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]
  Zhuwei Yang , Linsen Li , Yijie Lin , Xinyuan Tao , Xiao Liu , Lei Chen , Ming Ma , Li Lin , Riguang Zhang , Jiayuan Li , Zhao Jiang . Regulating the Oxygen Vacancies in Ni-CexZr1-xO2/ZSM-5 to Improve the Long-term Stability for Methane Dry Reforming. Chinese Journal of Structural Chemistry, 2025, 44(8): 100632-100632. doi: 10.1016/j.cjsc.2025.100632
2. [2]
  Yifan ZHAO , Qiyun MAO , Meijing GUO , Guoying ZHANG , Tongliang HU . Z-scheme bismuth-based multi-site heterojunction: Synthesis and hydrogen production from photocatalytic hydrogen production. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1318-1330. doi: 10.11862/CJIC.20250001
3. [3]
  Xin Feng , Kexin Guo , Chunguang Jia , Bowen Liu , Suqin Ci , Junxiang Chen , Zhenhai Wen . Hydrogen Generation Coupling with High-Selectivity Electrocatalytic Glycerol Valorization into Formate in an Acid-Alkali Dual-Electrolyte Flow Electrolyzer. Acta Physico-Chimica Sinica, 2024, 40(5): 2303050-0. doi: 10.3866/PKU.WHXB202303050
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]
  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 . Accelerating the reconstruction of NiSe₂ by Co/Mn/Mo doping for enhanced urea electrolysis. Acta Physico-Chimica Sinica, 2025, 41(8): 100083-0. doi: 10.1016/j.actphy.2025.100083
6. [6]
  Yi RU , Tao MENG , Zhaoteng XUE , Dongsen MAO . Synergistic catalysis of Al distribution and pore structure in ZSM-5 zeolite for bioethanol-to-propylene. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 247-262. doi: 10.11862/CJIC.20250255
7. [7]
  Xudong Lv , Tao Shao , Junyan Liu , Meng Ye , Shengwei Liu . Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals. Acta Physico-Chimica Sinica, 2024, 40(5): 2305028-0. doi: 10.3866/PKU.WHXB202305028
8. [8]
  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
9. [9]
  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
10. [10]
  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
11. [11]
  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
12. [12]
  Xinnan XIE , Boyu ZHANG , Jianxun YANG , Yi ZHONG , Younis Osama , Jianxiao YANG , Xinchun YANG . Ultrafine platinum clusters achieved by metal-organic framework derived cobalt nanoparticle/porous carbon: Remarkable catalytic performance in dehydrogenation of ammonia borane. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2095-2102. doi: 10.11862/CJIC.20250025
13. [13]
  Lixing LU , Shaoxian LIU , Jian XU , Ziqi JIN , Jiongjia CHENG , Jiyang ZHAO , Fubo WANG , Haiying WANG . [FeFe]-hydrogenase-containing compound and its photocatalytic H₂-production performance. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2584-2590. doi: 10.11862/CJIC.20250200
14. [14]
  Ruilong WANG , Jinlong MAO , Guoxia JIN , Jianping MA , Haiying WANG , Jie QIN . 2-Cyanobenzyl-substituted [FeFe]-hydrogenase compounds: Preparation, characterization, and photocatalytic H₂-production performance. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 817-825. doi: 10.11862/CJIC.20250376
15. [15]
  Xiaogang Liu , Mengyu Chen , Yanyan Li , Xiantao Ma . Experimental Reform in Applied Chemistry for Cultivating Innovative Competence: A Case Study of Catalytic Hydrogen Production from Liquid Formaldehyde Reforming at Room Temperature. University Chemistry, 2025, 40(7): 300-307. doi: 10.12461/PKU.DXHX202408007
16. [16]
  Xiao Liu , Haiyan Pang , Xinrui Kou , Zheng Tang , Bing Cui , Shihong Cen , Yuechang Wei . Synergistic interaction of ternary Pd−Cu−Ni confined in nanoparticles as pH-universal catalysts for enhanced hydrogen evolution reaction. Chinese Chemical Letters, 2026, 37(4): 111567-. doi: 10.1016/j.cclet.2025.111567
17. [17]
  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
18. [18]
  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
19. [19]
  Yajuan Xing , Hui Xue , Jing Sun , Niankun Guo , Tianshan Song , Jiawen Sun , Yi-Ru Hao , Qin Wang . Cu₃P-Induced Charge-Oriented Transfer and Surface Reconstruction of Ni₂P to Achieve Efficient Oxygen Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(3): 2304046-0. doi: 10.3866/PKU.WHXB202304046
20. [20]
  Qingyun Yang , Yue Ma , Quanyi Ye , Yiqing Liu , Yuhong Luo , Yongbo Wu , Zhiguang Xu , Xiaoming Lin . Prussian blue analogues derived MO/MFe2O4 (M = Ni, Cu, Zn) nanoparticles as a high-performance anode material for enhanced lithium storage. Chinese Journal of Structural Chemistry, 2025, 44(8): 100631-100631. doi: 10.1016/j.cjsc.2025.100631

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(1735)
HTML views(197)

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