CN107216262A - 一种均相体系中离子液体催化合成甘氨酸的方法 - Google Patents

一种均相体系中离子液体催化合成甘氨酸的方法 Download PDF

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CN107216262A
CN107216262A CN201710253070.1A CN201710253070A CN107216262A CN 107216262 A CN107216262 A CN 107216262A CN 201710253070 A CN201710253070 A CN 201710253070A CN 107216262 A CN107216262 A CN 107216262A
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glycine
ammoniacal liquor
ammonia
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CN107216262B (zh
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张锁江
王慧
孟祥展
张永强
王耀锋
李增喜
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Abstract

本发明涉及一种离子液体催化氯乙酸氨解合成甘氨酸的绿色方法，具体是指以离子液体为催化剂，氯乙酸和氨气(或氨水或碳酸氢铵)为反应原料在均相体系中进行氨解反应生成甘氨酸粗品，经重结晶得纯品甘氨酸。该方法操作简便、催化剂可循环利用、产品易分离、易于工业化生产，为解决甘氨酸合成中催化剂乌洛托品易分解、活性低、副反应严重、回收困难等难题提供了有效的解决途径。

Description

一种均相体系中离子液体催化合成甘氨酸的方法
技术领域
本发明涉及一种离子液体催化氯乙酸氨解合成甘氨酸的绿色方法，属于催化技术领域。
技术背景
甘氨酸是最简单的氨基酸，又名氨基乙酸，是组成人体及动物所需蛋白质的最基本单元，广泛存在于自然界中。甘氨酸作为一种重要的精细化工中间体，广泛应用于农药、医药、食品、饲料等领域。在农药方面，甘氨酸可制取新型农药除草剂草甘磷和植物生长调节剂增甘磷；医药方面，甘氨酸可用于各种氨基酸输液的配方、金霉素缓冲剂、L-多巴(L-DoPa) 和一些重要氨基酸的中间体等；食品方面，可用作食品添加剂、饮料去苦剂、食品抗氧化剂及防腐剂等；除此之外，甘氨酸在饲料添加剂、有机溶剂、日用化工产品中也得到了广泛的应用，是一类非常重要的化学品。
目前合成甘氨酸的方法主要有氯乙酸氨解工艺、Strecker工艺、Hydantion工艺以及生物法工艺等。其中氯乙酸氨化工艺以氯乙酸与氨水为原料，在乌洛托品催化剂作用下制得，反应过程中产生大量无机盐，使得产品的提纯非常困难，并产生富含氯化铵和甲醛(乌洛托品分解产物)的废水，所要求的环保处理费用高。此外，乌洛托品催化剂在反应过程中易分解、难以循环使用，使生产成本增加。Strecker工艺将甲醛水溶液、氰化钠和氯化铵混合后在低温下进行反应，反应结束后加入醋酸使亚氨基乙腈析出，然后溶解在乙醇内，加入硫酸后转化为氨基乙腈硫酸盐，最后加入化学计量的氢氧化钡生成硫酸钡和甘氨酸。该工艺同样存在生产成本高、产品质量差和环境污染严重的缺点。Hydantion工艺的发展源于寻找氢氰酸的替代品，以消除甘氨酸生产的地域局限性，目前技术尚不成熟。生物法制备甘氨酸工艺目前尚处于技术开发阶段，未有工业化的报道。由于氯乙酸氨解工艺简单且对设备要求不高，是目前国内外生产厂家主要采用的工艺。
本发明以氯乙酸、氨水(或氨气、碳酸氢铵)为原料，以系列功能化离子液体为催化剂，在温和的反应条件下合成甘氨酸。合成液经过浓缩后加入甲醇冷却重结晶，得到甘氨酸粗品，将粗品重结晶3次得甘氨酸纯品。本发明具有转化率高、产品易提纯、催化剂不易损失且可循环利用等优点，可用于规模化高效生产甘氨酸。
发明目的及内容
本发明目的是开发一种高效绿色的氯乙酸氨解合成甘氨酸的催化剂。本发明所采用的离子液体催化剂可有效解决乌洛托品催化效率不高、催化剂易损失、副反应严重等问题。本发明涉及一种离子液体催化氯乙酸氨解合成甘氨酸的方法，离子液体阳离子可以为式一结构式中的一种或多种，其中，R1-R32选自烷烃、卤代烃、羟基、芳烃、杂环烃类中的一种，可以相同，也可以不同，其中脂肪链有机取代基团的碳数在1-16之间；所述离子液体的阴离子为式二结构式中的一种或多种。
式一离子液体阳离子结构
式二离子液体阴离子结构(X为卤族元素)
氯乙酸氨解过程中以水、甲醇或乙醇为反应溶剂，离子液体用量与氯乙酸的质量比为 1:20～1:1，氨用量为氨气(或氨水、碳酸氢铵)与氯乙酸的摩尔比为1:1～100:1，氨水浓度为 1％～30％。加料的方式是向氨水或碳酸氢铵溶液中添加氯乙酸溶液，或是向氯乙酸溶液中添加氨水、碳酸氢铵溶液或通入氨气。其中，氯乙酸溶液的浓度为0.01mol/L～50mol/L，碳酸氢铵溶液的浓度为0.01mol/L～30mol/L。若以氨水为原料，氨水滴加速率为每秒1～10滴；若以氨气为原料，氨气的通入速率为每分钟0.1mL～1000mL，若以碳酸氢铵溶液为原料，滴加速率为每秒1～10滴。均相体系的pH为5～13，反应温度为30～100℃，反应时间为0.1～24h。重结晶过程中，甲醇的加入量为浓缩液体积的1～10倍，重结晶温度为0～80℃。
