CN104399438B - 碳纳米管吸附填料、其制备方法及应用 - Google Patents

碳纳米管吸附填料、其制备方法及应用 Download PDF

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CN104399438B
CN104399438B CN201410679918.3A CN201410679918A CN104399438B CN 104399438 B CN104399438 B CN 104399438B CN 201410679918 A CN201410679918 A CN 201410679918A CN 104399438 B CN104399438 B CN 104399438B
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李旭
龙惊惊
王远
沈丽红
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Shenyang Research Institute of Chemical Industry Co Ltd
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Abstract

本发明涉及分离纯化技术领域，具体公开一种碳纳米管吸附填料，其制备方法以及应用。本发明的碳纳米管吸附填料通过以下方式制备：将碳纳米管、核桃壳粉末、蓖麻壳粉末、硅藻土与海藻酸钠水溶液混合，形成水溶胶；将所述水溶胶滴入氯化钙水溶液，形成为凝胶球的碳纳米管吸附填料。如此得到的碳纳米管吸附填料既克服了单独使用碳纳米管的缺陷，还赋予吸附填料抗压能力和化学稳定性。非常适合用于通过色谱柱吸附法分离纯化天然产物，能够获得良好的分离效果且降低了制备成本。

Description

碳纳米管吸附填料、其制备方法及应用
技术领域
本发明涉及色谱分离技术领域，具体公开一种包含碳纳米管的填料，以及其制备方法，尤其可应用于色谱吸附柱。
背景技术
现阶段，天然产物的分离纯化仍存在分离效率低，回收率差，分离材料单一等缺陷。所以亟需寻找一种高效，低价的新型分离材料。柱层析技术，又称柱色谱技术，是对混合物进行分离纯化的一种手段。其广泛应用于生物、医药、食品、能源、材料等领域。
碳纳米管(carbonnanotubes，CNT)是日本NEC公司的电镜专家饭岛于1991年从电弧法生产的碳纤维中发现的一种新型的碳晶体。在结构上，它是由含六边形网格的石墨片层卷曲而成的无缝纳米级圆管，两端由五边形或七边形封闭。碳纳米管由于其疏松多孔的结构，巨大的比较面积，高的热稳定性和机械稳定性，在分离科学中具有广泛的应用前景和开发潜能。但由于其高昂的价格限制了单独应用碳纳米管作为分离纯化填料中的应用。而且单独使用碳纳米管还存在死吸附，样品不易洗脱等问题。
发明内容
为解决天然产物分离纯化过程复杂的问题，本发明提供一种碳纳米管凝胶球的新型色谱柱填料。
本发明一方面提供一种碳纳米管吸附填料的制备方法，包括：将碳纳米管、核桃壳粉末、蓖麻壳粉末、硅藻土与海藻酸钠水溶液混合，形成水溶胶；将所述水溶胶滴入氯化钙水溶液，形成为凝胶球的碳纳米管吸附填料。
一些实施例中，所述碳纳米管、核桃壳粉末、蓖麻壳粉末、硅藻土的用量分别可以为每50mL海藻酸钠水溶液0.5-1.5g、0.1-0.5g、0.1-0.5g、0.1-0.2g。
一些实施例中，所述核桃壳粉末、蓖麻壳粉末大小可以为200目-400目。
一些实施例中，所述海藻酸钠水溶液的浓度可以为0.8-5％(w/v)。
一些实施例中，所述碳纳米管可以包括单壁碳纳米管、双壁碳纳米管、多壁碳纳米管，或它们的任意组合。
一些实施例中，所述氯化钙水溶液的浓度可以为0.1-0.5M。
本发明另一方面提供一种碳纳米管吸附填料，其通过本发明的制备方法获得，并且所述凝胶球的粒径为1.2-2.0mm。
本发明再一方面提供一种色谱分离方法，使用本发明的所述碳纳米管吸附填料作为色谱柱填料。
本发明还提供一种色谱分离洋金花生物碱的方法，使用本发明的所述碳纳米管吸附填料填充的色谱吸附柱，并依次以水、5柱体积10％的乙醇、5柱体积20％的乙醇、4柱体积30％的乙醇和6柱体积40％的乙醇洗脱。
本发明将碳纳米管制成凝胶球形式，并在凝胶球的形成中添加核桃壳粉末和蓖麻壳粉末，既克服了单独使用碳纳米管的缺陷，还赋予吸附填料抗压能力和化学稳定性。非常适合用于通过色谱柱吸附法分离纯化天然产物，能够获得良好的分离效果且降低了制备成本。
附图说明
图1示出根据本发明一个实施例的碳纳米管凝胶球吸附填料，每个凝胶球直径约为1.5mm。
具体实施方式
本发明介绍了一种新型分离材料，在碳纳米管的基础上进行改进，用于天然产物的分离纯化，可以达到良好的分离效果并降低了制备成本。
本发明将碳纳米管海藻酸钠的水溶液滴加入氯化钙中，钙离子会与钠离子发生置换反应，生成不溶于水的海藻酸钙。因此将海藻酸钠以注射器滴加入氯化钙溶液之后会生成水滴状的凝胶球。
进一步地，在制作凝胶球的过程中加入核桃壳和蓖麻子壳。核桃壳和蓖麻壳经筛选、粉碎处理加工制成200目-400目的颗粒。其表面多微孔、吸附效果较好，能够赋予凝胶球具有良好的抗压能力和化学性质稳定，且不含有毒物质，在酸、碱、水中溶解量很小，不会引起水质恶化现象。
碳纳米管吸附填料的制备
根据本发明的原理，可以使0.5-1.5g的碳纳米管、0.1-0.5g的核桃壳粉末、0.1-0.5g的蓖麻壳粉末以及0.1-0.2g的硅藻土与50mL0.8-5％(w/v)的海藻酸钠水溶液混合。
将混合溶液置于磁力搅拌器中，以50-150rpm/min的转速室温搅拌10-60min。用注射器吸取混合溶液，滴加至0.1-0.5M的氯化钙水溶液中，形成凝胶球。图1示出该凝胶球的图片，可见该凝胶球的粒径在1.2-2.0mm之间，优选为约1.5mm。
分离纯化实验
根据本发明的一个实施例，可以将碳纳米管凝胶球吸附填料用于分离纯化洋金花生物碱。
洋金花生物碱的主要成份是阿托品和山莨菪碱。本实验采用乙醇冷浸的方法提取粗提物，之后用酸调节溶液的pH值使生物碱变成盐溶解于水中，再将酸水碱化并用二氯甲烷萃取生物碱。
具体实验步骤如下：
1.取500g洋金花生药材干燥粉碎，加入5L80％的乙醇水溶液冷浸提取48h。提取结束后采用滤纸过滤，提取重复2次，合并提取液，-0.09Mpa减压50℃旋转蒸发至干，置烘箱中105℃烘干3h。得到的粗提物浸膏为深棕色黏稠状固体，称重。
2.将粗提物浸膏用约300mL10％的乙酸液调pH至3。用二氯甲烷萃取三次。分别合并二氯甲烷液和酸水溶液，得到二氯相和酸水相。
3.酸水相加入约50mL氨水调节pH值到9。中和之后的水相用二氯萃取5次，合并二氯甲烷相。将溶液减压浓缩至干，即得到生物碱。
4.将生物碱分别用水，10％的乙醇5BV(柱体积)，20％的乙醇5BV，30％的乙醇4BV，40％的乙醇6BV洗脱碳纳米管凝胶球柱。
大部分的阿托品和山莨菪碱在20％-40％之间洗脱。最高含量的阿托品在20％的乙醇-水洗脱液中，最高含量的山莨菪碱在40％的乙醇-水洗脱液中。在洗脱液中杂质在水份含量为95.4％(W/V)，在10％的乙醇中为89.2％。
通过碳纳米管凝胶球分离后，阿托品和山莨菪碱的纯度分别达到83.55％(阿托品的质量/洗脱液的干重)和90.46％。回收率为88.21％和89.24％。分离提纯效果良好。
以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所作出的各种其他相应的改变与变形，均应包含在本发明权利要求的保护范围内。

