焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响

doi:10.16085/j.issn.1000-6613.2022-0630

化工进展 ›› 2023, Vol. 42 ›› Issue (2): 783-793.DOI: 10.16085/j.issn.1000-6613.2022-0630

焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响

李乃珍¹(), 孙瑞洁¹, 秦志峰¹^,²^,³(), 苗茂谦¹, 吴琼笑⁴, 常丽萍¹, 孙鹏程², 曾剑², 刘毅³

^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.山西省环境规划院博士后科研工作站，山西太原 030002
^3.清华大学环境科学与工程博士后流动站，北京 100084
^4.山西道生鑫宇清洁能源有限公司，山西忻州 036300

收稿日期:2022-04-12 修回日期:2022-06-19 出版日期:2023-02-25 发布日期:2023-03-13
通讯作者: 秦志峰
作者简介:李乃珍（1995—），女，硕士研究生，研究方向为气体净化与工业催化。E-mail：lnzlldmmmmd@163.com。
基金资助:
2016年度山西省科技重大专项(MJH2016-03);东莞市能源投资集团有限公司攻关项目(RH2000004464)

Effects of constant carbon atmosphere on the activity, selectivity and coking of catalysts in hydrodesulfurization of coke oven gas

LI Naizhen¹(), SUN Ruijie¹, QIN Zhifeng¹^,²^,³(), MIAO Maoqian¹, WU Qiongxiao⁴, CHANG Liping¹, SUN Pengcheng², ZENG Jian², LIU Yi³

^1.Provincial and Ministry Jointly Build the State Key Laboratory of Clean and Efficient Utilization of Coal-based Energy, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Postdoctoral Research Station, Environmental Planning Institute of Shanxi Province, Taiyuan 030002, Shanxi, China
^3.Environmental Science and Engineering Postdoctoral Mobile Station, Tsinghua University, Beijing 100084, China
^4.Daosheng Xinyu Clean Energy Company Limited, Xinzhou 036300, Shanxi, China

Received:2022-04-12 Revised:2022-06-19 Online:2023-02-25 Published:2023-03-13
Contact: QIN Zhifeng

摘要/Abstract

摘要：

利用微型固定床反应装置对工业Fe-Mo预加氢脱硫催化剂进行加氢脱硫（HDS）评价，研究焦炉煤气中不同常量含碳原料组分（CH₄、C₂H₄、C₂H₆、CO、CO₂）对催化剂加氢活性、选择性以及积炭的影响，并采用红外碳硫分析仪、N₂吸附-脱附、Raman以及TPRS-MS对催化剂进行表征。结果表明：在N₂气氛下，COS、CS₂和C₄H₄S加氢转化由易到难顺序为：COS>CS₂>C₄H₄S，但COS加氢转化受含碳气氛影响最明显，致使焦炉煤气加氢脱硫中COS难以完全脱除；不同气氛对硫化物加氢选择性都会产生影响，其中C₂H₄气氛对选择性影响最明显，而对H₂S收率影响最明显的是CO₂和CO；不同含碳气氛在410℃下稳定反应11h后催化剂均发生积炭，主要以石墨化炭为主，其中C₂H₄气氛下积炭最严重，气氛对积炭影响顺序为：C₂H₄>CO₂>CO>CH₄>N₂>C₂H₆。

关键词: 焦炉煤气, 含碳气氛, 加氢脱硫, 活性, 选择性, 积炭, 失活

Abstract:

Hydrodesulfurization (HDS) evaluation of the industrial Fe-Mo catalyst was carried out by using a micro fixed bed reactor. The influence of constant carbon components (CH₄、C₂H₄、C₂H₆、CO、CO₂) in coke oven gas on the hydrogenation activity, selectivity and carbon deposition were studied. The catalyst was characterized by infrared carbon sulfur analyzer, N₂ adsorption desorption, Raman and TPRS-MS. The results showed that the order of COS, CS₂ and C₄H₄S hydrogenation conversion from easy to difficult was COS>CS₂>C₄H₄S under the carbon-free atmosphere, but the hydroconversion of COS was obviously affected by the carbonaceous atmosphere, which made it difficult to completely remove COSs. The atmosphere also had an impact on the hydrogenation selectivity of sulfide, among which C₂H₄ had the most obvious effect, while CO₂ and CO had the most obvious effect on the yield of H₂S. After 11h stable reaction at 410℃ in different carbonaceous atmospheres, carbon deposition took place on the catalyst, mainly as graphitized carbon, and carbon deposition was the most serious in C₂H₄atmosphere. The influence order of atmosphere on carbon deposition was C₂H₄>CO₂>CO>CH₄>N₂>C₂H₆.

