Citation: ZHAO Yan-ling, DAI Rong, ZHENG Zi-liang, WANG Shi-yao, SUN Chen, LI Xing, XIE Xian-mei. Beta zeolite supported Cu/Ni catalyst for hydrogen production through ethanol steam reforming[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(11): 1392-1400. shu

Beta zeolite supported Cu/Ni catalyst for hydrogen production through ethanol steam reforming

ZHAO Yan-ling ^1,2 ,
DAI Rong ¹ ,
ZHENG Zi-liang ^1,3 ,
WANG Shi-yao ¹ ,
SUN Chen ¹ ,
LI Xing ¹ ,
XIE Xian-mei ^1,,

1.
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2.
Department of Medical Imaging, Shanxi Medical University, Taiyuan 030001, China
3.
Translational Medicine Research Center, Shanxi Medical University, Taiyuan 030001, China

Corresponding author: XIE Xian-mei, xxmsxty@sina.com
Received Date: 17 May 2017
Revised Date: 17 September 2017

Fund Project: Innovation Project of Shanxi Graduate Education 2016BY051The project was supported by the National Natural Science Foundation of China (51541210) and Innovation Project of Shanxi Graduate Education (2016BY051)the National Natural Science Foundation of China 51541210

Figures(8)

A group of multi-functional xCuyNi-ABZ catalysts supported on all-silicon Beta zeolite were prepared by an incipient wetness impregnation method. The xCuyNi-ABZ catalysts were characterized by a variety of techniques to obtain the information of their structures, the effect of different amounts of Cu and Ni active sites and understanding the reaction pathway. Compared with the traditional SiO₂ supported catalyst, the 2.5Cu2.5Ni-ABZ catalyst exhibited very good catalytic performance for the ethanol steam reforming, including 100% conversion of ethanol, high 67.23% H₂ selectivity (67.23%) and low by-product selectivity (CO=4.14%, CH₄=5.65%) at 450 ℃ due to the synergistic effects of Ni and Cu. The Cu sites preferentially facilitate the dehydrogenation of ethanol at the initial reaction step, and the Ni metal catalyzes subsequently dissociation of the C-C bond. With increase of reaction temperature, H₂ and CO₂ selectivity are progressively increased together with the significant decline of CO and CH₄ selectivity, which indicates that the dominant reaction is steam acetaldehyde reforming. This phenomenon suggests that there is a temperature-related competition between acetaldehyde decomposition and acetaldehyde steam reforming reaction. Moreover, the presence of Cu promoted the water-gas-shift reaction. The 2.5Cu2.5Ni-ABZ catalyst possesses good anti-sintering ability and anti-carbon deposition properties.
- ethanol steam reforming,
- hydrogen production,
- all-silica Beta zeolite,
- Ni,
- Cu
1. [1]
  FANG W, PAUL S, CAPRON M, BIRADAR A V, UMBARKAR S B, DONGARE M. K., DUMEIGNIL F., JALOWIECKI-DUHAMEL L. Highly loaded well dispersed stable Ni species in Ni_xMg₂AlO_y nanocomposites:Application to hydrogen production from bioethanol[J]. Appl Catal B:Environ, 2015,166:485-496.
2. [2]
  CROWLEY S, CASTALDI M J. Mechanistic insights into catalytic ethanol steam reforming using lsotope-labeled reactants[J]. Angew Chem Int Edit, 2016,55(36):10650-10655. doi: 10.1002/anie.201604388
3. [3]
  XU W, LIU Z, JOHNSTON-PECK A C, SENANAYAKE S D, ZHOU G, STACCHIOLA D, STACH E A, RODRIGUEZ J A. Steam reforming of ethanol on Ni/CeO₂:Reaction pathway and interaction between Ni and the CeO₂ support[J]. ACS Catal, 2013,3(5):975-984. doi: 10.1021/cs4000969