Claims (7)

1.一种碳纳米管吸附填料的制备方法，其特征在于，包括：
将碳纳米管、核桃壳粉末、蓖麻壳粉末、硅藻土与海藻酸钠水溶液混合，形成水溶胶；
将所述水溶胶滴入氯化钙水溶液，形成为凝胶球的碳纳米管吸附填料；
所述碳纳米管、核桃壳粉末、蓖麻壳粉末、硅藻土的用量分别为每50mL海藻酸钠水溶液0.5-1.5g、0.1-0.5g、0.1-0.5g、0.1-0.2g；
所述海藻酸钠水溶液的浓度为0.8-5％(w/v)。
2.如权利要求1所述的制备方法，其特征在于，所述核桃壳粉末、蓖麻壳粉末大小为200目-400目。
3.如权利要求1所述的制备方法，其特征在于，所述碳纳米管包括单壁碳纳米管、多壁碳纳米管，或它们的任意组合。
4.如权利要求1所述的制备方法，其特征在于，所述氯化钙水溶液的浓度为0.1-0.5M。
5.权利要求1-4所述的制备方法获得的碳纳米管吸附填料，其特征在于，所述凝胶球的粒径为1.2-2.0mm。
6.一种色谱分离方法，其特征在于，使用权利要求5所述的碳纳米管吸附填料作为色谱柱填料。
7.一种色谱分离洋金花生物碱的方法，其特征在于，使用权利要求5所述的碳纳米管吸附填料填充的色谱吸附柱，并依次以水、5柱体积10％的乙醇、5柱体积20％的乙醇、4柱体积30％的乙醇和6柱体积40％的乙醇洗脱。
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