Key words: coke oven gas, carbonaceous atmosphere, hydrodesulfurization, reactivity, selectivity, carbon deposition, deactivation

中图分类号:

TQ546.5

李乃珍, 孙瑞洁, 秦志峰, 苗茂谦, 吴琼笑, 常丽萍, 孙鹏程, 曾剑, 刘毅. 焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响[J]. 化工进展, 2023, 42(2): 783-793.

LI Naizhen, SUN Ruijie, QIN Zhifeng, MIAO Maoqian, WU Qiongxiao, CHANG Liping, SUN Pengcheng, ZENG Jian, LIU Yi. Effects of constant carbon atmosphere on the activity, selectivity and coking of catalysts in hydrodesulfurization of coke oven gas[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 783-793.

图/表 9

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气体名称	纯度（体积分数）或含量	平衡气体
甲烷	99.99%	—
乙烯	99.9%	—
乙烷	99.9%	—
一氧化碳	99.99%	—
二氧化碳	99.99%	—
预硫化气体	H₂S约3%	H₂
含硫反应气体	COS约119.48mg/m³、CS₂约91.28mg/m³、C₄H₄S约12.39mg/m³	H₂
TPRS反应气1	COS约2080mg/m³	H₂
TPRS反应气2	H₂S约500mg/m³	H₂
硫化物标气	H₂S约143.32mg/m³、COS约155.40mg/m³、CH₃SH约99.35mg/m³、C₂H₅SH约98.54mg/m³、CH₃SCH₃约102.23mg/m³、CS₂约157.02mg/m³、C₄H₄S约147.57mg/m³、CH₃S₂CH₃约148.57mg/m³、C₂H₅SCH₃约146.79mg/m³、(C₂H₅)S约146.45mg/m³	N₂

气体名称	纯度（体积分数）或含量	平衡气体
甲烷	99.99%	—
乙烯	99.9%	—
乙烷	99.9%	—
一氧化碳	99.99%	—
二氧化碳	99.99%	—
预硫化气体	H₂S约3%	H₂
含硫反应气体	COS约119.48mg/m³、CS₂约91.28mg/m³、C₄H₄S约12.39mg/m³	H₂
TPRS反应气1	COS约2080mg/m³	H₂
TPRS反应气2	H₂S约500mg/m³	H₂
硫化物标气	H₂S约143.32mg/m³、COS约155.40mg/m³、CH₃SH约99.35mg/m³、C₂H₅SH约98.54mg/m³、CH₃SCH₃约102.23mg/m³、CS₂约157.02mg/m³、C₄H₄S约147.57mg/m³、CH₃S₂CH₃约148.57mg/m³、C₂H₅SCH₃约146.79mg/m³、(C₂H₅)S约146.45mg/m³	N₂

序号	反应方程式	ΔG/kJ·mol^-1		lgK
序号	反应方程式	250℃	350℃	250℃	350℃
(1)	COS+H₂=CO+H₂S	-2.444	-3.277	1.021	1.149
(2)	COS+4H₂=H₂S+CH₄+H₂O	-20.480	-13.451	8.556	4.718
(3)	COS+H₂O=CO₂+H₂S	-10.755	-12.811	4.493	4.493
(4)	2COS+4H₂=CH₄+CS₂+2H₂O	-13.972	-8.843	5.837	3.102
(5)	CS₂+4H₂=2H₂S+CH₄	-34.279	-29.596	14.322	10.381
(6)	C₄H₄S+4H₂=H₂S+i-C₄H₁₀	-25.936	-17.916	10.836	6.284
(7)	CO₂+CS₂=2COS	-3.044	-3.335	1.272	1.170
(8)	CO₂+H₂=CH₄+2H₂O	-17.016	-12.178	7.109	4.271
(9)	H₂S+CO=COS+H₂+CH₄	-14.350	-6.113	5.996	-1.999
(10)	H₂+CO=CO₂+CH₄	-26.348	-19.708	11.008	6.912
(11)	COS+3H₂=CH₃SH+H₂O	-2.893	4.073	1.209	-1.429
(12)	CS₂+3H₂=CH₃SH+H₂S	-16.692	-12.072	6.974	4.234
(13)	2CH₃SH=(CH₃)₂S+H₂S	-0.146	0.284	0.061	-0.100
(14)	CH₃SH+H₂=CH₄+H₂S	-17.587	-17.524	7.348	6.147
(15)	(CH₃)₂S+2H₂=2CH₄+H₂S	-35.028	-35.332	14.634	12.393
(16)	C₂H₄+H₂S=C₂H₅SH	-2.850	0.202	1.191	-0.071
(17)	2C₂H₅SH=(C₂H₅)₂S+H₂S	-1.122	-0.968	0.469	0.340
(18)	C₂H₅SH+C₂H₄=(C₂H₅)₂S	-3.972	-0.767	1.660	0.269
(19)	C₂H₄+CH₃SH=CH₃SC₂H₅	-3.373	-0.021	1.409	0.007
(20)	C₂H₅SH+H₂=C₂H₆+H₂S	-14.574	-14.504	6.089	5.087
(21)	CO+3H₂=CH₄+H₂O	-18.036	-10.174	7.535	3.569
(22)	CO+H₂O=CO₂+H₂	-8.312	-9.534	3.473	3.344

