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 ›› 2024, Vol. 75 ›› Issue (10): 3623-3638.DOI: 10.11949/0438-1157.20240259

• 催化、动力学与反应器 • 上一篇下一篇

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:2024-10-25 发布日期:2024-11-04
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;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:2024-10-25 Published:2024-11-04
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。研究结果表明，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炭倾向，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的加氢脱硫活性上显示了优异性能。研究结果为高效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 was evaluated by 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 by using methods such as N₂-physisorption, infrared carbon-sulfur analysis instrument, XRD, NH₃-TPD, H₂-TPR, XPS, Raman and HRTEM. The results of the research indicate that the Al₂O₃ carrier hole structure has a significant effect on the catalyst activity of MoS₂ phase, which affects the hydrogen desulfurization activity and selectivity. Among them, the carrier of the larger pore diameter is more conducive to the effective conversion of COS and CS₂, while the carrier of the smaller pore diameter is more inclined to promote the conversion of 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:

TQ 546.5

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, 2024, 75(10): 3623-3638.

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, 2024, 75(10): 3623-3638.

图/表 17

表1 Al2O3载体孔结构参数和吸水率

Table 1 Pore structure parameters and 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	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 170.86 mg·m^-3、CS₂ 130.53 mg·m^-3、 C₄H₄S 18.45 mg·m^-3	H₂
硫化物标气	H₂S 204.95 mg·m^-3、COS 222.22 mg·m^-3、CH₃SH 142.07 mg·m^-3、C₂H₅SH 140.91 mg·m^-3、CH₃SCH₃ 146.19 mg·m^-3、CS₂ 224.54 mg·m^-3、C₄H₄S 210.93 mg·m^-3、CH₃S₂CH₃ 212.46 mg·m^-3、C₂H₅SCH₃ 209.91 mg·m^-3、(C₂H₅)S 209.42 mg·m^-3	N₂

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

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1.0 MPa,空速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吸附-脱附等温线(a)和孔径分布(b)

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

表3 FeMo/Al2O3催化剂反应前后物理性能

Table 3 Textural properties of the FeMo/Al2O3 catalysts before and after reaction

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/%（质量分数）	硫含量/%（质量分数）
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4 反应前后催化剂XRD谱图

Fig.4 XRD patterns of the catalysts before and after reaction

图5 反应前催化剂NH3-TPD谱图

Fig.5 NH3-TPD spectra of the catalysts before reaction

图6 反应前催化剂H2-TPR谱图

Fig.6 H2-TPR spectra of the catalysts before reaction

图7 反应前后催化剂XPS谱图

Fig.7 XPS spectra 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 of used catalysts calculated from XPS spectra for Mo and S elements

催化剂	Mo⁴⁺/%^①		Mo⁵⁺/%^①		Mo⁶⁺/%^①		S_Mo^②
催化剂	229.0 eV	232.2 eV	230.5 eV	233.6 eV	233.5 eV	236.2 eV	S_Mo^②
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8 反应前后催化剂Raman谱图

Fig.8 Raman spectras of the catalysts before and after reaction

图9 反应前催化剂HRTEM图

Fig.9 Typical HRTEM images of the catalysts before reaction

图10 反应前催化剂粒径分布

Fig.10 Size distribution of the catalysts before reaction

图11 反应后催化剂HRTEM图

Fig.11 Typical HRTEM images of the used catalysts

表5 反应后催化剂TEM统计结果

Table 5 TEM statistical results of the used catalysts

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

图12 反应后催化剂MoS2堆叠层数和长度分布

Fig.12 Distributions of stacking number and length of the MoS2 slabs of the used catalysts

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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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