CN106914036A - 一种有机酸的提纯方法 - Google Patents
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Abstract
本发明公开一种有机酸的提纯方法，其主要步骤包括：a)将所述有机酸的固体或者原液体加超纯水进行溶解或者稀释，得到有机酸水溶液；b)将所述的有机酸水溶液通过强酸型阳离子树脂柱，得到一次提纯溶液；c)将所述的一次提纯溶液通过螯合树脂柱，得到二次提纯溶液。本发明利用强酸型阳离子树脂与螯合树脂进行联用处理有机酸，最终所处理得到的有机酸中所含的金属离子的含量小于100ppb；本发明使用一根强酸型阳离子树脂柱加上一根螯合树脂柱作为一个单元，可根据需求选择一个或多个单元进行纯化操作；该纯化工艺操作简单，其纯化效果好；且环保，成本低，适于工业化应用。
Description
技术领域
本发明公开一种有机酸的提纯方法。
背景技术
通常，具有酸性的有机化合物被称为有机酸，最常见的有机酸为羧酸(不包括氨基酸)，其可分为脂肪羧酸和芳香羧酸两类。植物中常见的脂肪羧酸有一元、二元、多元羧酸几种，如：酒石酸、草酸、苹果酸、枸椽酸、抗坏血酸(即维生素C)等。脂肪酸多与甘油结合成酯或与高级醇结合成蜡。芳香族羧酸有苯甲酸、水杨酸、咖啡酸等。有机酸中含有的羧基(-COOH)，其对金属离子有着吸附作用，一般工业生产出来的有机酸中金属离子的含量均比较高，金属离子浓度均在几十到几百个ppm。然而在一些特殊领域中，如医药、食品、半导体行业中，需要使用高纯度的有机酸，其中的金属离子含量必须在100ppb以下，这就对有机酸的提纯提出了要求。
目前，常用的有机酸的提纯有溶剂萃取法，液膜分离法，电渗析法，超滤法以及离子交换法等。溶剂萃取法生产简单但是需要使用大量的有机溶剂，对环境污染比较严重，且得到的有机酸的纯度不高。液膜分离法集溶液萃取和反萃取于一体，有高效、节能的优点，但目前采用的载体、表面活性剂或多或少都有一定的毒性，达不到生产食用或医用产品的要求。电渗析法可以得到高纯度有机酸，但是使用时电耗较大，为了减少污染电极板，对溶液的预处理过程要求严格。相对于上述几种方法来说，离子交换法使用方便，能耗低，污染小，并且能够能到纯度较高的有机酸。如，CN101967091A提供了一种提纯有机酸的方法，将乳酸提取液经过活性炭脱色，再使用大孔阳离子树脂去除其中的矿物质，最后经过阴离子交换树脂除去阴离子再过滤精细纯化，最终得到的产品中杂质的浓度为0.1％；CN201210585310对柠檬酸进行了提纯，利用柠檬酸与阳离子交换树脂进行交换，然后采用色谱分离的方法得到的柠檬酸，产物浓度为20％～55％，金属阳离子的总浓度范围为50～1500ppm；CN201310102608也公开了一种柠檬酸提纯方法，其将阳离子交换树脂柱与活性炭柱连接，并进行脱色处理，得到柠檬酸，其中包含Fe离子的浓度低于1ppm。
由于有机酸对金属离子具有螯合能力，使得其中的金属离子含量很难降低。目前市场上，有机酸中的金属离子含量一般在1ppm以上，其相对含量较高，且有机酸提纯效率不高。所以，开发一种能够降低有机酸中金属离子含量，工艺操作简单，纯化效果好的有机酸提纯方法是极为重要和迫切的。
发明内容
本发明提供一种强酸型阳离子交换树脂与螯合树脂联用的方法提纯有机酸，可将有机酸中的金属离子含量降低到100ppb以下，可以有效降低有机酸中的金属离子的含量。本发明中涉及的所需去除的金属离子包括钠离子，镁离子，铝离子，钾离子，钙离子，铁离子，铜离子，锌离子等。
具体为，本发明公开一种提纯有机酸的方法，所述方法的步骤包括：a)将有机酸固体或者原液体加超纯水进行溶解或稀释(超纯水的电阻率大于18MΩ*cm)，稀释比例可按需要调节；b)将有机酸的水溶液首先通过强酸型阳离子树脂柱；c)将步骤b)中所得溶液再经过螯合树脂柱进行处理；d)一根强酸型阳离子树脂柱加一根螯合树脂柱作为一个单元，可增加多个单位进行纯化操作。具体流程可见下图1。
其中，本发明中所采用的强酸型阳离子树脂为含有磺酸基活性基团的阳离子树脂；螯合树脂为含有亚氨基二乙酸活性基团的阳离子树脂。
其中，本发明中所需提纯的有机酸为有机羧酸类以及有机磷酸类，有机羧酸为含有-COOH的有机酸，如乙酸，草酸，水杨酸，酒石酸，丁二酸，柠檬酸，乙二胺四乙酸，甘氨酸等，有机磷酸如氨基三亚甲基膦酸(ATMP)，羟基亚乙基二膦酸(HEDP)，乙二胺四亚甲基膦酸(EDTMP)，2-膦酸丁烷-1,2,3三羧酸(PBTCA)，羟基膦酰基乙酸(HPA)等。
