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NiO含量对NiMo/Al2O3催化剂在焦炉煤气中噻吩加氢脱硫性能的影响
Effect of NiO content on thiophene hydrodesulfurization performance of NiMo/Al2O3 catalyst in coke oven gas
- 低碳化学与化工 2025, 50(4): 71-79.
- 作者机构：
1.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
2.太原理工大学 化学工程与技术学院，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
- 作者简介：
李姣姣（1997—），硕士研究生，研究方向为气体净化与工业催化，E-mail：1832045258@qq.com。
秦志峰（1983—），博士，副教授，硕士研究生导师，研究方向为煤转化过程中污染物控制及治理，E-mail：qinzhifeng2022@163.com。
- 基金信息：山西省科技重大专项(MJH2016-03);山西浙大新材料与化工研究院研发项目(2021ST-AT-002);东莞市能源投资集团有限公司攻关项目(RH2000004464)
DOI：10.12434/j.issn.2097-2547.20240231
中图分类号： TQ426收稿：2024-05-24，
修回：2024-08-02，
纸质出版：2025-04-25
- 稿件说明：
移动端阅览
李姣姣,秦志峰,李晓红等.NiO含量对NiMo/Al2O3催化剂在焦炉煤气中噻吩加氢脱硫性能的影响[J].低碳化学与化工,2025,50(04):71-79.
LI Jiaojiao,QIN Zhifeng,LI Xiaohong,et al.Effect of NiO content on thiophene hydrodesulfurization performance of NiMo/Al2O3 catalyst in coke oven gas[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):71-79.
李姣姣,秦志峰,李晓红等.NiO含量对NiMo/Al2O3催化剂在焦炉煤气中噻吩加氢脱硫性能的影响[J].低碳化学与化工,2025,50(04):71-79. DOI： 10.12434/j.issn.2097-2547.20240231.
LI Jiaojiao,QIN Zhifeng,LI Xiaohong,et al.Effect of NiO content on thiophene hydrodesulfurization performance of NiMo/Al2O3 catalyst in coke oven gas[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):71-79. DOI： 10.12434/j.issn.2097-2547.20240231.
摘要
焦炉煤气作为气体资源，常被用作化工原料，然而其中噻吩（C
4
H
4
S）等硫化物杂质的存在对催化剂具有较强毒害作用，工业上常通过二级镍钼加氢脱硫对噻吩进行深度脱除。为探究金属负载量对催化剂性能的影响，采用浸渍法制备了不同NiO含量（5%、10%、15%和20%，质量分数）的NiMo/Al
2
O
3
催化剂；在反应温度250~390 ℃、压力1 MPa和原料空速4500 h
-1
条件下，对催化剂焦炉煤气噻吩加氢脱硫性能进行了测试；并通过N
2
吸/脱附、XRD、H
2
-TPR和XPS等表征手段，探究了NiO含量对NiMo/Al
2
O
3
催化剂性能的影响。结果表明，在270~370 ℃区间内，催化剂的C
4
H
4
S转化率从大到小依次为Ni
5
Mo
15
/Al
2
O
3
、Ni
10
Mo
15
/Al
2
O
3
、Ni
15
Mo
15
/Al
2
O
3
和Ni
20
Mo
15
/Al
2
O
3
。其中，Ni
5
Mo
15
/Al
2
O
3
催化剂，290 ℃时C
4
H
4
S转化率达到70%，330 ℃时达到90%，明显高于其他3种催化剂。这归因于该催化剂在预硫化过程中，生成了更多活性物种MoS
2
，硫化程度较高。但随着NiO含量增大，可能发生NiO包覆MoO
3
的现象，导致催化剂硫化程度下降，催化性能减弱。
Abstract
Coke oven gas
as a valuable gaseous resource
is often used as a chemical raw material. However
sulfur impurities such as thiophene (C
4
H
4
S) in the gas exhibit strong poisoning effects on catalysts. Industrially
deep removal of thiophene is typically achieved via secondary Ni-Mo hydrodesulfurization. To investigate the effect of metal loading on catalyst performance
NiMo/Al
2
O
3
catalysts with varying NiO contents (5%
10%
15% and 20%
mass fraction) were prepared using the impregnation method. The hydrodesulfurization performance of these catalysts in coke oven gas was tested under conditions of reaction temperatures from 250 ℃ to 390 ℃
the pressure of 1 MPa
and the gas hourly space velocity of 4500 h
-1
. The effects of NiO content on the catalyst performance were analyzed using characterization techniques such as N
2
adsorption/desorption
XRD
H
2
-TPR
and XPS. The results show that in the temperature range of 270 ℃ to 370 ℃
the C
4
H
4
S conversion rates of the catalysts decrease in the order of Ni
5
Mo
15
/Al
2
O
3
Ni
10
Mo
15
/Al
2
O
3
Ni
15
Mo
15
/Al
2
O
3
and Ni
20
Mo
15
/Al
2
O
3
. Among them
the Ni
5
Mo
15
/Al
2
O
3
catalyst achieves a C
4
H
4
S conversion rate of 70% at 290 ℃ and 90% at 330 ℃
significantly outperforming the other three catalysts. This is attributed to the formation of more active MoS
2
species during the presulfurization process
resulting in a higher degree of sulfuration. However
with increasing NiO content
the phenomenon of NiO encapsulating MoO
3
likely occurres
resulting in decreased sulfuration and diminished catalytic performance.
