杨永杰,刘萱,杨超,等. MOFs负载聚乙烯亚胺(PEI)对硫化氢的吸附[J]. 煤炭学报,xxxx,xx(x): x−xx. doi: 10.13225/j.cnki.jccs.2023.0351
引用本文: 杨永杰,刘萱,杨超,等. MOFs负载聚乙烯亚胺(PEI)对硫化氢的吸附[J]. 煤炭学报,xxxx,xx(x): x−xx. doi: 10.13225/j.cnki.jccs.2023.0351
YANG Yongjie,LIU Xuan,YANG Chao,et al. Adsorption of hydrogen sulfide by MOFs loaded with polyethyleneimine (PEI)[J]. Journal of China Coal Society,xxxx,xx(x): x−xx. doi: 10.13225/j.cnki.jccs.2023.0351
Citation: YANG Yongjie,LIU Xuan,YANG Chao,et al. Adsorption of hydrogen sulfide by MOFs loaded with polyethyleneimine (PEI)[J]. Journal of China Coal Society,xxxx,xx(x): x−xx. doi: 10.13225/j.cnki.jccs.2023.0351

MOFs负载聚乙烯亚胺(PEI)对硫化氢的吸附

Adsorption of hydrogen sulfide by MOFs loaded with polyethyleneimine (PEI)

  • 摘要: 煤炭清洁高效利用是当下煤炭资源发展的主题,煤炭加工利用过程中会产生以硫化氢(H2S)为主的硫化物,对生产和环境造成了不利影响。近年来,吸附脱硫因其高脱硫效率、高精度、操作简单等优点成为广泛使用的脱硫方法。金属−有机框架材料(MOFs)具有大的比表面积和孔隙率、易于修饰和功能化的优势,在气体吸附领域具有很大的潜力。聚乙烯亚胺(PEI)是同时含有伯、仲、叔胺的高分子聚合物,对H2S有强亲和力并发生可逆的化学反应,将PEI引入MOFs中有望进一步提升H2S吸附性能。为此,采用浸渍法制备了PEI负载的MIL-101(Cr)、UiO-66、MOF-801、ZIF-8吸附剂,研究了载体类型和PEI负载量对H2S吸附性能的影响,考察了吸附剂的循环使用能力。结果表明,负载PEI后,所有载体的吸附容量均有所提高,ZIF-8提高的最多,归因于ZIF-8载体本身大的比表面积、孔体积、负载后晶体结构的保持以及PEI与ZIF-8之间的相互作用。而其余MOFs由于比表面积和孔体积较小或负载PEI后结构发生破坏,负载PEI之后的吸附容量不理想。PEI的负载量会影响ZIF-8的孔隙结构和骨架的稳定性;50%(质量分数)PEI负载后的ZIF-8穿透硫容最高,为56.3 mg/g,是载体本身的55倍。再生循环实验表明,负载PEI的ZIF-8只能实现极少部分再生,并且负载量低的吸附剂的吸附循环性能比负载量高的更好,PEI的引入使ZIF-8更易遭受H2S的进攻生成ZnS。

     

    Abstract: The development of coal resources is currently focused on the clean and efficient use of coal. Coal processing and use generates sulfides, primarily hydrogen sulfide (H2S), which has a severe impact on production and the environment. Adsorption desulfurization has become a popular desulfurization process in recent years because of its high desulfurization effectiveness, high precision, and ease of operation. With their large specific surface area and porosity, ease of modification and functionalization, metal-organic frameworks(MOFs) have great potential in the field of gas adsorption. The introduction of polyethyleneimine (PEI), a polymer containing both primary, secondary and tertiary amines, has a strong affinity for H2S and undergoes reversible chemical reactions, and the introduction of PEI into MOFs is expected to further enhance the H2S adsorption performance. To this end, PEI-loaded MIL-101(Cr), UiO-66, MOF-801, and ZIF-8 adsorbents were prepared by the impregnation method. The effect of carrier type and PEI loading on the H2S adsorption performance was investigated, and the recyclability of the adsorbents was examined. The results showed that the adsorption capacity of all carriers increased after PEI loading, with ZIF-8 increasing the most, which was attributed to the large specific surface area and pore volume of the ZIF-8 carrier itself, the maintenance of the crystal structure after loading, and the interaction between PEI and ZIF-8. The rest of the MOFs showed unsatisfactory adsorption capacity after PEI loading due to their small specific surface area and pore volume or structural damage after PEI loading. The loading of PEI affects the pore structure and skeleton stability of ZIF-8; the highest ZIF-8 breakthrough capacity after 50% PEI loading was 56.3 mg/g, which is 55 times higher than the carrier itself. Regeneration cycling experiments showed that ZIF-8 loaded with PEI could only partially regenerate, that the adsorbent with low loadings had better adsorption cycling performance than those with high loadings, and that the introduction of PEI made ZIF-8 more susceptible to the attack of H2S to form ZnS.

     

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