Citation: LU Pei-jing, CAI Fu-feng, ZHANG Jun, LIU Yu-yu, SUN Yu-han. Hydrogen production from methanol steam reforming over B-modified CuZnAlO_x catalysts[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(7): 791-798. shu

Hydrogen production from methanol steam reforming over B-modified CuZnAlO_x catalysts

LU Pei-jing ^1,2 ,
CAI Fu-feng ² ,
ZHANG Jun ² ,
LIU Yu-yu ^1,3,, ,
SUN Yu-han ²

1.
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China
2.
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
3.
Sustainable Energy Research Institute, Shanghai University, Shanghai 200444, China

Corresponding author: LIU Yu-yu, liuyuyu2014@126.com
Received Date: 13 March 2019
Revised Date: 16 April 2019

Fund Project: The project was supported by the China Ministry of Science and Technology (2016YFA0202802)the China Ministry of Science and Technology 2016YFA0202802

Figures(8)

In this work, CuZnAlO_x (CZA) catalysts prepared by coprecipitation method and a series of yB/CZA catalysts with various boron loadings (y=0.28%, 0.38%, 0.73%, 0.89% and 4.10%) prepared by impregnation method were used in the methanol steam reforming for hydrogen production. In addition, the B-modified CZA catalysts were deeply characterized by different techniques such as ICP, BET, SEM, N₂O chemisorption, TEM, XRD, H₂-TPR and XPS to explore the structure-activity relationship. The characterization results revealed that the introduction primarily affected the Cu dispersion, reductibility and the interaction between the boron and copper species. The 0.38B/CZA catalyst revealed the optimum catalytic performance among the researched catalysts, which were due to the presence of highly dispersed Cu particles and the strong interaction between the boron and copper species. The 93% methanol conversion, the CO selectivity as low as 0.3%, and the long-time stability with 102 h time on stream were obtained over it when the reaction conditions were 250℃, n(H₂O):n(CH₃OH)=3 and GHSV=9000 mL/(g·h).
- boron,
- CuZnAlO_x catalysts,
- methanol steam reforming,
- hydrogen
1. [1]
  NIKOLAIDIS P, POULLIKKAS A. A comparative overview of hydrogen production processes[J]. Renewable Sustainable Energy Rev, 2017,67(Supplement C):597-611.
2. [2]
  SANDRA S Á, SILVA H, BRANDÃO L, SOUSA J, MENDES A. Catalysts for methanol steam reforming-A review[J]. Appl Catal B:Environ, 2010,99(1/2):43-57.
3. [3]
  FRANK B, JENTOFT F, SOERIJANTO H, KROHNERT J, SCHLOGL R, SCHOMACKER R. Steam reforming of methanol over copper-containing catalysts:Influence of support material on microkinetics[J]. J Catal, 2007,246(1):177-192.
4. [4]
  LIN L, ZHOU W, GAO R, YAO S, ZHANG X, XU W, ZHENG S, ZHENG J, YU Q, LI Y, SHI C, WEN X, MA D. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts[J]. Nature, 2017,544(7648):80-83. doi: 10.1038/nature21672
5. [5]
  XU T, ZOU J, TAO W, ZHANG S, CUI L, ZENG F, WANG D, CUI W. Co-nanocasting synthesis of Cu based composite oxide and its promoted catalytic activity for methanol steam reforming[J]. Fuel, 2016,183:238-244. doi: 10.1016/j.fuel.2016.06.081
6. [6]
  TAGHIZADEH M, AKHOUNDZADEH H, REZAYAN A, SADEGHIAN M. Excellent catalytic performance of 3D-mesoporous KIT-6 supported Cu and Ce nanoparticles in methanol steam reforming[J]. Int J Hydrogen Energy, 2018,43(24):10926-10937. doi: 10.1016/j.ijhydene.2018.05.034
7. [7]
  TALKHONCHEH S, HAGHIGHI M, MINAEI S, AJAMEIN H, ABDOLLAHIFAR M. Synthesis of CuO/ZnO/Al₂O₃/ZrO₂/CeO₂ nanocatalysts via homogeneous precipitation and combustion methods used in methanol steam reforming for fuel cell grade hydrogen production[J]. RSC Adv, 2016,6(62):57199-57209. doi: 10.1039/C6RA03858A
8. [8]
  KHZOUZ M, GKANAS E, DU S, WOOD J. Catalytic performance of Ni-Cu/Al₂O₃ for effective syngas production by methanol steam reforming[J]. Fuel, 2018,232:672-683. doi: 10.1016/j.fuel.2018.06.025
9. [9]
  YONG S, OOI C, CHAI S, WU X. Review of methanol reforming-Cu-based catalysts, surface reaction mechanisms and reaction schemes[J]. Int J Hydrogen Energy, 2013,38(22):9541-9552. doi: 10.1016/j.ijhydene.2013.03.023
10. [10]