关键词
Keywords
references
YU Z Y , XIE H Q , GUO R , et al . High-quality utilization of raw coke oven gas for hydrogen production based on CO 2 adsorption-enhanced reforming [J ] . Energy , 2024 , 305 : 132335 .
QIN Z F , ZHAO Y J , YI Q , et al . Methanation of coke oven gas over Ni-Ce/gamma-Al 2 O 3 catalyst using a tubular heat exchange reactor: Pilot-scale test and process optimization [J ] . Energy Conversion and Management , 2020 , 204 : 112302 .
PAN Z , CHAN W P , WANG H , et al . Regenerable Co-ZnO-based nanocomposites for high-temperature syngas desulfurization [J ] . Fuel Processing Technology , 2020 , 201 : 106344 .
李硕 , 刘熠斌 , 冯翔 , 等 . MoS 2 基催化剂加氢脱硫反应活性相和作用机理研究进展 [J ] . 化工进展 , 2019 , 38 ( 2 ): 867 - 875 .
LI S , LIU Y B , FENG X , et al . Research progress in active phase structure and reaction mechanism of MoS 2 -based catalysts for hydrodesulfurization [J ] . Chemical Industry and Engineering Progress , 2019 , 38 ( 2 ): 867 - 875 .
YANG C , FLORENT M G , FAN H , et al . ZnFe 2 O 4 /activated carbon as a regenerable adsorbent for catalytic removal of H 2 S from air at room temperature [J ] . Chemical Engineering Journal , 2020 , 394 : 124906 .
MORAL G , ORTIZ-IMEDIO R , ORTIZ A , et al . Hydrogen recovery from coke oven gas comparative analysis of technical altematives [J ] . Industrial & Engineering Chemistry Research , 2022 , 61 ( 18 ): 6106 - 6124 .
ZHOU J B , GUO Y J , HUANG Z W , et al . A review and prospects of gas mixture containing hydrogen as vehicle fuel in China [J ] . International Journal of Hydrogen Energy , 2019 , 44 ( 56 ): 29776 - 29784 .
RAZZAQR R , LI C S , ZHANF S J . Coke oven gas: Availability, properties, purification, and utilization in China [J ] . Fuel , 2013 , 113 : 287 - 299 .
WENG X Y , CAO L Y , ZHANG G H , et al . Ultradeep hydrodesulfurization of diesel: Mechanisms, catalyst design strategies, and challenges [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 49 ): 21261 - 21274 .
YANG R C , ZHANG Z H , WU J S , et al . Hydrotreating performance of La-modified Ni/Al 2 O 3 catalysts prepared by hydrothermal impregnation method [J ] . Kinetics and Catalysis , 2015 , 56 : 222 - 225 .
袁礼 , 王学谦 , 李翔 , 等 . 催化脱除钢铁副产煤气中COS和H 2 S的研究进展 [J ] . 化工进展 , 2023 , 42 ( 10 ): 5147 - 5161 .
YUAN L , WANG X Q , LI X , et al . Research advances on catalytic removal COS and H 2 S from by-product gas in iron and steel industry [J ] . Chemical Industry and Engineering Progress , 2023 , 42 ( 10 ): 5147 - 5161 .