序号	反应方程式	ΔG/kJ·mol^-1		lgK
序号	反应方程式	250℃	350℃	250℃	350℃
(1)	COS+H₂=CO+H₂S	-2.444	-3.277	1.021	1.149
(2)	COS+4H₂=H₂S+CH₄+H₂O	-20.480	-13.451	8.556	4.718
(3)	COS+H₂O=CO₂+H₂S	-10.755	-12.811	4.493	4.493
(4)	2COS+4H₂=CH₄+CS₂+2H₂O	-13.972	-8.843	5.837	3.102
(5)	CS₂+4H₂=2H₂S+CH₄	-34.279	-29.596	14.322	10.381
(6)	C₄H₄S+4H₂=H₂S+i-C₄H₁₀	-25.936	-17.916	10.836	6.284
(7)	CO₂+CS₂=2COS	-3.044	-3.335	1.272	1.170
(8)	CO₂+H₂=CH₄+2H₂O	-17.016	-12.178	7.109	4.271
(9)	H₂S+CO=COS+H₂+CH₄	-14.350	-6.113	5.996	-1.999
(10)	H₂+CO=CO₂+CH₄	-26.348	-19.708	11.008	6.912
(11)	COS+3H₂=CH₃SH+H₂O	-2.893	4.073	1.209	-1.429
(12)	CS₂+3H₂=CH₃SH+H₂S	-16.692	-12.072	6.974	4.234
(13)	2CH₃SH=(CH₃)₂S+H₂S	-0.146	0.284	0.061	-0.100
(14)	CH₃SH+H₂=CH₄+H₂S	-17.587	-17.524	7.348	6.147
(15)	(CH₃)₂S+2H₂=2CH₄+H₂S	-35.028	-35.332	14.634	12.393
(16)	C₂H₄+H₂S=C₂H₅SH	-2.850	0.202	1.191	-0.071
(17)	2C₂H₅SH=(C₂H₅)₂S+H₂S	-1.122	-0.968	0.469	0.340
(18)	C₂H₅SH+C₂H₄=(C₂H₅)₂S	-3.972	-0.767	1.660	0.269
(19)	C₂H₄+CH₃SH=CH₃SC₂H₅	-3.373	-0.021	1.409	0.007
(20)	C₂H₅SH+H₂=C₂H₆+H₂S	-14.574	-14.504	6.089	5.087
(21)	CO+3H₂=CH₄+H₂O	-18.036	-10.174	7.535	3.569
(22)	CO+H₂O=CO₂+H₂	-8.312	-9.534	3.473	3.344

样品	孔体积/cm³·g^-1	比表面积/m²·g^-1	平均孔径/nm	碳质量分数/%	硫质量分数/%
新鲜催化剂	0.47	210.4	4.4	0.12	0.12
硫化后催化剂	0.45	190.8	4.4	0.29	3.62
N₂反应后	0.43	185.6	4.5	0.38	2.48
CH₄反应后	0.41	181.9	4.5	0.44	2.64
C₂H₄反应后	0.41	178.1	4.6	0.77	2.56
C₂H₆反应后	0.41	181.4	4.5	0.29	2.72
CO反应后	0.42	182.5	4.5	0.47	2.56
CO₂反应后	0.42	184.4	4.5	0.54	2.58

焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响

Effects of constant carbon atmosphere on the activity, selectivity and coking of catalysts in hydrodesulfurization of coke oven gas

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