Ni/Al2O3与ZnO距离对含硫菲加氢性能的影响

doi:10.11949/0438-1157.20240466

摘要/Abstract

摘要：

将菲深度加氢制得全氢菲（航空燃料的主要成分），是实现煤焦油清洁高效利用的有效途径之一。为解决Ni基催化剂在深度加氢过程中的硫中毒问题，将具有优异加氢性能的Ni/Al₂O₃催化剂与脱硫剂ZnO以四种不同方式耦合，系统考察了Ni/Al₂O₃与ZnO距离对含硫菲加氢性能的影响，并借助X射线衍射仪和X射线光电子能谱仪对催化剂的结构进行表征。结果表明，距离最近的装填方式Ⅳ展现出最优异的催化性能，10 h后菲的转化率和二苯并噻吩的脱硫率仍能维持在100.0%，目标产物全氢菲的选择性为98.0%。表征结果显示，较近的距离促进了二苯并噻吩加氢脱硫产生的中间硫物种及时与ZnO作用生成ZnS。两种位点间相互作用的调控，使催化剂兼具深度加氢和加氢脱硫性能，进而提升了Ni/Al₂O₃催化剂在含硫菲加氢反应中的稳定性。

关键词: 催化剂, 加氢, 加氢脱硫, 氧化铝, 稳定性

Abstract:

The deep hydrogenation of phenanthrene into perhydrophenanthrene–a primary component of aviation fuel–has been acknowledged as a viable strategy for the clean exploitation of coal tar. To solve the problem of sulfur poisoning in the deep hydrogenation process on Ni-based catalysts, Ni/Al₂O₃ catalysts with sufficient hydrogenation centers was coupled with desulphurisation agent ZnO in four different ways. The effect of the distance between Ni/Al₂O₃ and ZnO on hydrogenation performance of sulfur-containing phenanthrene was systematically investigated. X-ray diffraction and X-ray photoelectron spectroscopy were used to characterize the structure of the catalyst. The IV filling method with the closest distance showed the excellent performance with phenanthrene conversion and desulfurization of 100.0% after 10 h, and the selectivity of perhydrophenanthrene reached at 98.0%. The characterization results showed that the close distance promoted the reaction of the intermediate sulfur species from dibenzothiophene with ZnO to form ZnS. This strategic proximity of interactive sites enhances the catalyst design, incorporating both hydrogenation and hydrodesulfurization functionalities, which in turn augments the stability of Ni/Al₂O₃ during the deep hydrogenation process of sulfur-containing phenanthrene.

Key words: catalyst, hydrogenation, HDS, alumina, stability

中图分类号:

TQ 426.64

潘越, 刘相洋, 黄奕晨, 李江涛, 邱丽, 李瑞丰, 李莎, 闫晓亮. Ni/Al₂O₃与ZnO距离对含硫菲加氢性能的影响[J]. 化工学报, DOI: 10.11949/0438-1157.20240466.

Yue PAN, Xiangyang LIU, Yichen HUANG, Jiangtao LI, Li QIU, Ruifeng LI, Sha LI, Xiaoliang YAN. Influence of distance between Ni/Al₂O₃ and ZnO for deep hydrogenation of sulfur-containing phenanthrene[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240466.

图/表 12

图1 Ni/Al2O3催化剂与ZnO装填方式示意图

Fig.1 Schematic diagram of Ni/Al2O3 catalyst and ZnO filling methods

表1 Ni/Al2O3催化剂与ZnO装填方式

Table 1 Ni/Al2O3 catalyst and ZnO filling methods

装填方式名称	装填方法
Ⅰ	由石英砂将Ni/Al₂O₃与ZnO分隔
Ⅱ	Ni/Al₂O₃和ZnO分别混合石英砂再分层装填
Ⅲ	石英砂、Ni/Al₂O₃和ZnO颗粒直接混合
Ⅳ	ZnO和Ni/Al₂O₃研磨均匀后与石英砂混合

图2 NiO/Al2O3和ZnO的XRD图谱

Fig.2 XRD patterns of NiO/Al2O3 and ZnO

图3 四种装填方式的PHE加氢性能（代表DHP的选择性，代表THP的选择性，代表s-OHP的选择性，代表as-OHP的选择性，代表PHP的选择性）

Fig.3 PHE hydrogenation performance on four filling methods ( represents DHP selectivity, represents THP selectivity, represents s-OHP selectivity, represents as-OHP selectivity, represents PHP selectivity)

图4 四种装填方式的DBT脱硫性能

Fig.4 DBT desulphurisation performance on four filling methods

表2 四种装填方式第10 h DBT脱硫产物选择性

Table 2 Selectivity of DBT desulfurization products on four filling methods

装填方式	DBT脱硫产物选择性（%）
装填方式	BCH	CHB	BP
Ⅰ	21.1	15.7	63.2
Ⅱ	10.5	20.6	68.9
Ⅲ	93.0	7.0	0
Ⅳ	98.2	1.8	0