4. [4]
  ROSSETTI I, LASSO J, NICHELE V, SIGNORETTOB M, FINOCCHIOC E, RAMISC G, MICHELED A D. Silica and zirconia supported catalysts for the low-temperature ethanol steam reforming[J]. Appl Catal B:Environ, 2014,150:257-267.
5. [5]
  CORONRLA L, MÚNERAA J F, TARDITIA A M, MORENOB M S, CORNAGLIA L M. Hydrogen production by ethanol steam reforming over Rh nanoparticles supported on lanthana/silica systems[J]. Appl Catal B:Environ, 2014,160:254-266.
6. [6]
  RAMOSA A C, MONTINIB T, LORENZUTB B, TROIANIA H, GENNARIA F C, GRAZIANIB M, FORNASIERO P. Hydrogen production from ethanol steam reforming on M/CeO₂/YSZ (M=Ru, Pd, Ag) nanocomposites[J]. Catal Today, 2012,180(1):96-104. doi: 10.1016/j.cattod.2011.03.068
7. [7]
  CHEN Y, SHAO Z, XU N. Ethanol steam reforming over Pt catalysts supported on Ce_xZr_1-xO₂ prepared via a glycine nitrate process[J]. Energy Fuels, 2008,22(3):1873-1879. doi: 10.1021/ef700576f
8. [8]
  SUN J, QIU X, WU F. H₂ from steam reforming of ethanol at low temperature over Ni/Y₂O₃, Ni/La₂O₃ and Ni/Al₂O₃ catalysts for fuel-cell application[J]. Int J Hydrogen Energy, 2005,30(4):437-445. doi: 10.1016/j.ijhydene.2004.11.005
9. [9]
  LIU Z, SENANAYAKE S D, RODRIGUEZ J A. Elucidating the interaction between Ni and CeO_x in ethanol steam reforming catalysts:A perspective of recent studies over model and powder systems[J]. Appl Catal B:Environ, 2016,197:184-197. doi: 10.1016/j.apcatb.2016.03.013
10. [10]
  HARYANTO A, FERNANDO S, MURALI N, ADHIKARI S. Current status of hydrogen production techniques by steam reforming of ethanol:a review[J]. Energy Fuels, 2005,19(5):2098-2106. doi: 10.1021/ef0500538
11. [11]
  MORAES T S, NETO R C R, RIBEIRO M C, MATTOS L V, KOURTELESIS M, LADAS S, VERYKIOS X, NORONHA F B. The study of the performance of PtNi/CeO₂-nanocube catalysts for low temperature steam reforming of ethanol[J]. Catal Today, 2015,242:35-49. doi: 10.1016/j.cattod.2014.05.045
12. [12]
  NICHELE V, SIGNORETTO M, PINNA F, COMPAGNONI E G M, ROSSETTI I, CRUCIANI G, MICHELE A D. Bimetallic Ni-Cu catalysts for the low-temperature ethanol steam reforming:Importance of metal-support interactions[J]. Catal Lett, 2015,145(2):549-558. doi: 10.1007/s10562-014-1414-2
13. [13]
  CONTRERAS J, SALMONES J, COLÍN-LUNA J, NUÑO L, QUINTANA B, CÓRDOVA I, ZEIFERTB B, TAPIA C, FUENTES G A. Catalysts for H₂ production using the ethanol steam reforming (a review)[J]. Int J Hydrogen Energy, 2014,39(33):18835-18853. doi: 10.1016/j.ijhydene.2014.08.072
14. [14]
  CAMPOS-SKROBOT F C, RIZZO-DOMINGUES R C P, FERNANDES-MACHADO N R C, CANTÃO M P. Novel zeolite-supported rhodium catalysts for ethanol steam reforming[J]. J Power Sources, 2008,183(2):713-716. doi: 10.1016/j.jpowsour.2008.05.066
15. [15]
  LANG L, ZHAO S, YIN X. Catalytic activities of K-modified zeolite ZSM-5 supported rhodium catalysts in low-temperature steam reforming of bioethanol[J]. Int J Hydrogen Energy, 2015,40(32):9924-9934. doi: 10.1016/j.ijhydene.2015.06.016
16. [16]
  DA COSTA-SERRA J F, NAVARRO M T, REY F, CHICA A. Bioethanol steam reforming on Ni-based modified mordenite[J]. Int J Hydrogen Energy, 2012,37(8):7101-7108. doi: 10.1016/j.ijhydene.2011.10.086
17. [17]
  INOKAWA H, NISHIMOTO S, KAMESHIMA Y, MIYAKE M. Promotion of H₂ production from ethanol steam reforming by zeolite basicity[J]. Int J Hydrogen Energy, 2011,36(23):15195-15202. doi: 10.1016/j.ijhydene.2011.08.099
