Effect of impregnation way of Ce on the performance of CoMo/CeAl2O3 catalysys in hydrodesulfurization

doi:10.16085/j.issn.1000-6613.2018-1833

Abstract

Abstract:

Series CoMo/CeAl₂O₃ catalysts were prepared by using different impregnation way of cerium and their performance in hydrodesulfurization was investigated. The results showed that the activity of the catalysts is in the following order CoMoCe/Al₂O₃＞CeCoMo/Al₂O₃＞CoMo/CeAl₂O₃. For the CoMoCe/Al₂O₃ catalyst, cerium was loaded on the Al₂O₃ at the first stage and thus can weaken the interaction between molybdenum and supporter, and are helpful for the sulfurization of molybdenum, which can promote the formation of CoMoS active phase and then enhance the catalytic performance of CoMoCe/Al₂O₃ in hydrodesulfurization. Heavy gas oil from Guangxi Petrochemical Company was processed with the CoMoCe/Al₂O₃ catalyst in a self-made fixed-bed micro reactor and the sulfur content of the product was reduced to 8.6μg/g, and the RON loss was 1.3.

Key words: hydrodesulfurization, cerium, impregnation way, supporter, reactivity

摘要：

针对具有较高脱硫活性的CoMo/CeAl₂O₃催化剂，考察了Ce的不同浸渍方式对催化剂表面金属性质及催化活性的影响。结果表明，Ce采用不同浸渍方式（CoMo共浸渍）制备催化剂的加氢脱硫活性大小顺序为：先浸渍Ce后浸渍CoMo催化剂（CoMoCe/Al₂O₃）＞先浸渍CoMo后浸渍Ce催化剂（CeCoMo/Al₂O₃）＞Ce与载体混粘后浸渍CoMo催化剂（CoMo/CeAl₂O₃）。对于CoMoCe/Al₂O₃催化剂，先浸渍Ce减弱了二次浸渍CoMo时载体与Mo物种间的相互作用力，有利于Mo物种硫化，提高了硫化度，生成了较多的CoMoS活性相，增加了脱硫率；用实验室自组装固定床微型反应装置对CoMoCe/Al₂O₃催化剂进行了活性评价，以广西石化分公司（广西石化）重馏分油（≥65℃）为原料油时，产物硫含量可以降至8.6μg/g，RON损失1.3个单位。

关键词: 加氢脱硫, 铈, 浸渍方式, 载体, 活性

CLC Number:

TE624.4

Qi WANG, Ming KE, Pei YU, Yang LIU, Lei ZHANG, Chengjie XIA, Wen LIU. Effect of impregnation way of Ce on the performance of CoMo/CeAl₂O₃ catalysys in hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3163-3169.

王奇, 柯明, 于沛, 刘洋, 张蕾, 夏成杰, 刘稳. Ce浸渍方式对CoMo/CeAl₂O₃催化剂反应性能影响[J]. 化工进展, 2019, 38(07): 3163-3169.

Figures/Tables 12

References 34

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催化剂	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1
CoMo/CeAl₂O₃	259.40	7.83	0.49
CeCoMo/Al₂O₃	244.70	7.58	0.48
CoMoCe/Al₂O₃	250.81	7.59	0.48

催化剂	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1
CoMo/CeAl₂O₃	259.40	7.83	0.49
CeCoMo/Al₂O₃	244.70	7.58	0.48
CoMoCe/Al₂O₃	250.81	7.59	0.48

催化剂	L酸量/μmol·g^-1		酸量/μmol·g^-1		酸分布/%
催化剂	200℃	350℃	L_w	L_s	L_w	L_s
CoMo/CeAl₂O₃	47.26	21.25	26.01	21.25	55.04	44.96
CoMoCe/Al₂O₃	66.42	32.88	33.54	32.88	50.50	49.50
CeCoMo/Al₂O₃	61.61	28.42	33.19	28.42	53.87	46.13

催化剂	L酸量/μmol·g^-1		酸量/μmol·g^-1		酸分布/%
催化剂	200℃	350℃	L_w	L_s	L_w	L_s
CoMo/CeAl₂O₃	47.26	21.25	26.01	21.25	55.04	44.96
CoMoCe/Al₂O₃	66.42	32.88	33.54	32.88	50.50	49.50
CeCoMo/Al₂O₃	61.61	28.42	33.19	28.42	53.87	46.13

催化剂	电子结合能/eV			Mo的硫化度/%
催化剂	Mo⁴⁺ 3d_5/2	Mo⁵⁺ 3d_5/2	Mo⁶⁺ 3d_5/2	Mo的硫化度/%
CoMo/CeAl₂O₃	228.81	229.84	232.61	49.21
CoMoCe/Al₂O₃	229.10	229.91	232.53	58.22
CeCoMo/Al₂O₃	228.83	229.92	232.82	55.80

Effect of impregnation way of Ce on the performance of CoMo/CeAl₂O₃ catalysys in hydrodesulfurization

Ce浸渍方式对CoMo/CeAl₂O₃催化剂反应性能影响

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催化剂	CoMoS		Co₉S₈		Co(Ⅱ)
催化剂	结合能/eV	相含量 /%	结合能/eV	相含量/%	结合能/eV	相含量 /%
CoMo/CeAl₂O₃	778.94	39.10	778.84	2.70	781.45	58.20
CoMoCe/Al₂O₃	779.07	49.39	777.81	2.20	781.80	48.41
CeCoMo/Al₂O₃	779.12	46.23	777.74	2.01	779.26	51.76

催化剂	平均层数	平均长度/nm
CoMo/CeAl₂O₃	2.79	3.82
CeCoMo/Al₂O₃	2.97	3.80
CoMoCe/Al₂O₃	3.12	3.81

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