图5 DBT加氢脱硫反应路径图

Fig.5 Diagram of hydrodesulfurization reaction pathways for DBT

图6 反应后Ni/Al2O3的XRD图谱

Fig.6 XRD patterns of the spent Ni/Al2O3

图7 反应后ZnO的XRD图谱（右图为左侧虚线范围内的局部放大图）

Fig.7 XRD patterns of the spent ZnO (the figure on the right shows a partial enlargement within the dotted line on the left)

表3 由XPS得到的四种装填方式反应后Ni/Al2O3的表面Ni物种峰位置

Table 3 Peak position of surface Ni species on four filling methods from XPS

催化剂名称	表面Ni物种峰位置（eV）
催化剂名称	Ni⁰	Ni²⁺
Ni/Al₂O_3-I	852.9	856.0
Ni/Al₂O₃-Ⅱ	852.8	855.9
Ni/Al₂O₃-Ⅲ	852.6	855.6
Ni/Al₂O₃-Ⅳ	852.2	855.5

图8 反应后Ni/Al2O3和ZnO的XPS光谱

Fig.8 XPS spectra of the spent Ni/Al2O3 and ZnO

图9 装填方式Ⅰ和装填方式Ⅳ的DBT加氢脱硫路径示意图

Fig.9 Schematic diagram of DBT hydrodesulfurization paths of Ⅰ and Ⅳ filling method