18. [18]
  KIM T W, KIM S Y, KIM J C, KIMB Y, RYOOB R, KIMA C-U. Selective p-xylene production from biomass-derived dimethylfuran and ethylene over zeolite beta nanosponge catalysts[J]. Appl Catal B:Environ, 2016,185:100-109. doi: 10.1016/j.apcatb.2015.11.046
19. [19]
  SERRANO D, GRIEKEN R V, SANCHEZ P, SANZ R, RODRIÓGUEZ L. Crystallization mechanism of all-silica zeolite beta in fluoride medium[J]. Microporous Mesoporous Mater, 2001,46(1):35-46. doi: 10.1016/S1387-1811(01)00272-4
20. [20]
  SAW E T, OEMAR U, TAN X R, DUB Y, BORGNAB A, HIDAJATA K, KAWI S. Bimetallic Ni-Cu catalyst supported on CeO₂ for high-temperature water-gas shift reaction:Methane suppression via enhanced CO adsorption[J]. J Catal, 2014,314:32-46. doi: 10.1016/j.jcat.2014.03.015
21. [21]
  VIZCAÍNO A J, CARRERO A, CALLES J A. Hydrogen production by ethanol steam reforming over Cu-Ni supported catalysts[J]. Int J Hydrogen Energy, 2007,32(10):1450-1461.
22. [22]
  ZHENG Z, YANG D, LI T, YIN X M, WANG S Y, WU X, AN X, XIE X M. A novel BEA-type zeolite core-shell multiple catalyst for hydrogen-rich gas production from ethanol steam reforming[J]. Catal Sci Technol, 2016,6(14):5427-5439. doi: 10.1039/C6CY00119J
23. [23]
  BREEN J P, BURCH R, COLEMAN H M. Metal-catalysed steam reforming of ethanol in the production of hydrogen for fuel cell applications[J]. Appl Catal B:Environ, 2002,39(1):65-74. doi: 10.1016/S0926-3373(02)00075-9
24. [24]
  GARBARINO G, WANG C, VALSAMAKIS I, CHITSAZAN S, RIANIC P, FINOCCHIO E, FLYTZANI-STEPHANOPOULOS M, BUSC G. A study of Ni/Al₂O₃ and Ni-La/Al₂O₃ catalysts for the steam reforming of ethanol and phenol[J]. Appl Catal B:Environ, 2015,174:21-34.
25. [25]
  KALAMARAS C M, PANAGIOTOPOULOU P, KONDARIDES D I, CHITSAZANA S, RIANIC P, FINOCCHIOA E, FLYTZANI-STEPHANOPOULOSB M, BUSCA G. Kinetic and mechanistic studies of the water-gas shift reaction on Pt/TiO₂ catalyst[J]. J Catal, 2009,264(2):117-129. doi: 10.1016/j.jcat.2009.03.002
26. [26]
  CALLES J A, CARRERO A, VIZCAÍNO A J. Effect of Ce and Zr addition to Ni/SiO₂ catalysts for hydrogen production through ethanol steam reforming[J]. Catal, 2015,5(1):58-76. doi: 10.3390/catal5010058
27. [27]
  JEONG D W, NA H S, SHIM J O, JANG W J, ROH H S, JUNG U H, YOON W L. Hydrogen production from low temperature WGS reaction on co-precipitated Cu-CeO₂ catalysts:An optimization of Cu loading[J]. Int J Hydrogen Energy, 2014,39(17):9135-9142. doi: 10.1016/j.ijhydene.2014.04.005
28. [28]
  KUBACKA A, FERNÁNDEZ-GARCÍA M, MARTÍNEZ-ARIAS A. Catalytic hydrogen production through WGS or steam reforming of alcohols over Cu, Ni and Co catalyst[J]. Appl Catal A:Gen, 2016,518:2-17. doi: 10.1016/j.apcata.2016.01.027
29. [29]
  ZENG G, LI Y, OLSBYE U. Kinetic and process study of ethanol steam reforming over Ni/Mg(Al)O catalysts:The initial steps[J]. Catal. Today, 2016,259:312-322. doi: 10.1016/j.cattod.2015.07.006
30. [30]
  MATTOS L V, JACOBS G, DAVIS B H, NORONHA F B. Production of hydrogen from ethanol:Review of reaction mechanism and catalyst deactivation[J]. Chem Rev, 2012,112(7):4094-4123. doi: 10.1021/cr2000114
31. [31]
  ZHAO X, LU G. Modulating and controlling active species dispersion over Ni-Co bimetallic catalysts for enhancement of hydrogen production of ethanol steam reforming[J]. Int J Hydrogen Energy, 2016,41(5):3349-3362. doi: 10.1016/j.ijhydene.2015.09.063