本发明提出的合成甘氨酸的方法，可有效解决乌洛托品催化效率不高、催化剂易损失、副反应严重等问题，具有转化率高、产品易提纯、催化剂不易损失且可循环利用等优点。该方法降低了生产成本，渐少了污染，具有很高的实用价值。
具体实施方式
下面以具体的实施例对本发明进行说明，但本发明的应用不仅局限于实施例所列出的范围。
实施例1
将10g氯乙酸(≥98％)溶于80ml水中置于250ml烧瓶中均匀搅拌，称取1g 1-甲基-3-乙基咪唑醋酸离子液体([Emim][OAc])缓慢加入氯乙酸的水溶液中。将9.5g氨水(25～28％)置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为40℃，同时以每秒1～3滴的速度滴加氨水，维持反应pH在6～8，滴加完成后升温至70℃，保温反应1.5h。将反应液浓缩至50ml，降至室温后加入50ml甲醇，搅拌均匀后降温静置2h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞90％，甘氨酸产率＞95％，甘氨酸纯度＞85％。
实施例2
将10g氯乙酸(≥98％)溶于80ml水中置于250ml烧瓶中均匀搅拌，称取1.25g 1-甲基-3- 丁基咪唑醋酸离子液体([Bmim][OAc])缓慢加入氯乙酸的水溶液中。将10g氨水(25～28％) 置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为45℃，同时以每秒1～3滴的速度滴加氨水，维持反应pH在6～8，滴加完成后升温至80℃，保温反应 1.5h。将反应液浓缩至50ml，降至室温后加入50ml甲醇，搅拌均匀后降温静置2h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞85％，甘氨酸产率＞90％，甘氨酸纯度＞85％。
实施例3
将15g氯乙酸(≥98％)溶于100ml水中置于250ml烧瓶中均匀搅拌，称取2g 1-甲基-3-丁基咪唑甲基咪唑离子液体([Bmim][Im])缓慢加入氯乙酸的水溶液中。将10g氨水(25～28％) 置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为45℃，同时以每秒1～3滴的速度滴加氨水，维持反应pH在6～8，滴加完成后升温至80℃，保温反应 1.5h。将反应液浓缩至50ml，降至室温后加入50ml甲醇，搅拌均匀后降温静置1h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞90％，甘氨酸产率＞90％，甘氨酸纯度＞95％。
实施例4
将15g氯乙酸(≥98％)溶于100ml水中置于250ml烧瓶中均匀搅拌，称取2g胆碱醋酸离子液体([Ch][OAc])缓慢加入氯乙酸的水溶液中。将15g氨水(25～28％)置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为45℃，同时以每秒1～3滴的速度滴加氨水，维持反应pH在6～8，滴加完成后升温至80℃，保温反应1.5h。将反应液浓缩至50ml，降至室温后加入50ml甲醇，搅拌均匀后降温静置1h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞90％，甘氨酸产率＞90％，甘氨酸纯度＞95％。
实施例5
将15g氯乙酸(≥98％)溶于100ml水中置于250ml烧瓶中均匀搅拌，称取1.2g三乙胺醋酸离子液体([N222][OAc])缓慢加入氯乙酸的水溶液中。将15g氨水(25～28％)置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为45℃，同时以每秒1～3 滴的速度滴加氨水，维持反应pH在6～8，滴加完成后升温至80℃，保温反应1.5h。将反应液浓缩至50ml，降至室温后加入50ml甲醇，搅拌均匀后降温静置1h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞90％，甘氨酸产率＞90％，甘氨酸纯度＞90％。
实施例6
将15g氯乙酸(≥98％)溶于100ml水中置于250ml烧瓶中均匀搅拌，称取1.2g胆碱缓慢加入氯乙酸的水溶液中。将15g氨水(25～28％)置于恒压滴液漏斗中，整个反应装置放入恒温搅拌水浴中。控制上述反应液氨化温度为45℃，同时以每秒1～3滴的速度滴加氨水，维持反应 pH在6～8，滴加完成后升温至80℃，保温反应1.5h。将反应液浓缩至50ml，降至室温后加入 50ml甲醇，搅拌均匀后降温静置1h，抽滤后得到白色固体，置于烘箱中干燥，得到甘氨酸产品，氯乙酸转化率＞90％，甘氨酸产率＞90％，甘氨酸纯度＞90％。