参考文献 31

1	韩辉, 田朋军, 王乐, 等. 中低温煤焦油加工利用现状及发展趋势[J]. 煤炭与化工, 2022, 45(4): 130-134.
	Han H, Tian P J, Wang L, et al. The present situation and development direction of medium/low temperature coal tar processing and utilization[J]. Coal and Chemical Industry, 2022, 45(4): 130-134.
2	程炎, 颜彬航, 李天阳, 等. 煤/煤焦油/沥青质的热等离子体裂解特性比较分析[J]. 化工学报, 2015, 66(8): 3210-3217.
	Cheng Y, Yan B H, Li T Y, et al. Comparison of pyrolysis performances of coal/coal tar/asphaltene in thermal plasmas[J]. CIESC Journal, 2015, 66(8): 3210-3217.
3	Brito L, Pirngruber G D, Guillon E, et al. Hydroconversion of perhydrophenanthrene over bifunctional Pt/H-USY zeolite catalyst[J]. ChemCatChem, 2020, 12(13): 3477-3488.
4	Neurock M, Klein M T. Linear free energy relationships in kinetic analyses: applications of quantum chemistry[J]. Polycyclic Aromatic Compounds, 1993, 3(4): 231-246.
5	Dang Y, Liu Y B, Feng X, et al. Effect of dispersion on the adsorption of polycyclic aromatic hydrocarbons over the γ-Al₂O₃ (110) surface[J]. Applied Surface Science, 2019, 486: 137-143.
6	Liu D C, Chen Y, Jing J Y, et al. Synthesis of Ni/ NiAlO_x catalysts for hydrogenation saturation of phenanthrene[J]. Frontiers in Chemistry, 2021, 9: 757908.
7	贺新福, 尚军, 周均, 等. 煤焦油中多环芳烃菲、蒽加氢裂化的研究进展[J]. 应用化工, 2020, 49(8): 2080-2086.
	He X F, Shang J, Zhou Jet al. Research progress on hydrocracking of polycyclic aromatic hydrocarbons phenanthrene and anthracene in coal tar[J]. Applied Chemical Industry, 2020, 49(8): 2080-2086.
8	Chen Y, Zhao Z M, Li Z, et al. Enhanced phenanthrene hydrogenation saturation performance of Ni-Co/NiAlO_x catalysts and its catalytic mechanism[J]. Fuel Processing Technology, 2023, 250: 107902.
9	林俊明, 岑洁, 李正甲, 等. Ni基重整催化剂失活机理研究进展[J]. 化工进展, 2022, 41(1): 201-209.
	Lin J M, Cen J, Li Z J, et al. Development on deactivation mechanism of Ni-based reforming catalysts[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 201-209.
10	Liu X P, Yan J K, Mao J, et al. Inhibitor, co-catalyst, or intermetallic promoter? Probing the sulfur-tolerance of MoO_x surface decoration on Ni/SiO₂ during methane dry reforming[J]. Applied Surface Science, 2021, 548: 149231.
11	Liu D J, Wang Q, Wu J, et al. A review of sorbents for high-temperature hydrogen sulfide removal from hot coal gas[J]. Environmental Chemistry Letters, 2019, 17(1): 259-276.
12	刘玉良, 王文寿, 邹亢, 等. 硅酸锌生成对S Zorb吸附剂活性的影响[J]. 石油炼制与化工, 2022, 53(2): 63-68.
	Liu Y L, Wang W S, Zou K, et al. Effect of zinc silicate on desulfurization activity of S Zorb adsorbent [J]. Petroleum Processing and Petrochemicals, 2022, 53(2): 63-68.
13	Zhang J C, Liu Y Q, Tian S, et al. Reactive adsorption of thiophene on Ni/ZnO adsorbent: Effect of ZnO textural structure on the desulfurization activity[J]. Journal of Natural Gas Chemistry, 2010, 19(3): 327-332.
14	Zhang Y L, Yang Y X, Han H X, et al. Ultra-deep desulfurization via reactive adsorption on Ni/ZnO: The effect of ZnO particle size on the adsorption performance[J]. Applied Catalysis B: Environmental, 2012, 119: 13-19.
15	Gao P, Li S G, Bu X N, et al. Direct conversion of CO₂ into liquid fuels with high selectivity over a bifunctional catalyst[J]. Nature Chemistry, 2017, 9(10): 1019-1024.
16	Li Y B, Wang M H, Liu S H, et al. Distance for communication between metal and acid sites for syngas conversion[J]. ACS Catalysis, 2022, 12(15): 8793-8801.
17	马庆国, 孟德乔, 王如迎, 等. 铜铝复合氧化物的制备及催化甲醛降解反应[J]. 水处理技术, 2024, 50(1): 90-93, 99.
	Ma Q G, Meng D Q, Wang R Y, et al. Preparation of Cu-Al composite oxide and its catalytic degradation of formaldehyde[J]. Technology of Water Treatment, 2024, 50(1): 90-93, 99.
18	李思嵚, 吕建国, 陆波静, 等. Sn-Al共掺对非晶ZnO忆阻器的改性[J]. 材料科学与工程学报, 2023, 41(4): 532-539, 552.
	Li S Q, Lv J G, Lu B J, et al. Modification of amorphous ZnO memristor by Sn-Al co-doping[J]. Journal of Materials Science and Engineering, 2023, 41(4): 532-539, 552.
19	Jang J G, Lee Y K. Promotional effect of Ga for Ni₂P catalyst on hydrodesulfurization of 4,6-DMDBT[J]. Applied Catalysis B: Environmental, 2019, 250: 181-188.
20	Huang L C, Ge H, Yan L, et al. Competitive reactive adsorption desulphurization of dibenzothiophene and hydrogenation of naphthalene over Ni/ZnO[J]. The Canadian Journal of Chemical Engineering, 2018, 96(4): 865-872.
21	Zheng P, Li T S, Chi K B, et al. DFT insights into the direct desulfurization pathways of DBT and 4, 6-DMDBT catalyzed by Co-promoted and Ni-promoted MoS₂ corner sites[J]. Chemical Engineering Science, 2019, 206: 249-260.
22	Chen X J, Jiang J G, Yan F, et al. Dry reforming of model biogas on a Ni/SiO₂ catalyst: overall performance and mechanisms of sulfur poisoning and regeneration[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(11): 10248-10257.
23	Li N, Meng T, Ma L, et al. Curtailing carbon usage with addition of functionalized NiFe₂O₄ quantum dots: Toward more practical S cathodes for Li-S cells[J]. Nano-Micro Letters, 2020, 12(1):145.
24	Ibrahim M M, Naghmash M A. Physicochemical and optical studies of novel heterogeneous oxysulfide catalyst based on Mo for potential application in reduction reactions[J]. Materials Chemistry and Physics, 2023, 295: 127116.
25	Liu M T, Fu Y, Ma H W, et al. Flower-like manganese-cobalt oxysulfide supported on Ni foam as a novel faradaic electrode with commendable performance[J]. Electrochimica Acta, 2016, 191: 916-922.
26	Jena K K, Suresh Kumar Reddy K, Karanikolos G N, et al. Structure-property relationship of zeolite-Y/cubic ZnS nanohybrid material and its utilization for gaseous phase mercury removal[J]. Chemical Engineering Journal, 2023, 469: 143771.
27	Piña-Pérez Y, Samaniego-Benítez E, Sierra-Uribe J H, et al. Ethylenediamine-assisted solvothermal synthesis of ZnS/ZnO photocatalytic heterojunction for high-efficiency hydrogen production[J]. Environmental Science and Pollution Research, 2024: 31(25): 36118-36135.
28	Gupta M, He J, Nguyen T, et al. "Nanowire catalysts for ultra-deep hydro-desulfurization and aromatic hydrogenation"[J]. Applied Catalysis B: Environmental, 2016, 180: 246-254.
29	展学成, 王斌, 陈明林, 等. 裂解汽油一段选择加氢镍基催化剂失活因素及初活性钝化研究进展[J]. 现代化工, 2020, 40(11): 49-52, 57.
	Zhan X C, Wang B, Chen M L, et al. Review on deactivation factors and initial activity passivation of Ni-based catalyst for first stage selective hydrogenation of pyrolysis gasoline[J]. Modern Chemical Industry, 2020, 40(11): 49-52, 57.
30	李楠, 侯蕾, 杜霞茹, 等. 合成天然气Ni基甲烷化催化剂的研究进展[J]. 天然气化工(C1化学与化工), 2015, 40(3): 76-82.
	Li N, Hou L, Du X R, et al. Research progress in Ni-based methanation catalysts for synthesis of natural gas [J]. Natural Gas Chemical Industry, 2015, 40(3): 76-82.
31	Feng J P, Liu J J, Tang M X, et al. Effect of sulfur–carbon interaction on sulfur poisoning of Ni/Al₂O₃ catalysts for hydrogenation[J]. International Journal of Hydrogen Energy, 2017, 42(10): 6727-6737.