本发明的积极进步效果在于：利用强酸型阳离子树脂与螯合树脂进行联用处理有机酸，最终所处理得到的有机酸中所含的金属离子的含量小于100ppb；可根据需求选择一个或多个单元进行纯化操作；该纯化工艺操作简单，其纯化效果好；无多余能源消耗，环保，成本低。
附图说明
图1显示了本发明提纯方法的工艺流程图。
具体实施方式
下面通过具体实施例进一步阐述本发明的优点，但本发明的保护范围不仅仅局限于下述实施例。
对比例1：将固体酒石酸加超纯水稀释，得到含有2ppm金属离子含量的30％酒石酸水溶液，将其通过强酸型阳离子树脂，流出溶液的金属离子含量为646ppb。
对比例2：将固体酒石酸加超纯水稀释，得到含有2ppm金属离子含量的30％酒石酸水溶液，将其通过螯合树脂，流出溶液的金属离子含量为862ppb。
具体实施例1：将固体柠檬酸加超纯水稀释，得到含有2ppm金属离子含量的50％柠檬酸水溶液，将其通过强酸型阳离子树脂柱，流出溶液继续通过螯合树脂柱，流出溶液的金属离子含量为84ppb。
具体实施例2：将固体丁二酸加超纯水稀释，得到含有1ppm金属离子含量的10％丁二酸水溶液，将其通过强酸型阳离子树脂柱，流出溶液继续通过螯合树脂柱，流出溶液的金属离子含量为37ppb。
具体实施例3：将固体草酸加超纯水稀释，得到含有500ppb金属离子含量的草酸水溶液，将其通过强酸型阳离子树脂柱，流出溶液继续通过螯合树脂柱，流出溶液的金属离子含量为12ppb。
具体实施例4：将固体ATMP加超纯水稀释，得到含有1ppm金属离子含量的5％ATMP水溶液，将其通过强酸型阳离子树脂柱，流出溶液继续通过螯合树脂柱，流出溶液的金属离子含量为25ppb。
具体实施例5：将固体柠檬酸加超纯水稀释，得到含有5ppm金属含量的25％柠檬酸水溶液，将其通过强酸型阳离子树脂柱，流出液继续通过螯合树脂柱，然后再通过新的强酸型阳离子树脂柱，再通过新的螯合树脂柱，流出溶液的金属离子含量为76ppb。
具体实施例6：将固体HEDP加超纯水稀释，得到含有20ppm金属离子含量的5％HEDP水溶液，将其通过强酸型阳离子树脂柱，流出溶液继续通过螯合树脂柱，然后流出溶液再经过新的强酸型阳离子树脂柱，再经过新的螯合树脂柱，得到的溶液的金属离子含量为69ppb。
综上可见，本发明的积极进步效果在于：利用强酸型阳离子树脂与螯合树脂进行联用处理有机酸，最终所处理得到的有机酸中所含的金属离子的含量小于100ppb；该纯化工艺操作简单，其纯化效果好。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。
Claims (5)
1.一种提纯有机酸的方法，其特征在于，所述方法包括步骤：
a.将有机酸的固体或者原液体加超纯水进行溶解或者稀释，得到有机酸水溶液；
b.将所述有机酸水溶液通过强酸型阳离子树脂柱，得到一次提纯溶液；
c.将所述一次提纯溶液通过螯合树脂柱，得到二次提纯溶液。
2.如权利要求1所述的提纯有机酸的方法，其特征在于，所述强酸型阳离子树脂为含有磺酸基活性基团的阳离子树脂。
3.如权利要求1所述的提纯有机酸的方法，其特征在于，所述螯合树脂为含有亚氨基二乙酸活性基团的阳离子树脂。
4.如权利要求1所述的提纯有机酸的方法，其特征在于，所述有机酸为有机羧酸类以及有机磷酸类。
5.如权利要求1所述的提纯有机酸的方法，其特征在于，一根所述强酸型阳离子树脂柱与一根所述螯合树脂柱形成一个单元，可增加多个所述单元进行纯化操作。
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| CN104129831A (zh) * | 2014-07-29 | 2014-11-05 | 南京大学 | 一种利用螯合树脂同时去除和回收重金属离子和有机酸的方法 |
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| CN1071662A (zh) * | 1991-10-18 | 1993-05-05 | 英国石油化学品有限公司 | 从羧酸和羧酸酐中除去碘化物的方法 |
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