复合改性硅胶的制备及用于噻吩类化合物分离的研究

Preparation of composite modified silica gel and its use for the separation of thiophene compounds

摘要

采用固相萃取法分离煤焦油中的噻吩类化合物,将酸和金属复合改性的硅胶作为固相萃取柱填料,以正戊烷与二氯甲烷的混合溶液(体积比为7∶1)作为洗脱溶剂,探究在芳烃等竞争吸附化合物存在下,酸种类、质量浓度、用量及金属种类、负载量、反应温度对硅胶分离噻吩类化合物的影响.结果表明,14mL 50%(质量分数)的 HNO₃及负载10%(质量分数)Cu⁺,60 ℃的反应温度为最优的酸氧化和金属改性条件.HNO₃和Cu⁺复合改性硅胶对煤焦油中BT/C₁₀H₈、3,5-DMBT/C₁₂H₁₀、4-MDBT/C₁₄H₁₀之间的分离因子分别为1.57、1.27、1.26,高于 HNO₃或Cu⁺改性硅胶的分离因子,因此 HNO₃和Cu⁺复合改性硅胶的选择性分离性能更优.通过对比改性前后硅胶的结构,发现HNO₃氧化在硅胶表面引入了含氧官能团,优化了硅胶的孔结构,为 Cu⁺的负载提供了理想的基底,显著提高了Cu⁺在硅胶表面的负载量.复合改性之间存在协同作用,能够进一步提升硅胶对噻吩类化合物的分离性能.

Abstract

The separation of thiophene compounds in coal tar was carried out by solid-phase extraction, in which silica gel modified with acid and metal complexes was used as the packing material of the SPE column, and a mixture of n-pentane and dichloromethane (volume ratio 7∶1) was used as the elution solvent to investigate the effects of the type, mass concentration, and dosage of acid, as well as the type, loading, and reaction temperature of metals on the separation of thiophene compounds by silica gel in the presence of competing adsorption compounds, such as aromatic hydrocarbons. The results showed that the optimal conditions for acid oxidation and metal modification were, respectively, 50% (mass fraction) HNO ₃ concentration, 14 mL dosage, Cu ⁺ as the loaded metal ion, 10% (mass fraction) loading, and a reaction temperature of 60 ℃. The separation factors of BT/C ₁₀H ₈, 3,5-DMBT/C ₁₂H ₁₀, and 4-MDBT/C ₁₄H ₁₀ in coal tar modified by HNO ₃ and Cu ⁺ composite silica gel were 1.57, 1.27, and 1.26 respectively, which were higher than those of HNO ₃ or Cu ⁺ modified silica gel. Therefore, the selective separation performance of HNO ₃ and Cu ⁺ composite modified silica gel is better. By comparing the structure of silica gel before and after modification, it was found that the oxidation of HNO ₃ introduced oxygen-containing functional groups on the silica gel surface, optimized the pore structure of the silica gel, provided an ideal substrate for the loading of Cu ⁺, and significantly increased the loading of Cu ⁺ on the silica gel surface. There was a synergistic effect between the composite modifications, which could further enhance the separation performance of silica gel for thiophene compounds.

关键词

复合改性 / 硅胶 / 选择性分离 / 噻吩类化合物 / 固相萃取

Key words

complex modification / silica / selective separation / thiophene compounds / solid-phase extraction

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基金资助

国家自然科学基金(22278295)

国家自然科学基金(22378291)

中央引导地方科技发展资金项目(YDZJSX2024D025)

山西省科技创新人才团队专项项目(202304051001027)