磷添加方式对NiMo/Al2O3催化剂加氢脱硫性能的影响

doi:10.16085/j.issn.1000-6613.2020-0584

化工进展 ›› 2021, Vol. 40 ›› Issue (2): 890-900.DOI: 10.16085/j.issn.1000-6613.2020-0584

磷添加方式对NiMo/Al₂O₃催化剂加氢脱硫性能的影响

汪佩华¹(), 秦志峰¹^,²^,³(), 吴琼笑⁴, 李聪明¹, 苗茂谦¹, 常丽萍¹, 孙鹏程², 曾剑², 王立华², 谢克昌¹

^1.太原理工大学煤科学与技术教育部与山西省重点实验室，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，山西岢岚 036300

收稿日期:2020-04-14 修回日期:2020-06-15 出版日期:2021-02-05 发布日期:2021-02-09
通讯作者: 秦志峰
作者简介:汪佩华（1995—），男，硕士研究生，研究方向为工业催化。E-mail：1285141411@qq.com。
基金资助:
山西省科技重大专项(MJH2016-03);山西省优秀人才科技创新项目(201805D211037)

Effect of phosphorus adding manners on the performance of NiMo/Al₂O₃ catalyst in hydrodesulfurization

Peihua WANG¹(), Zhifeng QIN¹^,²^,³(), Qiongxiao WU⁴, Congming LI¹, Maoqian MIAO¹, Liping CHANG¹, Pengcheng SUN², Jian ZENG², Lihua WANG², Kechang XIE¹

^1.Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, 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, Kelan 036300, Shanxi, China

Received:2020-04-14 Revised:2020-06-15 Online:2021-02-05 Published:2021-02-09
Contact: Zhifeng QIN

摘要/Abstract

摘要：

采用分步浸渍法制备了不同磷添加方式改性的NiMo/Al₂O₃催化剂，在固定床微反装置上考察了该系列催化剂对焦炉煤气中噻吩加氢脱硫（HDS）性能的影响，采用BET、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、NH₃程序升温脱附（NH₃-TPD）、C₄H₄S(H₂)程序升温脱附[C₄H₄S(H₂)-TPD]、X射线光电子能谱（XPS）、高清透射电镜（HRTEM）和拉曼（Raman）等分析手段对催化剂进行表征。结果表明，不同磷添加方式制备NiMo/Al₂O₃催化剂的HDS性能存在较大差异。其中，催化剂PNi-Mo/Al和PMo-Ni/Al表面弱吸附解离活性位增强，对焦炉煤气中噻吩有较好的低温加氢脱硫活性，以含292.5mg/m³噻吩的模拟焦炉煤气为原料时，PNi-Mo/Al在250℃下对噻吩的脱硫率达61%。对于PNi-Mo/Al和PMo-Ni/Al催化剂，先浸渍P、Ni或者P、Mo时，P优先和载体Al₂O₃作用，减弱了活性金属组分Ni、Mo与载体间的相互作用，而又防止Ni或者Mo与载体间相互作用过低而聚集，提高了Ni、Mo在载体表面的均匀分散，生成能够促进硫化形成Ⅱ型活性相Ni-Mo-S的NiMoO₄物种。NiMoO₄和MoO₃之间的协同作用提高了催化剂的硫化度，使HDS活性得以提高。

关键词: 加氢脱硫, 磷, 焦炉煤气, 噻吩, 载体, 活性

Abstract:

