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)

作　　者：杨永杰 刘萱 杨超 王业双 樊惠玲[1] YANG Yongjie;LIU Xuan;YANG Chao;WANG Yeshuang;FAN Huiling(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan030024,China;College of Environmental Science and Engineering,Taiyuan University of Technology,Jinzhong 030600,China)

机构地区：[1]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024 [2]太原理工大学环境科学与工程学院,山西晋中030600

出　　处：《煤炭学报》2024年第7期3225-3234,共10页Journal of China Coal Society

基　　金：国家自然科学基金资助项目(21878209)。

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(H_(2)S)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H_(2)S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H_(2)S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H_(2)S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H_(2)S的进攻生成ZnS。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(H_(2)S),which has a severe impact on production and 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,the 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 H_(2)S and undergoes reversible chemical reactions,and the introduction of PEI into MOFs is expected to further enhance the H_(2)S adsorption performance.To this end,the 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 H_(2)S adsorption performance was investigated,and the recyclability of the adsorbents was examined.The results showed that the adsorp-tion 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 an unsatisfactory adsorption capacity after PEI load-ing due to their small specific surface area and pore volume or structural damage after PEI loading.The loading of PEI af-fected 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 a better adsorption cycling performance than those with high loa

关 键 词：MOFS 吸附脱硫 PEI 再生循环 

分 类 号：TQ546.5[化学工程—煤化学工程]