穆福军 , 隋宝宽 , 刘文洁 , 等 . 渣油加氢处理催化剂失活研究 [J ] . 石油化工 , 2022 , 51 ( 9 ): 1044 - 1051 .
MU F J , SUI B K , LIU W J , et al . Study on deactivation of residue hydrotreating catalyst [J ] . Petrochemical Technology , 2022 , 51 ( 9 ): 1044 - 1051 .
汪佩华 . NiMo催化剂应用于焦炉煤气加氢脱硫性能研究 [D ] . 太原 : 太原理工大学 , 2020 .
WANG P H . Study on the application of NiMo catalyst to hydrodesulfurization of coke oven gas [D ] . Taiyuan : Taiyuan University of Technology , 2020 .
LIU H , LI Y P , YIN C L , et al . One-pot synthesis of ordered mesoporous NiMo-Al 2 O 3 catalysts for dibenzothiophene hydrodesulfurization [J ] . Applied Catalysis B: Environment and Energy , 2016 , 198 : 493 - 507 .
KVĚTA J , ALLA S . Hydrodesulfurization activities of NiMo catalysts supported on mechanochemically prepared Al-Ce mixed oxides [J ] . Chinese Journal of Catalysis , 2016 , 37 ( 2 ): 258 - 267 .
刘理华 , 刘迪 , 刘宾 , 等 . NiMo催化剂上MoS 2 形貌与其DBT加氢脱硫选择性的关系 [J ] . 燃料化学学报 , 2011 , 39 ( 11 ): 838 - 843 .
LIU L H , LIU D , LIU B , et al . The relationship between MoS 2 morphology and DBT hydrodesulfurization selectivity on NiMo catalyst [J ] . Journal of Fuel Chemistry , 2011 , 39 ( 11 ): 838 - 843 .
蒋绍洋 , 刘秀娜 , 刘志坚 , 等 . NiMo/Al 2 O 3 催化剂性质与加氢脱硫转化率的定量关系模型 [J ] . 石油炼制与化工 , 2018 , 49 ( 1 ): 54 - 59 .
JIANG S Y , LIU X N , LIU Z J , et al . Quantitative relationship model of NiMo/Al 2 O 3 catalyst properties and hydrodesulfurization conversion [J ] . Petroleum Processing and Petrochemicals , 2018 , 49 ( 1 ): 54 - 59 .
王宇 , 宋华 . Ni掺杂量对高活性NiMoS 2 /TiO 2 催化剂加氢脱硫性能的影响 [J ] . 能源化工 , 2020 , 41 ( 4 ): 20 - 24 .
WANG Y , SONG H . Effect of Ni doping amount on hydrodesulfurization performance of highly active NiMoS 2 /TiO 2 catalyst [J ] . Energy Chemical Industry , 2020 , 41 ( 4 ): 20 - 24 .
李乃珍 , 孙瑞洁 , 秦志峰 , 等 . 焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响 [J ] . 化工进展 , 2023 , 42 ( 2 ): 783 - 793 .
LI N Z , SUN R J , QIN Z F , et al . Effects of constant carbon atmosphere on the activity, selectivity and coking of catalysts in hydrodesulfurization of coke oven gas [J ] . Chemical Industry and Engineering Progress , 2023 , 42 ( 2 ): 783 - 793 .
LI G C , LIU W Q , TANG Z , et al . Effects of rehydration of alumina on its structural properties, surface acidity, and HDN activity of quinoline-ScienceDirect [J ] . Applied Catalysis A , 2012 , 437/438 : 79 - 89 .
DIGNE M , SAUTET P , RAYBAUD P , et al . Structure and stability of aluminum hydroxides: A theoretical study [J ] . The Journal of Chemical Physics , 2002 , 106 ( 20 ): 5155 - 5162 .
张大龙 , 徐永卫 , 李孟华 , 等 . 溶胶-凝胶法制备体相型Mo-Ni复合氧化物催化剂及其加氢脱硫性能研究 [J ] . 石油炼制与化工 , 2016 , 47 ( 5 ): 67 - 73 .
ZHANG D L , XU Y W , LI M H , et al . Synthesis of MO-Ni bulk catalyst by sol-gel methodand its hydrodesulfurization performance [J ] . Petroleum Processing and Petrochemicals , 2016 , 47 ( 5 ): 67 - 73 .
