Ni/Fe/Co助剂对ZnO/MCM-41高温煤气脱硫过程中放硫的抑制作用及改性脱硫剂再生行为  

Inhibition effect of Ni/Fe/Co additives on sulfur-emission behavior during coal gas desulfurization over ZnO/MCM-41 at high temperatures and the regeneration behavior of modified sorbents

作　　者：张然 杨梦滋 武蒙蒙[1,2] 米杰[1,2] 王建成[1,2,3] ZHANG Ran;YANG Mengzi;WU Mengmeng;MI Jie;WANG Jiancheng(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;Key Laboratory of Coal Science and Technology,Ministry of Education,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;College of Environmental Science and Engineering,Taiyuan University of Technology,Jinzhong 030600,Shanxi,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]太原理工大学煤科学与技术教育部重点实验室,山西太原030024 [3]太原理工大学环境科学与工程学院,山西晋中030600

出　　处：《化工进展》2024年第11期6173-6183,共11页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(22278294,21978188);山西省自然科学基金(20210302123191);山西省科技创新人才团队项目(202204051002025);山西省环境催化材料技术创新中心项目(202104010911008)。

摘　　要：高温煤气脱硫是煤炭清洁高效利用的关键步骤之一。前期研究发现,MCM-41负载ZnO高温煤气脱硫剂(ZnO/MCM-41)脱硫性能优良,但其脱硫过程中存在生成COS的放硫现象;尽管提出了引入助剂调变上述放硫行为的策略,但缺乏助剂与脱硫剂匹配特性及改性脱硫剂再生行为的研究。本研究表明,在ZnO/MCM-41中引入质量分数1%~5%助剂(Ni/Fe/Co),均可有效抑制COS释放(释放量分别降低99.4%~99.9%、73.1%~93.4%和69.0%~98.4%),这主要归因于助剂对COS氢解的催化作用;脱硫剂中镍、铁分别以Ni^(2+)和Fe^(3+)形式存在,而钴以Co^(2+)和Co^(3+)形式共存;对于性能最优的Ni掺杂(质量分数3%)脱硫剂,其再生温度应不低于600℃(低温再生仍存在部分ZnS);且脱硫剂经四次循环再生实验后可维持高硫容(初次的91.5%)及低COS释放量(4.8×10^(-2)g羰基硫/100g脱硫剂),轻微的性能下降可归因于活性组分及助剂的少部分损失。上述研究可为高性能脱硫剂构筑提供理论指导。High temperature desulfurization of coal gas is one of the key steps for clean and efficient utilization of coal resources.Previous studies had found that MCM-41 supported ZnO sorbents(ZnO/MCM-41)exhibit outstanding hot-coal-gas desulfurization performance.However,there was COS formation(sulfur-release)during desulfurization process.Although the strategy of introducing additives into ZnO/MCM-41 for modifying sulfur-release behavior had been proposed,there was still a lack of research on the matching characteristics between additives and sorbents and the regeneration behavior of modified sorbents.The work showed that the doping of 1%—5%Ni/Fe/Co into ZnO/MCM-41 could effectively inhibit the release of COS by decreasing the corresponding COS-release amount of 99.4%—99.9%,73.1%—93.4%,and 69.0%—98.4%,respectively.The decrease is mainly attributed to the catalytic effect of additives on the hydrogenolysis of COS.Ni and Fe in modified sorbents exist in the form of Ni^(2+)and Fe^(3+),respectively,while Co coexists in the form of Co^(2+)and Co^(3+).For the optimized Ni-doping sorbent(3%),the regeneration temperature should not be lower than 600℃because low-temperature regeneration leads to the presence of ZnS in regenerated sorbents.The optimized sorbent could maintain high sulfur capacity(91.5%of that for fresh sorbents)and low COS-release amount(4.8×10^(-2)g COS/100g sorbents)after four desulfurization-regeneration cycles.The slight decrease in the ability of desulfurization and inhibiting sulfur-release is ascribed to the loss of a small fraction of active components and additives.The research could provide theoretical guidance for the preparation of high-performance sorbents.

关 键 词：热煤气 氧化锌脱硫剂 硫化碳 催化 再生 稳定性 

分 类 号：TQ51[化学工程]