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Sn(II)/PN@AC催化剂:合成、物理化学表征及应用

Sn(II)/PN@AC catalysts: synthesis, physical-chemical characterization, and applications.

作者信息

Wu Yibo, Li Fuxiang, Li Qinbin, Han Yongjun, Wang Li, Ma Wei, Xv Fu

机构信息

College of Chemistry and Environmental Engineering, Pingding Shan University, Pingding Shan China.

College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan China.

出版信息

Turk J Chem. 2021 Oct 19;45(5):1476-1487. doi: 10.3906/kim-2103-9. eCollection 2021.

Abstract

In this study, the novel tin-based catalysts (Sn(II)/PN@AC) were prepared using the phosphorus and nitrogen dual-modified activated carbon as support and SnCl as active compounds, as well as then evaluated in acetylene hydrochlorination. Under the reaction temperature of 180 °C and an acetylene gas hourly space velocity (GHSV-CH) of 30 h, the 15%Sn(II)/PN@AC-550 showed the initial acetylene conversion of 100% and vinyl chloride selectivity over 98.5%. Additionally, the deactivation rate of 15%Sn(II)/PN@AC-550 reached 0.47% h, which was lower than that of 15%Sn(II)/AC-550 (1.02% h), suggesting that PN@AC-550 as novel support can retarded the deactivation of Sn(II)/AC-550 catalysts during acetylene hydrochlorination. Based on the catalytic tests and characterization results (XRD, Raman, BET surface area, TEM, CH-TPD, H-TPR, XPS, FT-IR, TGA, and ICP), it demonstrated that PN@AC-550 as support could effectively improve the dispersion of tin species, retard the formation of coke deposition, lessen the oxidation of SnCl during the preparation process, as well as relatively inhibit the leach of tin species during the reaction. By combing the FTIR results and Rideal-Eley mechanism, we proposed that that HSnCl was transition state of SnCl in catalysis acetylene hydrochlorination and then adsorbed the acetylene to produce the vinyl chloride.

摘要

在本研究中,以磷氮双改性活性炭为载体、SnCl为活性化合物制备了新型锡基催化剂(Sn(II)/PN@AC),并对其进行乙炔氢氯化反应评价。在反应温度为180℃、乙炔气体空速(GHSV-CH)为30 h⁻¹的条件下,15%Sn(II)/PN@AC-550的初始乙炔转化率为100%,氯乙烯选择性超过98.5%。此外,15%Sn(II)/PN@AC-550的失活速率为0.47% h⁻¹,低于15%Sn(II)/AC-550(1.02% h⁻¹),这表明PN@AC-550作为新型载体可延缓Sn(II)/AC-550催化剂在乙炔氢氯化反应中的失活。基于催化测试和表征结果(XRD、拉曼、BET比表面积、TEM、CH-TPD、H-TPR、XPS、FT-IR、TGA和ICP)表明,PN@AC-550作为载体可有效改善锡物种的分散性,延缓焦炭沉积的形成,减少制备过程中SnCl的氧化,以及相对抑制反应过程中锡物种的浸出。结合FTIR结果和里迪尔-埃利机理,我们提出HSnCl是SnCl在催化乙炔氢氯化反应中的过渡态,然后吸附乙炔生成氯乙烯。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/56a8/8596525/1a243840ec76/turkjchem-45-1476-fig001.jpg

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