[1]	王天闻, 闫肃, 赵梦园, 杨天让, 刘建国. 固体氧化物电池空气电极铬中毒机理及抗铬性能研究进展[J]. 化工学报, 2024, 75(6): 2091-2108.
[2]	黄志鸿, 周利, 柴士阳, 吉旭. 耦合加氢装置优化的多周期氢网络集成[J]. 化工学报, 2024, 75(5): 1951-1965.
[3]	丁禹, 杨昌泽, 李军, 孙会东, 商辉. 原子尺度钼系加氢脱硫催化剂的研究进展与展望[J]. 化工学报, 2024, 75(5): 1735-1749.
[4]	李静, 张方芳, 王帅帅, 徐建华, 张朋远. 凹腔结构对正丁烷部分预混火焰可燃极限的影响[J]. 化工学报, 2024, 75(5): 2081-2090.
[5]	赵亭亭, 鄢立祥, 唐福利, 肖敏之, 谭烨, 宋刘斌, 肖忠良, 李灵均. 光辅助锂-二氧化碳电池催化剂的设计策略与反应机理研究进展[J]. 化工学报, 2024, 75(5): 1750-1764.
[6]	莫锦洪, 韩雪, 朱毅翔, 李菁, 王旭裕, 纪红兵. Pt-Ga/CeO₂-ZrO₂-Al₂O₃脱氢裂解双功能催化剂用于正丁烷催化制烯烃研究[J]. 化工学报, 2024, 75(5): 1855-1869.
[7]	范以薇, 刘威, 李盈盈, 王培霞, 张吉松. 有机液体储氢中全氢化乙基咔唑催化脱氢研究进展[J]. 化工学报, 2024, 75(4): 1198-1208.
[8]	贾旭东, 杨博龙, 程前, 李雪丽, 向中华. 分步负载金属法制备铁钴双金属位点高效氧还原电催化剂[J]. 化工学报, 2024, 75(4): 1578-1593.
[9]	严孝清, 赵瑛, 张宇哲, 欧鸿辉, 黄起中, 胡华贵, 杨贵东. 五重孪晶铜纳米线@聚吡咯制备及其电催化硝酸盐还原制氨[J]. 化工学报, 2024, 75(4): 1519-1532.
[10]	李添翼, 武玉泰, 王永胜, 顾佳锐, 宋沂恒, 杨丰铖, 郝广平. 轻同位素分离纯化与催化标记研究进展[J]. 化工学报, 2024, 75(4): 1284-1301.
[11]	孙铭泽, 黄鹤来, 牛志强. 铂基氧还原催化剂：从单晶电极到拓展表面纳米材料[J]. 化工学报, 2024, 75(4): 1256-1269.
[12]	申州洋, 薛康, 刘青, 史成香, 邹吉军, 张香文, 潘伦. 吸热型纳米流体燃料研究进展[J]. 化工学报, 2024, 75(4): 1167-1182.
[13]	程骁恺, 历伟, 王靖岱, 阳永荣. 镍催化可控/活性自由基聚合反应研究进展[J]. 化工学报, 2024, 75(4): 1105-1117.
[14]	韩宇, 周乐, 张鑫, 罗勇, 孙宝昌, 邹海魁, 陈建峰. 高黏附性Pd/SiO₂/NF整体式催化剂的制备及加氢性能研究[J]. 化工学报, 2024, 75(4): 1533-1542.
[15]	李昂, 赵振宇, 李洪, 高鑫. 微波诱导高分散Pd/FeP催化剂构筑及其电催化性能研究[J]. 化工学报, 2024, 75(4): 1594-1606.

Ni/Al₂O₃与ZnO距离对含硫菲加氢性能的影响

Influence of distance between Ni/Al₂O₃ and ZnO for deep hydrogenation of sulfur-containing phenanthrene

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价