高炉煤气中羰基硫水解吸附催化剂的制备及性能研究

doi:10.11949/0438-1157.20211039

化工学报 ›› 2022, Vol. 73 ›› Issue (1): 275-283.DOI: 10.11949/0438-1157.20211039

• 催化、动力学与反应器 • 上一篇下一篇

高炉煤气中羰基硫水解吸附催化剂的制备及性能研究

马铭宇^1,²(),王超³,李运甲⁴,李长明⁵,刘雪景¹,高士秋²,余剑²()

^1.沈阳化工大学化学工程学院，辽宁沈阳 110142
^2.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^3.中国石油大学（北京）重质油国家重点实验室，北京 102249
^4.北京航天环境工程有限公司，北京 102300
^5.北京工商大学生态环境学院，北京 100048

收稿日期:2021-07-23 修回日期:2021-10-11 出版日期:2022-01-05 发布日期:2022-01-18
通讯作者: 余剑
作者简介:马铭宇（1997—），男，硕士研究生，ma-mingyu@foxmail.com

Preparation and performance study of catalyst for COS hydrolysis and adsorption in blast furnace gas

Mingyu MA^1,²(),Chao WANG³,Yunjia LI⁴,Changming LI⁵,Xuejing LIU¹,Shiqiu GAO²,Jian YU²()

^1.College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^2.Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
^4.Beijing Aerospace Environmental Engineering Co. , Ltd. , Beijing 102300, China
^5.School of Ecology and Environment, Beijing Technology and Business University, Beijing 100048, China

Received:2021-07-23 Revised:2021-10-11 Online:2022-01-05 Published:2022-01-18
Contact: Jian YU

摘要/Abstract

摘要：

以移动床活性焦烟气净化工艺运转中产生的磨损废活性焦（EAC）为原料制备羰基硫（COS）水解吸附材料，结合XRD、TG、BET、TPD、FTIR、SEM、XPS手段对EAC进行表征，发现磨损废焦具有发达的表面孔道结构与丰富的表面官能团，比表面积达445.38 m²/g。研究不同碱量改性及工艺参数对COS催化水解脱除效率的影响，结果表明在100℃下，负载0.450%NaOH时EAC催化剂活性最强，穿透硫容达126.58 mg/g。对反应后样品进行分析表明COS在废焦中主要以S存在，这种固硫方式增大了硫容量，为废焦的梯级利用与硫资源化提供了一条新途径。

关键词: 废活性焦, 羰基硫, 催化, 水解, 回收, 性能研究

Abstract:

The COS hydrolysis and sorption catalyst was prepared by exhausted activated coke (EAC) produced in the activated coke purification process in the moving bed. Combining with the results characterized by multiple methods (XRD, TG, BET, TPD, FTIR, SEM, and XPS), it was found that the more developed pore structures and more abundant surface groups appeared in the EAC, and the specific surface area reached 445.38 m²/g. The effects of different alkali loading and process parameters on COS catalytic hydrolysis efficiency were investigated, and the results showed the activity was strongest when the NaOH loading was 0.450% at 100℃ which the breakthrough sulfur capacity reached 126.58 mg/g. The analysis of the sample after reaction showed that the COS mainly exists as S in the waste coke. This sulfur fixation method increases the sulfur capacity and provides a new way for the cascade utilization of waste coke and sulfur resource utilization.

Key words: exhausted activated coke, COS, catalysis, hydrolysis, recovery, performance study

中图分类号:

X511

马铭宇, 王超, 李运甲, 李长明, 刘雪景, 高士秋, 余剑. 高炉煤气中羰基硫水解吸附催化剂的制备及性能研究[J]. 化工学报, 2022, 73(1): 275-283.

Mingyu MA, Chao WANG, Yunjia LI, Changming LI, Xuejing LIU, Shiqiu GAO, Jian YU. Preparation and performance study of catalyst for COS hydrolysis and adsorption in blast furnace gas[J]. CIESC Journal, 2022, 73(1): 275-283.

图/表 8

图1 催化剂活性评价体系

Fig.1 Catalyst activity evaluation unit

图2 废活性焦的XRD谱图（a）、TG曲线（b）、N2等温吸附脱附曲线（c）及孔径分布（d）

Fig.2 XRD patten (a), TG curve (b), nitrogen adsorption-desorption isotherms (c) and pore size distribution (d) of EAC

图3 废活性焦的TPD曲线（a）与FTIR曲线（b）

Fig.3 TPD curves (a) and FTIR curve (b) of EAC

图4 不同温度（a）与NaOH负载量（b）对水解COS的影响

Fig.4 Effect of different temperature (a) and NaOH loading (b) on COS removal ability

图5 不同空速（a）、装填量（b）与气体浓度（c）对水解COS的影响；碱改性废活性焦对模拟高炉煤气中含硫气体的脱除能力（d）

Fig.5 Effect of different space velocity (a), loading quantity (b) and gas concentration (c) on COS removal ability, and the removal capacity of base modified EAC on sulfur-containing substance in simulated blast furnace gas (d)

图6 EAC-0.450%NaOH样品失活前（a）与失活后（b）的高分辨率S 2p曲线

Fig 6 High-resolution S 2p spectrums of EAC-0.450%NaOH before (a) and after (b) inactivation

图7 EAC-0.450%NaOH样品失活前（a）与失活后（b）的SEM与EDS图像

Fig.7 SEM and EDS images of EAC-0.450%NaOH before (a) and after (b) inactivation

表1 EAC-0.450%NaOH样品失活前后EDS线扫描结果

Table 1 The EDS results of EAC-0.450%NaOH before and after inactivation

样品	元素/%（质量）
样品	C	O	S	Na	Al	Si	Cl	Ca	Fe
EAC-0.450%NaOH失活前	87.28	11.13	0.30	0.74	0.06	0.11	0.04	0.14	0.10
EAC-0.450%NaOH失活后	83.23	12.34	3.15	0.82	0.07	0.09	0.03	0.21	0.06

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高炉煤气中羰基硫水解吸附催化剂的制备及性能研究

Preparation and performance study of catalyst for COS hydrolysis and adsorption in blast furnace gas

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