1. [1]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Cu基和Pt基甲醇水蒸气重整制氢催化剂研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-. doi: 10.1016/j.actphy.2025.100049
2. [2]
  Mingjie Lei , Wenting Hu , Kexin Lin , Xiujuan Sun , Haoshen Zhang , Ye Qian , Tongyue Kang , Xiulin Wu , Hailong Liao , Yuan Pan , Yuwei Zhang , Diye Wei , Ping Gao . Co/Mn/Mo掺杂加速NiSe₂重构以提高其电催化尿素氧化性能. Acta Physico-Chimica Sinica, 2025, 41(8): 100083-. doi: 10.1016/j.actphy.2025.100083
3. [3]
  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
4. [4]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
5. [5]
  Hao GUO , Tong WEI , Qingqing SHEN , Anqi HONG , Zeting DENG , Zheng FANG , Jichao SHI , Renhong LI . Electrocatalytic decoupling of urea solution for hydrogen production by nickel foam-supported Co₉S₈/Ni₃S₂ heterojunction. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2141-2154. doi: 10.11862/CJIC.20240085
6. [6]
  Junyi Yu , Yin Cheng , Anhong Cai , Xianfeng Huang , Qingrui Zhang . Synthetic Cu(Ⅲ) from copper plating wastewater for onsite decomplexation of Cu(Ⅱ)- and Ni(Ⅱ)-organic complexes. Chinese Chemical Letters, 2025, 36(2): 110549-. doi: 10.1016/j.cclet.2024.110549
7. [7]
  Yufei Liu , Liang Xiong , Bingyang Gao , Qingyun Shi , Ying Wang , Zhiya Han , Zhenhua Zhang , Zhaowei Ma , Limin Wang , Yong Cheng . MOF-derived Cu based materials as highly active catalysts for improving hydrogen storage performance of Mg-Ni-La-Y alloys. Chinese Chemical Letters, 2024, 35(12): 109932-. doi: 10.1016/j.cclet.2024.109932
8. [8]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
9. [9]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
10. [10]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
11. [11]
  Junqing WEN , Ruoqi WANG , Jianmin ZHANG . Regulation of photocatalytic hydrogen production performance in GaN/ZnO heterojunction through doping with Li and Au. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 923-938. doi: 10.11862/CJIC.20240243
12. [12]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
13. [13]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
14. [14]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
15. [15]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
16. [16]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
17. [17]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . 用于高效制氢的双S型ZnS/ZnO/CdS异质结构光催化剂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-. doi: 10.3866/PKU.WHXB202406020
18. [18]
  Yongmei Liu , Lisen Sun , Yongmei Hao , Zhanxiang Liu , Shuyong Zhang . Innovative Design of Chemistry Experiment Courses with Ideological and Political Education: A Case Study of Catalytic Hydrogen Production Experiments. University Chemistry, 2025, 40(5): 224-229. doi: 10.12461/PKU.DXHX202412144
19. [19]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
20. [20]
  Kaihui Huang , Dejun Chen , Xin Zhang , Rongchen Shen , Peng Zhang , Difa Xu , Xin Li . Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu₂O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(12): 2407020-. doi: 10.3866/PKU.WHXB202407020

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(1216)
HTML views(149)

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