Claims (14)

1.一种均相体系中离子液体催化合成甘氨酸的方法，其特征在于以离子液体为催化剂、氯乙酸和氨气(或为氨水或碳酸氢铵)为反应原料、水或甲醇或乙醇为反应溶剂在均相体系中进行氨解反应生成甘氨酸粗品，以甲醇或乙醇为重结晶溶剂进行重结晶纯化得纯品甘氨酸。
2.根据权利要求1所述的方法，其特征在于所述离子液体的阳离子为式一结构式中的一种或多种，其中，R1-R32选自烷烃、卤代烃、羟基、芳烃、杂环烃类中的一种，可以相同，也可以不同，其中脂肪链有机取代基团的碳数在1-16之间；所述离子液体的阴离子为式二结构式中的一种或多种。
3.根据权利要求1所述的方法，其特征在于所述的离子液体用量与氯乙酸的质量比为1:20～1:1。
4.根据权利要求1所述的方法，其特征在于所述的氨用量为氨气(或氨水、碳酸氢铵)与氯乙酸的摩尔比为1:1～100:1。
5.根据权利要求1所述的方法，其特征在于所述的氨水浓度为1％～30％。
6.根据权利要求1所述的方法，其特征在于氯乙酸氨解溶剂为水、甲醇或乙醇。
7.根据权利要求1所述的方法，其特征在于加料的方式是向氨水或碳酸氢铵溶液中添加氯乙酸溶液，或是向氯乙酸溶液中添加氨水、碳酸氢铵溶液或通入氨气。
8.根据权利要求6所述的方法，其特征在于所述的氯乙酸溶液的浓度为0.01mol/L～50mol/L。
9.根据权利要求6所述的方法，其特征在于所述的碳酸氢铵溶液的浓度为0.01mol/L～30mol/L。
10.根据权利要求6所述的方法，其特征在于若以氨水为原料，氨水滴加速率为每秒1～10滴；若以氨气为原料，氨气的通入速率为每分钟0.1mL～1000mL，若以碳酸氢铵溶液为原料，滴加速率为每秒1～10滴。
11.根据权利要求1所述的方法，其特征在于所述的氨解反应的pH为5～13。
12.根据权利要求1所述的方法，其特征在于所述的氨解反应温度为30～100℃。
13.根据权利要求1所述的方法，其特征在于所述的氨解反应时间为0.1～24h。
14.根据权利要求1所述的方法，其特征在于所述的重结晶过程中，甲醇的加入量为浓缩液体积的1～10倍，重结晶温度为0～80℃。
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