  LIU X, MEN Y, WANG J, HE R, WANG Y. Remarkable support effect on the reactivity of Pt/In₂O₃/MO_x catalysts for methanol steam reforming[J]. J Power Sources, 2017,364(Supplement C):341-350.
11. [11]
  CHANG C, CHANG C, CHIANGS J, LIAW B, CHEN Y. Oxidative steam reforming of methanol over CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts[J]. Int J Hydrogen Energy, 2010,35(15):7675-7683. doi: 10.1016/j.ijhydene.2010.05.066
12. [12]
  MATTER P, OZKAN U. Effect of pretreatment conditions on Cu/Zn/Zr-based catalysts for the steam reforming of methanol to H₂[J]. J Catal, 2005,234(2):463-475.
13. [13]
  GANG H, LIAW B, JHANG C, CHEN Y. Steam reforming of methanol over CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts[J]. Appl Catal A:Gen, 2009,358(1):7-12. doi: 10.1016/j.apcata.2009.01.031
14. [14]
  TOYIR J, PISCINA P, HOMS N. Ga-promoted copper-based catalysts highly selective for methanol steam reforming to hydrogen; relation with the hydrogenation of CO₂ to methanol[J]. Int J Hydrogen Energy, 2015,40(34):11261-11266. doi: 10.1016/j.ijhydene.2015.04.039
15. [15]
  YANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu. Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming[J]. J Fuel Chem Technol, 2018,46(2):179-188.
16. [16]
  PARK J, YIM S, KIM C, PARK E. Steam reforming of methanol over Cu/ZnO/ZrO₂/Al₂O₃ catalyst[J]. Int J Hydrogen Energy, 2014,39(22):11517-11527. doi: 10.1016/j.ijhydene.2014.05.130
17. [17]
  MINAEI S, HAGHIGHI M, JODEIRI N, AJAMEIN H, ABDOLLAHIFAR M. Urea-nitrates combustion preparation of CeO₂-promoted CuO/ZnO/Al₂O₃ nanocatalyst for fuel cell grade hydrogen production via methanol steam reforming[J]. Adv Powder Technol, 2017,28(3):842-853. doi: 10.1016/j.apt.2016.12.010
18. [18]
  BAGHERZADEH S, HAGHIGHI M, RAHEM N. Novel oxalate gel coprecipitation synthesis of ZrO₂-CeO₂-promoted CuO-ZnO-Al₂O₃ nanocatalyst for fuel cell-grade hydrogen production from methanol:Influence of ceria-zirconia loading[J]. Energy Convers Manage, 2017,134:88-102. doi: 10.1016/j.enconman.2016.12.005
19. [19]
  NANDA M, YUAN Z, SHUI H, XU C. Selective hydrogenolysis of glycerol and crude glycerol (a By-Product or Waste Stream from the Biodiesel Industry) to 1, 2-propanediol over B₂O₃ promoted Cu/Al₂O₃ catalysts[J]. Catalysts, 2017,7(7)196. doi: 10.3390/catal7070196
20. [20]
  ZHU S, GAO X, ZHU Y, ZHU Y, ZHENG H, LI Y. Promoting effect of boron oxide on Cu/SiO₂ catalyst for glycerol hydrogenolysis to 1, 2-propanediol[J]. J Catal, 2013,303(7):70-79.
21. [21]
  AI P, TAN M, YAMANE N, LIU G, FAN R, YANG G, YONEYAMA Y, YANG R, TSUBAKI N. Synergistic effect of a boron-doped carbon-nanotube-supported Cu catalyst for selective hydrogenation of dimethyl oxalate to ethanol[J]. Chem Eur J, 2017,23(34):8252-8261. doi: 10.1002/chem.v23.34
22. [22]
  HE Z, LIN H, HE P, YUAN Y. Effect of boric oxide doping on the stability and activity of a Cu-SiO₂ catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol[J]. J Catal, 2011,277(1):54-63. doi: 10.1016/j.jcat.2010.10.010
23. [23]
  LIU Yu-juan, WANG Dong-zhe, ZHANG Lei, WANG Hong-hao, CHEN Lin, LIU Dao-sheng, HAN Jiao, ZHANG Cai-shun. Effect of support calcination atmospheres on the activity of CuO/CeO₂ catalysts for methanol steam reforming[J]. J Fuel Chem Technol, 2018,46(8):992-999.
24. [24]
  ZHAO S, YUE H, ZHAO Y, WANG B, GENG Y, LV J, WANG S, GONG J, MA X. Chemoselective synthesis of ethanol via hydrogenation of dimethyl; oxalate on Cu/SiO₂:Enhanced stability with boron dopant[J]. J Catal, 2013,297(1):142-150.
25. [25]
  AJAMEIN H, HAGHIGHI M, SHOKRANI R, ABDOLLAHIFAR M. On the solution combustion synthesis of copper based nanocatalysts for steam methanol reforming:Effect of precursor, ultrasound irradiation and urea/nitrate ratio[J]. J Mol Catal A:Chem, 2016,421:222-234. doi: 10.1016/j.molcata.2016.05.028
26. [26]
  FIGEN A. Dehydrogenation characteristics of ammonia boraneviaboron-basedcatalysts (Co-B, Ni-B, Cu-B) under different hydrolysis conditions[J]. Int J Hydrogen Energy, 2013,38(22):9186-9197. doi: 10.1016/j.ijhydene.2013.05.081
27. [27]
