Al2O3载体孔结构优化：提升FeMo/Al2O3催化剂在焦炉煤气加氢脱硫性能

doi:10.11949/0438-1157.20240259

化工学报

• •

Al₂O₃载体孔结构优化：提升FeMo/Al₂O₃催化剂在焦炉煤气加氢脱硫性能

王龙龙¹^,²(), 秦志峰¹^,²(), 班红艳¹^,², 李乃珍¹^,², 杜朕屹¹^,², 于峰², 翟志强³, 吴琼笑⁴

^1.太原理工大学化学工程与技术学院，山西太原 030024
^2.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
^3.山西东义煤电铝集团煤化工有限公司，山西孝义 032200
^4.东莞市能源投资集团有限公司，广东东莞 523000

收稿日期:2024-03-04 修回日期:2024-06-18 出版日期:2024-07-08
通讯作者: 秦志峰
作者简介:王龙龙（1999—），男，硕士研究生， 15383414720@163.com
基金资助:
2020年度东莞市能源投资集团有限公司攻关项目“焦炉煤气深度净化预加氢脱硫催化剂的升级开发”;2023年度山西省吕梁市校地合作重点研发专项(2023XDHZ08);2023年度山西省中央引导地方科技发展资金项目(YDZJSX20231C006)

Optimization of Al₂O₃ support pore structure: enhancing the hydrodesulfurization performance of FeMo/Al₂O₃ catalyst in coke oven gas

Longlong WANG¹^,²(), Zhifeng QIN¹^,²(), Hongyan BAN¹^,², Naizhen LI¹^,², Zhenyi DU¹^,², Feng YU², Zhiqiang ZHAI³, Qiongxiao WU⁴

^1.College of Chemical Engineering and Technology Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.Shanxi Dongyi Coal Electric Aluminum Group Co. , Ltd. , Xiaoyi 032200, Shanxi, China
^4.Dongguan Energy Investment Group Co. , Ltd. , Dongguan 523000, Guangdong, China

Received:2024-03-04 Revised:2024-06-18 Online:2024-07-08
Contact: Zhifeng QIN

摘要/Abstract

摘要：

探讨了Al₂O₃载体孔结构对FeMo/Al₂O₃预加氢脱硫（HDS）催化剂活性和选择性的影响，采用浸渍法成功制备了一系列具有不同孔结构的FeMo/Al₂O₃催化剂，并通过微型固定床技术对其在模拟焦炉煤气中COS、CS₂、C₄H₄S和C₂H₄的HDS活性和选择性进行了系统评价，通过N₂吸附-脱附、红外碳硫、XRD、NH₃-TPD、H₂-TPR、XPS、Raman以及HRTEM等技术对催化剂进行了表征。研究结果揭示了Al₂O₃载体孔结构对催化剂活性相MoS₂有显著影响，从而影响加氢脱硫活性和选择性，其中较大孔径的载体更有利于COS和CS₂的有效转化，而较小孔径的载体则更倾向于促进C₄H₄S和C₂H₄的转化；此外，具有较大孔径的催化剂不仅展现出更低的积碳倾向，还通过提高Mo物种的分散性，有效调控了MoS₂片晶的生长尺寸和层数，从而在COS和CS₂的加氢脱硫活性上实现了优异性能，这些发现为高效HDS催化剂的设计与开发开辟了新途径。

关键词: Al₂O₃载体, 孔结构, FeMo/Al₂O₃催化剂, 焦炉煤气, 加氢脱硫

Abstract:

This investigation examines the influence of the Al₂O₃ support pore structure on the activity and selectivity of FeMo/Al₂O₃ pre-hydrodesulfurization (HDS) catalysts. A series of FeMo/Al₂O₃ catalysts with different pore structures were synthesized by the impregnation method. The catalytic HDS performance were evaluated using COS, CS₂, C₄H₄S and C₂H₄ as the probe molecules in a micro-fixed bed reactor. The physico-chemical properties of γ-Al₂O₃ supports and the corresponding FeMo catalysts were characterized using methods such as N₂-physisorption, infrared carbon-sulfur analysis instrument, XRD, NH₃-TPD, H₂-TPR, XPS, Raman and HRTEM. The characterization results showed that the Al₂O₃ support's pore structure markedly impacts the MoS₂ phase's catalytic activity, which in turn influences the HDS activity and selectivity. Supports with larger pore sizes facilitated more efficient conversion of COS and CS₂, while those with smaller pore sizes were more effective for converting C₄H₄S and C₂H₄. Furthermore, catalysts with larger pore sizes not only showed reduced tendencies for carbon accumulation but also enhanced the dispersion of Mo species, effectively modulating the growth dimensions and layer counts of MoS₂ crystallites. This led to exceptional HDS activity performance for COS and CS₂, offering novel avenues for the engineering and development of highly effective HDS catalysts.

Key words: Al₂O₃ support, pore structure, FeMo/Al₂O₃ catalyst, coke oven gas, hydrodesulfurization

中图分类号:

TQ546.5

王龙龙, 秦志峰, 班红艳, 李乃珍, 杜朕屹, 于峰, 翟志强, 吴琼笑. Al₂O₃载体孔结构优化：提升FeMo/Al₂O₃催化剂在焦炉煤气加氢脱硫性能[J]. 化工学报, DOI: 10.11949/0438-1157.20240259.

Longlong WANG, Zhifeng QIN, Hongyan BAN, Naizhen LI, Zhenyi DU, Feng YU, Zhiqiang ZHAI, Qiongxiao WU. Optimization of Al₂O₃ support pore structure: enhancing the hydrodesulfurization performance of FeMo/Al₂O₃ catalyst in coke oven gas[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240259.

图/表 17

表1 Al2O3载体孔结构参数和吸水率

Table 1 Pore structure parameters and the water absorption of the Al2O3 supports

样品	孔体积(cm³·g^-1)	比表面积(m²·g^-1)	平均孔径(nm)	吸水率(ml·g^-1)
a-Al₂O₃载体	0.86	246.4	12.4	129.41
b-Al₂O₃载体	0.78	285.8	10.2	148.91
c-Al₂O₃载体	0.65	263.2	9.6	107.53
d-Al₂O₃载体	0.62	214.2	8.8	116.30
e-Al₂O₃载体	0.49	254.7	8.2	70.33

表2 实验所用气体组分和纯度

Table 2 Test gas composition and concentration

气体名称	纯度或含量	平衡气体
乙烯	99.9 %	-----
氮气	99.99 %	-----
预硫化气体	H₂S ~ 3%	H₂
含硫反应气体	COS ~ 170.86mg/m³、CS₂ ~ 130.53mg/m³、C₄H₄S~ 18.45mg/m³	H₂
硫化物标气	H₂S ~ 204.95mg/m³、COS ~ 222.22mg/m³、CH₃SH ~ 142.07mg/m³、C₂H₅SH~ 140.91mg/m³、CH₃SCH₃~ 146.19mg/m³、CS₂ ~ 224.54mg/m³、C₄H₄S ~ 210.93mg/m³、 CH₃S₂CH₃ ~ 212.46mg/m³、C₂H₅SCH₃ ~ 209.91mg/m³、(C₂H₅)S ~ 209.42mg/m³	N₂

图1 不同孔结构载体FeMo/Al2O3催化剂HDS活性(反应条件:压力为1.0 MPa,空速为5400 h-1(含硫反应气体与C2H4体积比为5:1);a:FeMo/a-Al2O3催化剂,b:FeMo/b-Al2O3催化剂,c:FeMo/c-Al2O3催化剂,d:FeMo/d-Al2O3催化剂,e:FeMo/e-Al2O3催化剂,下同)

Fig.1 HDS performance of FeMo/Al2O3 catalysts of different support pore structures

图2 不同孔结构载体FeMo/Al2O3催化剂加氢产物分布(反应条件:压力为1.0 MPa,空速为5400 h-1(含硫反应气体与C2H4体积比为5:1))

Fig. 2 HDS reaction product composition of FeMo/Al2O3 catalyst at different support pore structures

图3 不同载体新鲜催化剂N2吸-脱附等温线(a)和孔径分曲线(b)

