硫化氢对负载型钴铈双金属吸附剂脱除模拟煤气中单质汞的促进机理

doi:10.16085/j.issn.1000-6613.2018-0143

化工进展 ›› 2018, Vol. 37 ›› Issue (11): 4493-4499.DOI: 10.16085/j.issn.1000-6613.2018-0143

硫化氢对负载型钴铈双金属吸附剂脱除模拟煤气中单质汞的促进机理

李学谦, 周劲松, 周启昕, 茅珏榛, 曹辉

浙江大学能源清洁利用国家重点实验室, 浙江杭州 310012

收稿日期:2018-01-16 修回日期:2018-06-27 出版日期:2018-11-05 发布日期:2018-11-05
通讯作者: 周劲松,教授,博士生导师,研究方向为生物质利用和煤气脱汞。E-mail:zhoujs@zju.edu.cn。
作者简介:李学谦(1993-),男,硕士研究生,研究方向为煤气脱汞。
基金资助:
国家自然科学基金项目（51576173）。

Promotion mechanism of hydrogen sulfide on elemental mercury removal from simulated syngas by supported cobalt-cerium bimetallic sorbent

LI Xueqian, ZHOU Jinsong, ZHOU Qixin, MAO Juezhen, CAO Hui

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310012, Zhejiang, China

Received:2018-01-16 Revised:2018-06-27 Online:2018-11-05 Published:2018-11-05

摘要/Abstract

摘要： 采用共沉淀法制备了一系列不同配比的钴铈双金属吸附剂（Ce_xCo_yTi），在固定床实验台上探究低温（80～240℃）下脱除模拟煤气中Hg⁰的特性及机理。结果表明，Ce、Co负载比为0.2、0.1时，在120℃、N₂+H₂S气氛下吸附剂表现出最佳的脱汞效果，其效率为95.3%；Ce_0.2Co_0.1Ti在N₂气氛下不仅存在物理吸附而且存在较强的化学吸附；在考察范围内，Ce_0.2Co_0.1Ti脱汞效率随H₂S浓度的增加而增加。采用基于DFT的第一性原理软件VASP模拟H₂S和Hg在Ce_0.2Co_0.1Ti表面的吸附及反应过程，表明Hg化学吸附于吸附剂表面，H₂S易解离形成S，且S极易与吸附态的Hg反应生成HgS，活化能垒为0.214eV，反应遵循Langmuir-Hinshelwood机理。

关键词: 汞, 硫化氢, 吸附, 计算化学

Abstract: Co-Ce bimetallic sorbents were loaded on TiO₂ by precipitation method to remove Hg⁰ and explored the reaction mechanism from simulated syngas at low temperature(80-240℃). Results showed that up to 95.3% Hg⁰ removal efficiency could be obtained over Ce_0.2Co_0.1Ti under N₂+H₂S atmosphere. There is not only physical adsorption but also chemical adsorption over Ce_0.2Co_0.1Ti in N₂ atmosphere. Ce_0.2Co_0.1Ti sorbents exhibited higher removal activity when H₂S was introduced. And mercury removal efficiency increased with increasing H₂S concentration. First principle calculations based on density functional theory (DFT) were used to elucidate the adsorption and mechanism of H₂S and Hg over Ce_0.2Co_0.1Ti sorbents. Hg chemically adsorbed on the sorbent surface. Besides, the reaction mechanism showed that the S formed by the dissociation of H₂S could easily react with adsorbed Hg to form HgS with the activation energy of 0.214eV, following the Langmuir-Hinshelwood mechanism.

Key words: mercury, hydrogen sulfide, adsorption, computational chemistry

中图分类号:

X701

李学谦, 周劲松, 周启昕, 茅珏榛, 曹辉. 硫化氢对负载型钴铈双金属吸附剂脱除模拟煤气中单质汞的促进机理[J]. 化工进展, 2018, 37(11): 4493-4499.

LI Xueqian, ZHOU Jinsong, ZHOU Qixin, MAO Juezhen, CAO Hui. Promotion mechanism of hydrogen sulfide on elemental mercury removal from simulated syngas by supported cobalt-cerium bimetallic sorbent[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4493-4499.

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硫化氢对负载型钴铈双金属吸附剂脱除模拟煤气中单质汞的促进机理

Promotion mechanism of hydrogen sulfide on elemental mercury removal from simulated syngas by supported cobalt-cerium bimetallic sorbent

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