GUTIÉRREZ O Y , KLIMOVA T . Effect of the support on the high activity of the (Ni)Mo/ZrO 2 SBA15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT [J ] . Journal of Catalysis , 2011 , 281 ( 1 ): 50 - 62 .
GONZÁLEZ-CORTÉS S L , RUGMINI S , XIAO T , et al . Deep hydrotreating of different feedstocks over a highly active Al 2 O 3 -supported NiMoW sulfide catalyst [J ] . Applied Catalysis A , 2014 , 475 : 270 - 281 .
ESWARAMOORTHI I , SUNDARAMURTHY V , NIKHIL DAS . Application of multi-walled carbon nanotubes as efficient support to NiMo hydrotreating catalyst [J ] . Applied Catalysis A , 2008 , 339 ( 2 ): 187 - 195 .
ESCOBAR J , BARRERA , M C , GUTIERREZ , A W , et al . Benzothiophene hydrodesulfurization over NiMo/alumina catalysts modified by citric acid. Effect of addition stage of organic modifier [J ] . Fuel Processing Technology , 2017 , 156 : 33 - 42 .
LAURITSEN J V , KIBSGAARD J , OLESEN G H , et al . Location and coordination of promoter atoms in Co- and Ni-promoted MoS 2 -based hydrotreating catalysts [J ] . Journal of Catalysis , 2007 , 249 ( 2 ): 220 - 233 .
BADOGA S , SHARMA R V , DALAI A K , et al . Hydrotreating of heavy gas oil on mesoporous zirconia supported NiMo catalyst with EDTA [J ] . Fuel , 2014 , 128 : 30 - 38 .
LI M F , LI H F , JIANG F , et al . Effect of surface characteristics of different alumina on metal-support interaction and hydrodesulfurization activity [J ] . Fuel , 2009 , 88 ( 7 ): 1281 - 1285 .
LI Y Y , MEN Y , LIU S , et al . Remarkably efficient and stable Ni/Y 2 O 3 catalysts for CO 2 methanation: Effect of citricacid addition [J ] . Applied Catalysis B , 2021 , 293 : 120206 .
MADEIRA L M , MARTIN-ARANDA R M , MALDONADO-HODAR F J , et al . Oxidative dehydrogenation of n -butane over alkali and alkaline earth-promoted α -NiMoO 4 catalysts [J ] . Journal of Catalysis , 1997 , 169 ( 2 ): 469 - 479 .
LI Q , SUI Z J , ZHOU X G , et al . Coke formation on Pt-Sn/Al 2 O 3 catalyst in propane dehydrogenation: Coke characterization and kinetic study [J ] . Topics in Catalysis , 2011 , 54 ( 13 ): 888 - 896 .
ROCHET A , BAUBET B , MOIZAN V , et al . Influence of the preparation conditions of oxidic NiMo/Al 2 O 3 catalysts on the sulfidation ability: A quick-XAS and Raman spectroscopic study [J ] . The Journal of Physical Chemistry C , 2015 , 119 ( 42 ): 23928 - 23942 .
NAVEENJI A , JASON M , NING C , et al . NiMo nitride supported on gamma-Al 2 O 3 for hydrodeoxygenation of oleic acid: Novel characterization and activity study [J ] . Catalysis Today , 2017 , 291 : 153 - 159 .
NICOSIA D , PRINS R . The effect of phosphate and glycol on the sulfidation mechanism of CoMo/Al 2 O 3 hydrotreating catalysts: An in situ QEXAFS study [J ] . Journal of Catalysis , 2005 , 231 ( 2 ): 259 - 268 .
YAMAMOTO T , KUBOTA T , OKAMOTO Y . Effect of phosphorus addition on the active sites of a Co-Mo/Al 2 O 3 catalyst for the hydrodesulfurization of thiophene [J ] . Applied Catalysis A , 2007 , 328 ( 2 ): 219 - 225 .
LIU B S , JIANG L , SUN H , et al . XPS, XAES, and TG/DTA characterization of deposited carbon in methane dehydroaromatization over Ga-Mo/ZSM-5 catalyst [J ] . Applied Surface Science , 2007 , 253 ( 11 ): 5092 - 5100 .
WANG J M , SONG Z , HAN M X , et al . Molybdenum-based catalysts supported on alumina for direct dehydrogenation of isobutane [J ] . Molecular Catalysis , 2021 , 511 : 111746 .
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