Fig. 3 N2 adsorption-desorption isotherms(a)and pore size distributions (b) of the catalysts before reaction

表3 不同孔结构载体FeMo/c-Al2O3催化剂反应前后物理性能

Table 3 Textural properties of the before and after the reaction samples at different support

催化剂样品		比表面积(m²·g^-1)	孔体积(cm³·g^-1)	平均孔径(nm)	碳含量(wt.%)	硫含量(wt.%)
FeMo/a-Al₂O₃	新鲜催化剂	226.3	0.82	13.1	0.03	0.36
FeMo/a-Al₂O₃	反应后催化剂	210.6	0.81	13.6	0.37	3.41
FeMo/b-Al₂O₃	新鲜催化剂	276.1	0.72	10.7	0.03	0.20
FeMo/b-Al₂O₃	反应后催化剂	227.2	0.65	11.1	0.48	3.08
FeMo/c-Al₂O₃	新鲜催化剂	218.6	0.61	10.3	0.03	0.21
FeMo/c-Al₂O₃	反应后催化剂	200.9	0.59	10.7	1.07	3.37
FeMo/d-Al₂O₃	新鲜催化剂	207.4	0.60	10.2	0.04	0.23
FeMo/d-Al₂O₃	反应后催化剂	170.2	0.56	10.8	1.04	3.46
FeMo/e-Al₂O₃	新鲜催化剂	221.8	0.45	8.6	0.02	0.21
FeMo/e-Al₂O₃	反应后催化剂	194.3	0.41	8.9	1.06	2.87

图3 反应前后催化剂XRD图谱

Fig.3 XRD patterns of the catalysts before and after reaction

图4 反应前催化剂NH3-TPD图谱

Fig.4 NH3-TPD patterns of the catalysts before reaction

图5 反应前催化剂H2-TPR图谱

Fig.5 H2-TPR patterns of the catalysts before reaction

图6 反应前后催化剂XPS图谱

Fig.6 XPS patterns of the catalysts before and after reaction

表4 反应后催化剂XPS表面元素含量

Table 4 Surface compositions calculated from XPS spectra for Mo and S elements in catalysts after reaction

反应后催化剂	Mo⁴⁺		Mo⁵⁺		Mo⁶⁺		S_Mo
反应后催化剂	ar.%¹(229.0eV)	ar.%(232.2eV)	ar.%(230.5eV)	ar.%(233.6eV)	ar.%(233.5eV)	ar.%(236.2eV)	S_Mo
FeMo/a-Al₂O₃	29	25	8	1	21	17	54
FeMo/b-Al₂O₃	21	25	7	6	20	21	46
FeMo/c-Al₂O₃	15	28	4	6	20	17	43
FeMo/d-Al₂O₃	15	27	14	4	19	22	42
FeMo/e-Al₂O₃	20	19	7	3	30	21	40

图7 反应前后催化剂Raman图谱

Fig.7 Raman spectrums of the catalysts before and after reaction

图8 反应前催化剂HRTEM图

Fig.8 Typical HRTEM images of the before catalysts

图9 反应前催化剂粒径分布图

Fig.9 Size distribution of the before catalysts

图10 反应后催化剂HRTEM图

Fig.10 Typical HRTEM images of the used catalysts

图11 反应后催化剂MoS2堆叠层数和长度分布

Fig.11 Distributions of stacking number and lenth of the MoS2 slabs of the used catalysts

表5 反应后催化剂TEM统计结果

Table 5 TEM statistical results in catalysts after reaction

反应后催化剂	平均堆叠层数	平均片晶长度/nm
FeMo/a-Al₂O₃	2.56	4.52
FeMo/b-Al₂O₃	2.75	4.72
FeMo/c-Al₂O₃	3.31	8.56
FeMo/d-Al₂O₃	5.25	9.4
FeMo/e-Al₂O₃	8.28	10.88

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Al₂O₃载体孔结构优化：提升FeMo/Al₂O₃催化剂在焦炉煤气加氢脱硫性能

Optimization of Al₂O₃ support pore structure: enhancing the hydrodesulfurization performance of FeMo/Al₂O₃ catalyst in coke oven gas

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