  WU J, SAITO M, MABUSE H. Activity and stability of Cu/ZnO/Al₂O₃ catalyst promoted with B₂O₃ for methanol synthesis[J]. Catal Lett, 2000,68(1):55-58.
28. [28]
  GAO P, ZHONG L, ZHANG L, WANG H, ZHAO N, WEI W, SUN Y. Yttrium oxide modified Cu/ZnO/Al₂O₃ catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catal Sci Technol, 2015,5(9):4365-4377. doi: 10.1039/C5CY00372E
29. [29]
  YIN A, QU J, GUO X, DAI W, FAN K. The influence of B-doping on the catalytic performance of Cu/HMS catalyst for the hydrogenation of dimethyloxalate[J]. Appl Catal A:Gen, 2011,400(1):39-47.
30. [30]
  SHOKRANI P, HAGHIGHI M, JODEIRI N, AJAMEIN H, ABDOLLAHIFAR M. Fuel cell grade hydrogen production via methanol steam reforming over CuO/ZnO/Al₂O₃ nanocatalyst with various oxide ratios synthesized via urea-nitrates combustion method[J]. Int J Hydrogen Energy, 2014,39(25):13141-13155. doi: 10.1016/j.ijhydene.2014.06.048
31. [31]
  CHEN H, TAN J, CUI J, YANG X, ZHENG H, ZHU Y, LI Y. Promoting effect of boron oxide on Ag/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to methyl glycolate[J]. Mol Catal, 2017,433:346-353. doi: 10.1016/j.mcat.2017.02.039
1. [1]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-0. doi: 10.1016/j.actphy.2025.100067
2. [2]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
3. [3]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Construction of Electron Bridge and Activation of MoS₂ Inert Basal Planes by Ni Doping for Enhancing Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-0. doi: 10.3866/PKU.WHXB202406024
4. [4]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
5. [5]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
6. [6]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
7. [7]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
8. [8]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017
9. [9]
  Fangxuan Liu , Ziyan Liu , Guowei Zhou , Tingting Gao , Wenyu Liu , Bin Sun . 中空结构光催化剂. Acta Physico-Chimica Sinica, 2025, 41(7): 100071-0. doi: 10.1016/j.actphy.2025.100071
10. [10]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
11. [11]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
12. [12]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . Research Progress on Carbon-based Catalysts for Catalytic Dehydrogenation of Liquid Organic Hydrogen Carriers. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-0. doi: 10.1016/j.actphy.2024.100044
13. [13]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
14. [14]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
15. [15]
  Haodong JIN , Qingqing LIU , Chaoyang SHI , Danyang WEI , Jie YU , Xuhui XU , Mingli XU . NiCu/ZnO heterostructure photothermal electrocatalyst for efficient hydrogen evolution reaction. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1068-1082. doi: 10.11862/CJIC.20250048
16. [16]
  Lele Feng , Xueying Bai , Jifeng Pang , Hongchen Cao , Xiaoyan Liu , Wenhao Luo , Xiaofeng Yang , Pengfei Wu , Mingyuan Zheng . Single-atom Pd boosted Cu catalysts for ethanol dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(9): 100100-0. doi: 10.1016/j.actphy.2025.100100
17. [17]
  Huiwei Ding , Bo Peng , Zhihao Wang , Qiaofeng Han . Advances in Metal or Nonmetal Modification of Bismuth-Based Photocatalysts. Acta Physico-Chimica Sinica, 2024, 40(4): 2305048-0. doi: 10.3866/PKU.WHXB202305048
18. [18]
  Yushan Cai , Fang-Xing Xiao . Revisiting MXenes-based Photocatalysis Landscape: Progress, Challenges, and Future Perspectives. Acta Physico-Chimica Sinica, 2024, 40(8): 2306048-0. doi: 10.3866/PKU.WHXB202306048
19. [19]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-0. doi: 10.3866/PKU.WHXB202312024
20. [20]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-0. doi: 10.3866/PKU.WHXB202405016

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(920)
HTML views(106)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Hydrogen production from methanol steam reforming over B-modified CuZnAlOx catalysts

Metrics

通讯作者: 陈斌, bchen63@163.com

Hydrogen production from methanol steam reforming over B-modified CuZnAlO_x catalysts