甲醇水蒸气重整制氢CuO/La1−xCe x CrO3 催化剂

乔韦军; 肖国鹏; 张磊; 庆绍军; 赵瑛祁; 耿忠兴; 高志贤

doi:10.19906/j.cnki.JFCT.2021012

甲醇水蒸气重整制氢CuO/La_1−xCe _x CrO₃ 催化剂

doi: 10.19906/j.cnki.JFCT.2021012

1.
辽宁石油化工大学石油化工学院，辽宁抚顺　113001
2.
中国科学院山西煤炭化学研究所，山西太原　030001

基金项目: 国家自然科学基金(21673270)资助

详细信息

通讯作者:
E-mail: lnpuzhanglei@163.com

中图分类号: O643
计量
- 文章访问数: 443
- HTML全文浏览量: 152
- PDF下载量: 36
- 被引次数: 0
出版历程
- 收稿日期: 2020-09-03
- 修回日期: 2020-10-06
- 刊出日期: 2021-02-08

Catalytic performance of CuO/La_1−xCe_xCrO₃ in the steam reforming of methanol

1.
School of Petrochemical Engineering, Liaoning Shihua University, Fushun　113001, China
2.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan　030001, China

Funds: The project was supported by the National Natural Science Foundation of China (21673270)

摘要

摘要: 采用溶胶凝胶法制备了负载型CuO/La_1−xCe_xCrO₃催化剂，研究了A位中Ce元素掺杂量对CuO/La_1−xCe_xCrO₃催化剂结构、性质及其催化甲醇水蒸气重整制氢性能的影响。结果表明，掺杂Ce元素影响了CuO的还原性能和钙钛矿载体与CuO之间的作用力，进而影响了CuO/La_1−xCe_xCrO₃催化剂对甲醇水蒸气重整制氢反应的催化性能。其中，CuO/La_0.8Ce_0.2CrO₃具有较好的催化性能，在280 °C、水醇物质的量比为1.2、甲醇气体空速为800 h⁻¹的条件下，甲醇转化率达到100%。
- 钙钛矿 /
- 甲醇水蒸气重整 /
- 氢气 /
- 溶胶凝胶法
Abstract: A series of supported CuO/La_1−xCe_xCrO₃ catalysts were prepared by the sol-gel method and the effect of Ce doping in the A site on their structure, properties and catalytic performance in the steam reforming of methanol were investigated. The results indicate that the Ce doping impacts mainly on the reduction performance of CuO and the interaction between the perovskite support and CuO, which in turn influences the catalytic performance of CuO/La_1−xCe_xCrO₃ in methanol steam reforming. In particular, the CuO/La_0.8Ce_0.2CrO₃ catalyst demonstrates adequate performance in methanol steam reforming; over it, the methanol conversion reaches 100% under 280 °C, water/methanol molar ratio of 1.2 and methanol gas hourly space velocity of 800 h⁻¹.
- perovskite /
- methanol steam reforming /
- hydrogen /
- sol-gel method

HTML全文

下载: 全尺寸图片幻灯片

图 1 La_1−xCe_xCrO₃钙钛矿载体的XRD谱图

Figure 1 XRD patterns of the La_1−xCe _x CrO₃ perovskite supports

a: LaCrO₃; b: La_0.8Ce_0.2CrO₃; c: La_0.5Ce_0.5CrO₃; d: La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 2 CuO/La_1−xCe_xCrO₃催化剂的XRD谱图

Figure 2 XRD patterns of various CuO/La_1−xCe _x CrO₃ catalysts

a: CuO/LaCrO₃; b: CuO/La_0.8Ce_0.2CrO₃; c: CuO/La_0.5Ce_0.5CrO₃; d: CuO/La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 3 La_1−xCe_xCrO₃钙钛矿的晶胞参数与Ce/ La物质的量比关系图

Figure 3 Relationship between the unit cell parameters of the La_1−xCe _x CrO₃ perovskite and the Ce/La molar ratio

a: La_0.8Ce_0.2CrO₃; b: La_0.5Ce_0.5CrO₃; c: La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 4 La_1−xCe_xCrO₃载体的N₂吸附-脱附等温线

Figure 4 N₂ adsorption-desorption isotherms of various CuO/ La_1−xCe _x CrO₃ catalysts

a: LaCrO₃; b: La_0.8Ce_0.2CrO₃; c: La_0.5Ce_0.5CrO₃; d: La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 5 不同CuO/La_1−xCe_xCrO₃催化剂的氢气程序升温还原谱图

