面向工业应用的焦炉煤气预加氢脱硫催化剂失活机理

doi:10.16085/j.issn.1000-6613.2023-1656

化工进展 ›› 2024, Vol. 43 ›› Issue (10): 5543-5554.DOI: 10.16085/j.issn.1000-6613.2023-1656

• 工业催化 • 上一篇

面向工业应用的焦炉煤气预加氢脱硫催化剂失活机理

谭天兵¹(), 秦志峰¹^,²(), 李乃珍¹, 常丽萍¹, 武蒙蒙¹, 于峰¹, 吴琼笑³^,⁴, 陷艳莉³, 景建宁³

^1.太原理工大学化学工程与技术学院，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.山西浙大新材料与化工研究院，山西太原 030002
^3.山西道生鑫宇清洁能源有限公司，山西岢岚 036300
^4.东莞市能源投资集团有限公司，广东东莞 523000

收稿日期:2023-09-19 修回日期:2023-11-29 出版日期:2024-10-15 发布日期:2024-10-29
通讯作者: 秦志峰
作者简介:谭天兵（1999—），男，硕士研究生，研究方向为气体净化与工业催化。E-mail：15034596213@163.com。
基金资助:
2016年度山西省科技重大专项(MJH2016-03);2018年度山西省优秀人才科技创新项目(201805D211037);山西浙大新材料与化工研究院研发项目(2021ST-AT-002);东莞市能源投资集团有限公司攻关项目(RH2000004464)

Deactivation mechanism of coke oven gas prehydrogenation desulfurization catalyst for industrial application

TAN Tianbing¹(), QIN Zhifeng¹^,²(), LI Naizhen¹, CHANG Liping¹, WU Mengmeng¹, YU Feng¹, WU Qiongxiao³^,⁴, XIAN Yanli³, JING Jianning³

^1.State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Shanxi?Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030002, Shanxi, China
^3.Daosheng Xinyu Clean Energy Company Limited, Kelan 036300, Shanxi, China
^4.Dongguan Energy Investment Group Co. , Ltd. , Dongguan 523000, Guangdong, China

Received:2023-09-19 Revised:2023-11-29 Online:2024-10-15 Published:2024-10-29
Contact: QIN Zhifeng

摘要/Abstract

摘要：

以焦炉煤气深度净化过程使用的预加氢转化新鲜催化剂和失活催化剂为研究对象，利用微型固定床反应装置对新鲜催化剂和再生催化剂进行加氢脱硫（HDS）活性评价，并采用N₂-吸脱附仪、X射线衍射、Raman光谱、热重分析仪、扫描电子显微镜、电子能谱仪、紫外可见分光光度计和高频红外碳硫仪进行表征，深入研究了预加氢转化催化剂的积炭失活机理。研究结果发现，积炭覆盖催化剂表面活性位和堵塞催化剂孔道是导致预加氢转化催化剂失活的主要原因，同时积炭过程伴随活性组分（Fe和Mo）流失及再生过程中催化剂的烧结对催化剂失活也有贡献；积炭的形态以球形石墨化碳为主，其分布形式从催化剂内部向外逐渐增加；除异形条状和五齿球的失活催化剂外，其他催化剂再生（600℃，空气气氛）后可继续使用，再生后催化剂加氢活性下降，这主要是因为催化剂比表面积、孔容的下降及活性组分的流失。

关键词: 焦炉煤气, FeMo/Al₂O₃催化剂, 加氢脱硫, 催化剂积炭, 失活机理

Abstract:

Taking the pre-hydrogenation conversion fresh catalyst and deactivated catalyst used in the deep purification process of coke oven gas as the research object, we used a micro-fixed-bed reaction device to carry out the hydrodesulfurization (HDS) activity evaluation. The carbon deposition and deactivation mechanisms of pre-hydrogenation reforming catalyst were explored by characterizations using N₂-sorption desorption apparatus, X-ray diffraction (XRD), Raman spectroscopy, thermo-gravimetric analysis (TG-DTG), scanning electron microscope with energy dispersive spectrometer (SEM-EDS), UV-Vis spectroscopy and high-frequency infrared carbon-sulfur analyzer. The research result showed that the carbon deposition covering the active sites on the catalyst surface and the catalyst pore blocking were the main deactivation reasons. Meanwhile, the loss of active components (Fe and Mo) during the process of carbon deposition and the catalyst sintering during regeneration process also contributed to the deactivation of the catalysts. Secondly, the form of carbon deposition is dominated by spherical graphitic carbon, increasing gradually from the inside of the catalyst to outside. Finally, except for the catalysts of anisotropic strips and pentagonal spheres, other deactivated catalysts can be reused after regeneration (600 °C, air atmosphere). However, the hydrotreating activity of the catalysts decreased after regeneration, mainly due to the reduction of the catalysts' surface, pore volume and the loss of active components.

Key words: coke oven gas, FeMo/Al₂O₃ catalyst, hydrodesulfurization, catalyst coking, deactivation mechanism

中图分类号:

TQ546.5

谭天兵, 秦志峰, 李乃珍, 常丽萍, 武蒙蒙, 于峰, 吴琼笑, 陷艳莉, 景建宁. 面向工业应用的焦炉煤气预加氢脱硫催化剂失活机理[J]. 化工进展, 2024, 43(10): 5543-5554.

