1:
The operating temperature (inner wall temperature) of the evaporator was 160 to 190 ° C, the temperature of the reaction tube (inner wall temperature) was 450 ° C, and the temperature of the connecting tube (inner wall temperature) was 220 ° C. 1.5% by weight of formamide is added to liquid N- (α-methoxyethyl) formamide and fed from the top of the evaporator at a feeding rate of 2 Kg / hr, and the inner wall of the evaporator is allowed to flow down to evaporate. It was led to a tube and thermally decomposed, and the generated pyrolysis gas was rapidly liquefied to obtain a pyrolysis solution. The inside of the reaction tube from the evaporator was decompressed so that the entire reaction tube would be 120 mmHg, and continuous operation was performed for 2 weeks. The one-pass evaporation rate in the evaporator was 90%. After two weeks of continuous operation, the evaporator was disassembled and checked. As a result, the inside of the three vertical tubes remained clean and no deposits were observed.
実施例２：
実施例１において、ホルムアミドの添加量を３重量％に変更した以外は、実施例１と同一条件で２週間の連続運転を行った。ワンパスの蒸発率は９０％であった。また、２週間の連続運転の後、蒸発器を解体してチェックした結果、３本の垂直管の内部はきれいなままで付着物はみられなかった。
Example 2:
In Example 1, continuous operation was performed for 2 weeks under the same conditions as in Example 1 except that the amount of formamide added was changed to 3% by weight. The one-pass evaporation rate was 90%. Also, after two weeks of continuous operation, the evaporator was disassembled and checked. As a result, the inside of the three vertical tubes remained clean and no deposits were seen.
実施例３：
実施例１において、ホルムアミドの添加量を１５重量％に変更した以外は、実施例１と同一条件で２週間の連続運転を行った。ワンパスの蒸発率は９０％であった。また、２週間の連続運転の後、蒸発器を解体してチェックした結果、３本の垂直管の内部はきれいなままで付着物はみられなかった。
Example 3:
In Example 1, continuous operation was performed for 2 weeks under the same conditions as in Example 1 except that the amount of formamide added was changed to 15% by weight. The one-pass evaporation rate was 90%. Also, after two weeks of continuous operation, the evaporator was disassembled and checked. As a result, the inside of the three vertical tubes remained clean and no deposits were seen.
上記で得られた熱分解液の軽沸分を除去した後、薄膜蒸発器にて蒸発させ、Ｎ−ビニルホルムアミド６７重量％、ホルムアミド３１重量％、Ｎ−（α−メトキシエチル）ホルムアミド２重量％の混合液を得た。更に、この混合液を、精留塔（１０段）で３ｍｍＨｇ、還流比２の条件で連続精留し、純度９８重量％のＮ−ビニルホルムアミドを得た。 After removing the light boiling component of the pyrolysis solution obtained above, it was evaporated in a thin film evaporator, N-vinylformamide 67% by weight, formamide 31% by weight, N- (α-methoxyethyl) formamide 2% by weight. To obtain a mixed solution. Further, this mixed solution was continuously rectified in a rectification column (10 stages) under the conditions of 3 mmHg and a reflux ratio of 2 to obtain N-vinylformamide having a purity of 98% by weight.
比較例１：
実施例１において、Ｎ−（α−メトキシエチル）ホルムアミドへのホルムアミドの添加を止めた以外は、、実施例１と同一条件で２週間の連続運転を行った。ワンパスの蒸発率は９０％であった。また、２週間の連続運転の後、蒸発器を解体してチェックした結果、３本の垂直管の内部の主に下端から３０ｃｍ部分に茶褐色のタール状物質が付着していると共に、中間部にも一部褐色の塊状物がみられた。これらの附着物を掻き取って重量を測定したところ１５ｇであった。
Comparative Example 1:
In Example 1, continuous operation for 2 weeks was performed under the same conditions as in Example 1 except that the addition of formamide to N- (α-methoxyethyl) formamide was stopped. The one-pass evaporation rate was 90%. In addition, after two weeks of continuous operation, the evaporator was disassembled and checked. As a result, brown tar-like substances adhered to the 30 cm portion mainly from the lower end inside the three vertical tubes, and in the middle portion. Some of them were brown lumps. These attachments were scraped off and weighed to find 15 g.
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| JP2019528324A (en) * | 2016-08-29 | 2019-10-10 | タミンコ・ビー・ヴイ・ビー・エイ | Synthesis of 1-hydroxyethylformamide and N-vinylformamide |
| JP7055138B2 (en) | 2016-08-29 | 2022-04-15 | タミンコ・ビー・ヴイ | Synthesis of 1-hydroxyethylformamide and N-vinylformamide |
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