Figure 5 H₂-TPR profiles of various CuO/La_1−xCe _x CrO₃ catalysts

a: CuO/LaCrO₃; b: CuO/La_0.8Ce_0.2CrO₃; c: CuO/La_0.5Ce_0.5CrO₃; d: CuO/La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 6 反应温度对催化剂活性的影响

Figure 6 Activity of various CuO/La_1−xCe _x CrO₃ catalysts as a function of temperature in the methanol steam reforming

a: CuO/LaCrO₃; b: CuO/La_0.8Ce_0.2CrO₃; c: CuO/La_0.5Ce_0.5CrO₃; d: CuO/La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

图 7 温度对重整气中CO含量的影响

Figure 7 Effect of reaction temperature on the CO content in reformate over various CuO/La_1−xCe _x CrO₃ catalysts

a: CuO/LaCrO₃; b: CuO/La_0.8Ce_0.2CrO₃; c: CuO/La_0.5Ce_0.5CrO₃; d: CuO/La_0.2Ce_0.8CrO₃

下载: 全尺寸图片幻灯片

表 1 La_1-xCe_xCrO₃载体和CuO/La_1-xCe_xCrO₃催化剂的比表面积及孔结构参数

Table 1 Surface area and pore structure parameters of La_1−xCe _x CrO₃ support and CuO/La_1−xCe _x CrO₃ catalysts

Catalyst	A_BET/ (m²·g⁻¹)	Pore volume v/ (cm³·g⁻¹)	Bore diameter/nm	Cu surface area A/ (m²·g_cat⁻¹)	H₂ production rate/ (mL·kg_cat⁻¹·s⁻¹)
LaCrO₃	10.6	0.02	3.06	−	−
La_0.8Ce_0.2CrO₃	15.3	0.06	3.44	−	−
La_0.5Ce_0.5CrO₃	22.6	0.12	3.66	−	−
La_0.2Ce_0.8CrO₃	24.1	0.15	3.91	−	−
CuO/LaCrO₃	12.1	0.03	3.09	2.1	651
CuO/La_0.8Ce_0.2CrO₃	16.6	0.06	3.54	3.1	1056
CuO/La_0.5Ce_0.5CrO₃	25.5	0.13	3.73	2.8	746
CuO/La_0.2Ce_0.8CrO₃	27.1	0.15	3.92	2.8	669

下载: 导出CSV

表 2 催化剂的产氢速率对比

Table 2 A comparison of various catalysts in the hydrogen production rate

Catalyst	Temperature t/℃	Water/methanol mol/%	GHSV/h⁻¹	H₂ production rate/(mL·kg⁻¹·s⁻¹)
CuO/La_0.8Ce_0.2CrO₃	280	1.2:1	800	1056
CuO/CeO₂-R^[12]	240	1.2:1	800	378
CuO/CeO₂^[17]	280	1.2:1	800	380
CuZnCeZr^[18]	240	1.2:1	1200	510
Zn_0.5Ce₁Zr₉O_x^[19]	450	1.4:1	1500	808

下载: 导出CSV

参考文献(19)