TAN Tianbing, QIN Zhifeng, LI Naizhen, CHANG Liping, WU Mengmeng, YU Feng, WU Qiongxiao, XIAN Yanli, JING Jianning. Deactivation mechanism of coke oven gas prehydrogenation desulfurization catalyst for industrial application[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5543-5554.

图/表 14

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名称	表示方式	Fe₂O₃	NiO	MoO₃
工业催化剂A	Fe-Mo/Al₂O₃	3.53	—	7.76
工业催化剂B	Fe-Mo/Al₂O₃	2.86	—	8.15
工业催化剂C	Fe-Mo/Al₂O₃	2.76	—	9.41
工业催化剂D	Fe-Mo/Al₂O₃	2.47	—	8.67
工业催化剂E	Ni-Mo/Al₂O₃	—	2.12	8.40

名称	表示方式	Fe₂O₃	NiO	MoO₃
工业催化剂A	Fe-Mo/Al₂O₃	3.53	—	7.76
工业催化剂B	Fe-Mo/Al₂O₃	2.86	—	8.15
工业催化剂C	Fe-Mo/Al₂O₃	2.76	—	9.41
工业催化剂D	Fe-Mo/Al₂O₃	2.47	—	8.67
工业催化剂E	Ni-Mo/Al₂O₃	—	2.12	8.40

气体	纯度或含量	平衡气体
乙烯	99.9%	—
预硫化气体	H₂S 3%	H₂
含硫反应气体	COS 321.43mg/m³、CS₂ 309.70mg/m³、C₄H₄S 113.96mg/m³	H₂
硫化物标气	H₂S 217.54mg/m³、COS 416.25mg/m³、CH₃SH 212.89mg/m³、 C₂H₅SH 272.74mg/m³、CH₃SCH₃ 282.96mg/m³、CS₂ 532.74mg/m³、 C₄H₄S 553.38mg/m³、CH₃S₂CH₃ 623.46mg/m³、C₂H₅SCH₃ 498.03mg/m³、(C₂H₅)₂S 589.59mg/m³	N₂

气体	纯度或含量	平衡气体
乙烯	99.9%	—
预硫化气体	H₂S 3%	H₂
含硫反应气体	COS 321.43mg/m³、CS₂ 309.70mg/m³、C₄H₄S 113.96mg/m³	H₂
硫化物标气	H₂S 217.54mg/m³、COS 416.25mg/m³、CH₃SH 212.89mg/m³、 C₂H₅SH 272.74mg/m³、CH₃SCH₃ 282.96mg/m³、CS₂ 532.74mg/m³、 C₄H₄S 553.38mg/m³、CH₃S₂CH₃ 623.46mg/m³、C₂H₅SCH₃ 498.03mg/m³、(C₂H₅)₂S 589.59mg/m³	N₂

样品	比表面积/m²·g^-1	孔体积/mL·g^-1	平均孔径/nm
工业催化剂A
新鲜催化剂样品	296.3	0.26	3.5
失活催化剂样品	8.5	0.03	5.0
催化剂表面炭粉	4.3	0.05	46.9
再生催化剂样品	230.2	0.22	3.9
工业催化剂B
新鲜催化剂样品	210.4	0.38	8.7
失活催化剂样品	43.4	0.08	7.8
催化剂表面炭粉	26.2	0.09	14.0
再生催化剂样品	173.9	0.35	6.7
工业催化剂C
新鲜催化剂样品	206.5	0.41	8.0
失活催化剂样品	73.8	0.16	6.2
催化剂表面炭粉	4.8	0.02	15.2
再生催化剂样品	156.3	0.35	8.9
工业催化剂D
新鲜催化剂样品	212.9	0.39	7.4
失活催化剂样品	78.1	0.19	9.7
催化剂表面炭粉	3.1	0.07	87.2
再生催化剂样品	170.3	0.35	8.2
工业催化剂E
新鲜催化剂样品	135.7	0.48	14.6
失活催化剂样品	52.9	0.16	10.9
催化剂表面炭粉	3.0	0.01	16.1
再生催化剂样品	125.5	0.41	12.0

面向工业应用的焦炉煤气预加氢脱硫催化剂失活机理

Deactivation mechanism of coke oven gas prehydrogenation desulfurization catalyst for industrial application

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样品	新鲜催化剂样品/%					失活催化剂样品/%						催化剂表面炭粉/%
样品	O	Al	Fe	Mo	Ni	O	Al	Fe	Mo	S	C	O	Al	Fe	S	C
工业催化剂A	74.1	23.7	0.8	1.4	—	52.1	21.8	0.7	0.6	1.4	23.4	23.8	0.2	0.3	2.1	73.6
工业催化剂B	65.2	33.3	0.6	0.9	—	51.1	16.1	0.5	0.4	1.5	30.4	20.7	6.1	0.4	1.7	71.1
工业催化剂C	66.0	32.3	0.6	1.1	—	41.9	18.6	0.6	0.4	1.3	37.2	23.2	0.2	0.3	0.1	76.2
工业催化剂D	65.8	32.4	0.5	1.3	—	53.5	22.5	0.5	0.8	2.0	20.7	24.5	2.0	0.4	1.5	71.6
工业催化剂E	68.8	29.5	—	1.1	0.6	53.8	17.7	—	0.7	0.7	27.1	25.5	0.1	—	2.4	72.0

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