NiMo/Al₂O₃ catalysts modified by phosphorus addition in different manners were prepared by step impregnation method. The effect of these catalysts on the performance of thiophene hydrodesulfurization (HDS) in coke oven gas was investigated on a fixed bed microreactor. The catalysts were characterized by BET, XRD, H₂-TPR, NH₃-TPD, C₄H₄S(H₂)-TPD, XPS, HRTEM and Raman. The results showed that the HDS performance of the NiMo/Al₂O₃ catalysts was greatly different. The weak adsorption dissociation on the activity sites of the catalysts of PNi-Mo/Al and PMo-Ni/Al was enhanced, and the catalysts had better low temperature HDS activity. When the simulated coke oven gas containing 292.5mg/m³ thiophene was used as raw material, the desulfurization rate of thiophene by PNi-Mo/Al at 250℃ was more than 61%. For PNi-Mo/Al and PMo-Ni/Al catalysts, the first impregnation of P and Ni or P and Mo made P preferentially interact with Al₂O₃, and weakened the interactions between Ni or Mo with the support of the active metal component but not too much so that the Ni or Mo could evenly disperse on the surface of the support, and hence NiMoO₄ were generated which can promote the formation of type Ⅱ active phase Ni-Mo-S by the sulfidation of Ni in the catalyst. The synergistic effect between NiMoO₄ and MoO₃ increased the sulfidation of the catalyst, resulting in the increased HDS activity.

Key words: hydrodesulfurization, phosphorus, coke oven gas, thiophene, support, reactivity

中图分类号:

TQ546.5

汪佩华, 秦志峰, 吴琼笑, 李聪明, 苗茂谦, 常丽萍, 孙鹏程, 曾剑, 王立华, 谢克昌. 磷添加方式对NiMo/Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2021, 40(2): 890-900.

Peihua WANG, Zhifeng QIN, Qiongxiao WU, Congming LI, Maoqian MIAO, Liping CHANG, Pengcheng SUN, Jian ZENG, Lihua WANG, Kechang XIE. Effect of phosphorus adding manners on the performance of NiMo/Al₂O₃ catalyst in hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 890-900.

图/表 11

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气体组分	体积分数/%	气体组分	体积分数/%
H₂	57.46	N₂	3.95
CO	6.90	O₂	0.48
CO₂	2.99	C_nH_m	2.42
CH₄	25.80	C₄H₄S	438.75mg/m³

气体组分	体积分数/%	气体组分	体积分数/%
H₂	57.46	N₂	3.95
CO	6.90	O₂	0.48
CO₂	2.99	C_nH_m	2.42
CH₄	25.80	C₄H₄S	438.75mg/m³

样品	各组分质量分数/%			比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径 /nm
样品	MoO₃	NiO	P	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径 /nm
γ-Al₂O₃	—	—	—	212	0.39	7.91
P/Al	0	0	1	181	0.36	7.58
PNi/Al	0	5	1	181	0.34	7.58
PMo/Al	15	0	1	185	0.34	7.93
P-NiMo/Al	15	5	1	139	0.36	8.06
PNi-Mo/Al	15	5	1	126	0.31	8.97
PMo-Ni/Al	15	5	1	144	0.29	8.07
NiMo-P/Al	15	5	1	161	0.30	7.84
NiMoP/Al	15	5	1	179	0.31	7.36

样品	各组分质量分数/%			比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径 /nm
样品	MoO₃	NiO	P	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径 /nm
γ-Al₂O₃	—	—	—	212	0.39	7.91
P/Al	0	0	1	181	0.36	7.58
PNi/Al	0	5	1	181	0.34	7.58
PMo/Al	15	0	1	185	0.34	7.93
P-NiMo/Al	15	5	1	139	0.36	8.06
PNi-Mo/Al	15	5	1	126	0.31	8.97
PMo-Ni/Al	15	5	1	144	0.29	8.07
NiMo-P/Al	15	5	1	161	0.30	7.84
NiMoP/Al	15	5	1	179	0.31	7.36

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磷添加方式对NiMo/Al₂O₃催化剂加氢脱硫性能的影响

Effect of phosphorus adding manners on the performance of NiMo/Al₂O₃ catalyst in hydrodesulfurization

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样品	表面Mo组成/%			原子比
样品	n(Mo⁴⁺)/n(Mo)	n(Mo⁶⁺)/n(Mo)	n(Mo⁵⁺)/n(Mo)	Ni/(Ni+Mo)	S/Mo
NiMo/Al	21	58	21	0.14	0.27
P-NiMo/Al	26	51	23	0.14	0.35
PNi-Mo/Al	58	35	7	0.17	1.37
PMo-Ni/Al	43	25	32	0.19	1.16
NiMoP/Al	32	43	25	0.16	0.39
NiMo-P/Al	35	48	17	0.16	1.13