原位红外研究噻吩在硫化后Co-Mo/γ-Al2O3催化剂上吸附行为

doi:10.16085/j.issn.1000-6613.2020-0413

摘要/Abstract

摘要：

在原油质量下降的趋势和柴油硫含量标准不断提升的背景下，为提升加氢脱硫催化剂催化活性及改进清洁油品的生产工艺，本文采用原位红外技术研究工业用直接脱硫路径活性较高的Co-Mo/γ-Al₂O₃催化剂的硫化行为和噻吩的吸附行为。实验结果表明，Co-Mo/γ-Al₂O₃催化剂的表面在约320℃硫化，噻吩在硫化后的Co-Mo/γ-Al₂O₃催化剂上原位升温脱附的过程中，噻吩的CC伸缩振动峰（1558cm^-1）和CH面内弯曲振动峰（1413cm^-1）在约250℃消失（对应π络合吸附）；CC伸缩振动峰（1679、1575cm^-1）和CH面内弯曲振动峰（1396cm^-1）在约350℃消失（对应M-S吸附）；而CC伸缩振动峰（1537、1513cm^-1）和CH面内弯曲振动峰（1338cm^-1）持续增强（对应π络合吸附）。这明晰了噻吩的吸附方式与其脱附温度之间的关系，为新型加氢脱硫催化剂的设计开发提供了试验数据支持。

关键词: 加氢脱硫, 催化剂, 吸附, 噻吩, Co-Mo/γ-Al₂O₃, 原位红外, 硫化

Abstract:

Against the background of declining heavy oil quality and rising diesel sulfur standards, in order to improve hydrodesulfurization catalysts and production processes, the in-situ IR was used to study the sulfurization behavior of Co-Mo/γ-Al₂O₃catalyst whose industrial direct desulfurization activity is higher and adsorption behavior of thiophene. Co-Mo/γ-Al₂O₃ catalyst surface was sulfided at 320℃, and during thiophene-temperature programmed desorption on sulfided catalyst, the thiophene adsorption characteristic peaks at 1558cm^-1 (CC vibration) and 1413cm^-1 (CH vibration) disappeared at 250℃(π complex adsorption); peaks at 1679, 1575cm^-1 (CC vibration ) and 1396cm^-1 (CH vibration) disappeared at 350℃(M-S adsorption), but peaks at 1537cm^-1, 1513cm^-1 (CC vibration) and 1338cm^-1 (CH vibration) strengthened (π complex adsorption). This clarifies the relationship between adsorption mode and desorption temperature of thiophene, which provides experimental data support for the design and development of higher activity catalysts.

Key words: HDS, catalyst, adsorption, thiophene, Co-Mo/γ-Al₂O₃, in-situ IR, sulfurization

中图分类号:

TQ426.95

陈俊霖, 赵基钢, 江洪波, 陈文斌, 秦康, 沈本贤. 原位红外研究噻吩在硫化后Co-Mo/γ-Al₂O₃催化剂上吸附行为[J]. 化工进展, 2020, 39(S2): 221-226.

Junlin CHEN, Jigang ZHAO, Hongbo JIANG, Wenbin CHEN, Kang QIN, Benxian SHEN. Adsorption behavior of thiophene on Co-Mo/γ-Al₂O₃ catalyst by in-situ IR[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 221-226.

图/表 7

参考文献 22

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波长范围/cm^-1	噻吩特征峰/cm^-1	物理脱附特征峰/cm^-1	化学吸附特征峰/cm^-1	分布
3200～2800	3105	3100		ν(CH)(伸缩)
	3071			ν(CH)(伸缩)
2800～1730		1795		组频峰
	1743	1770		组频峰
1730～1600			1700	ν(CC)(伸缩)1
			1679	ν(CC)(伸缩)1
			1650	ν(CC)(伸缩)1
			1646	ν(CC)(伸缩)1
			1619	ν(CC)(伸缩)1
1600～1485	1575	1577	1575	ν(CC)(伸缩)2
			1560	ν(CC)(伸缩)2
		1537	1537	ν(CC)(伸缩)2
	1470		1513	ν(CC)(伸缩)2
1485～1310			1456	δ(CH)(面内弯曲)1
	1407	1405	1413	δ(CH)(面内弯曲)1
			1396	δ(CH)(面内弯曲)1
1310～1179	1358			ν(R)(环伸缩)
	1253	1253	1214	δ(CH)(面内弯曲)2
		1197	1197	δ(CH)(面内弯曲)2
1179～700	1083	1080	1080	δ(CH)(面外弯曲)
	714			δ(CH)(面外弯曲)

波长范围/cm^-1	噻吩特征峰/cm^-1	物理脱附特征峰/cm^-1	化学吸附特征峰/cm^-1	分布
3200～2800	3105	3100		ν(CH)(伸缩)
	3071			ν(CH)(伸缩)
2800～1730		1795		组频峰
	1743	1770		组频峰
1730～1600			1700	ν(CC)(伸缩)1
			1679	ν(CC)(伸缩)1
			1650	ν(CC)(伸缩)1
			1646	ν(CC)(伸缩)1
			1619	ν(CC)(伸缩)1
1600～1485	1575	1577	1575	ν(CC)(伸缩)2
			1560	ν(CC)(伸缩)2
		1537	1537	ν(CC)(伸缩)2
	1470		1513	ν(CC)(伸缩)2
1485～1310			1456	δ(CH)(面内弯曲)1
	1407	1405	1413	δ(CH)(面内弯曲)1
			1396	δ(CH)(面内弯曲)1
1310～1179	1358			ν(R)(环伸缩)
	1253	1253	1214	δ(CH)(面内弯曲)2
		1197	1197	δ(CH)(面内弯曲)2
1179～700	1083	1080	1080	δ(CH)(面外弯曲)
	714			δ(CH)(面外弯曲)

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原位红外研究噻吩在硫化后Co-Mo/γ-Al₂O₃催化剂上吸附行为

Adsorption behavior of thiophene on Co-Mo/γ-Al₂O₃ catalyst by in-situ IR

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