[1]	ZAICENKO V M, SHPILRAIN E E, SHTERENBERG V Y. Hydrogen energy: Present state and lines of future development[J]. Teploenergetika,2003,1(5):61−67.
[2]	HERDEM M S, SINAKI M Y, FARHAD S, HAMDULLAHPUR F. An overview of the methanol reforming process: comparison of fuels, catalysts, reformers, and systems[J]. Int J Hydrogen Energy,2019,43:5076−5085.
[3]	CLAUDE L. From hydrogen production by water electrolysis to its utilization in a PEM fuel cell or in a SO fuel cell: Some considerations on the energy efficiencies[J]. Int J Hydrogen Energy,2016,41(34):15415−15425. doi: 10.1016/j.ijhydene.2016.04.173
[4]	HOSSAIN M A, JEWARATNAM J, GANESAN P. Prospect of hydrogen production from oil palm biomass by thermochemical process-A review[J]. Int J Hydrogen Energy,2016,41(38):16637−16655. doi: 10.1016/j.ijhydene.2016.07.104
[5]	SA S, SILVA H, BRANDAO L, SOUSA J M, MENDES A. Catalysts for methanol steam reforming—A review[J]. Appl Catal B: Environ,2010,99(1-2):43−57. doi: 10.1016/j.apcatb.2010.06.015
[6]	LYTKINA A A, ZHILYAEVA N A, ERMILOVA M M, OREKHOVA N V, YAROSLAVTSEV A B. Influence of the support structure and composition of Ni-Cu-based catalysts on hydrogen production by methanol steam reforming[J]. Int J Hydrogen Energy,2015,40(31):9677−9684. doi: 10.1016/j.ijhydene.2015.05.094
[7]	HE J P, YANG Z X, ZHANG L, LI Y, PAN L W. Cu supported on ZnAl-LDHs precursor prepared by in-situ synthesis method on γ-Al₂O₃ as catalytic material with high catalytic activity for methanol steam reforming[J]. Int J Hydrogen Energy,2017,42(15):9930−9937. doi: 10.1016/j.ijhydene.2017.01.229
[8]	WANG Z J, WANG C X, CHEN S Q, LIU Y. Co-Ni bimetal catalyst supported on perovskite-type oxide for steam reforming of ethanol to produce hydrogen[J]. Int J Hydrogen Energy,2014,39(11):5644−5652. doi: 10.1016/j.ijhydene.2014.01.151
[9]	GLISENTI A, GALENDA A, NATILE M M. Steam reforming and oxidative steam reforming of methanol and ethanol: The behaviour of LaCo_0.7Cu_0.3O₃[J]. Appl Catal A: Gen,2013,453:102−112. doi: 10.1016/j.apcata.2012.11.031
[10]	肖国鹏, 乔韦军, 王丽宝, 张磊, 张健, 王宏浩. LaNiO₃的焙烧温度对甲醇水蒸气重整制氢CuO/LaNiO₃催化剂的影响[J]. 燃料化学学报,2020,48(2):213−240. doi: 10.3969/j.issn.0253-2409.2020.02.011 XIAO Guo-peng, QIAO Wei-jun, WANG Li-bao, ZHANG Lei, ZHANG Jian, WANG Hong-hao. The effect of LaNiO₃ roasting temperature on CuO/LaNiO₃ catalysts for hydrogen production by methanol steam reforming[J]. J Fuel Chem Technol,2020,48(2):213−240. doi: 10.3969/j.issn.0253-2409.2020.02.011
[11]	KHALESI A, ARANDIYAN H R, PARVARI M. Effects of Lanthanum Substitution by Strontium and Calcium in La-Ni-Al Perovskite Oxides in Dry Reforming of Methane[J]. J Catal,2008,29(10):18−26.
[12]	YANG S Q, ZHOU F, LIU Y J, ZHANG L, YU C, WANG H H, TIAN Y, ZHANG C S, LIU D S. Morphology effect of ceria on the performance of CuO/CeO₂ catalysts for hydrogen production by methanol steam reforming[J]. Int J Hydrogen Energy,2019,44(14):7252−7261. doi: 10.1016/j.ijhydene.2019.01.254
[13]	XI H J, HOU X N, LIU Y J, QING S J, GAO Z X. Cu–Al spinel oxide as an efficient catalyst for methanol steam reforming[J]. Angew Chem Int Ed,2014,126:12080−12083.
[14]	王丽宝, 王东哲, 张磊, 庆绍军, 韩蛟, 张财顺, 高志贤, 张海娟, 冯旭浩. 铈源对甲醇水蒸气重整制氢CuO/CeO₂催化剂的影响[J]. 燃料化学学报,2020,48(7):852−859. WANG Li-bao, WANG Dong-zhe, ZHANG Lei, QING Shao-jun, HAN Jiao, ZHANG Cai-shun, GAO Zhi-xian, ZHANG Hai-juan, FENG Xu-hao. Effect of cerium source on CuO/CeO₂ catalysts for hydrogen production by methanol steam reforming[J]. J Fuel Chem Technol,2020,48(7):852−859.
[15]	苏石龙, 张磊, 张艳, 雷俊腾, 桂建舟, 刘丹, 刘道胜, 潘立卫. 千瓦级PEMFC甲醇水蒸气重整制氢过程热力学模拟[J]. 石油化工高等学校学报,2015,28(2):21−25. SU Shi-long, ZHANG Lei, ZHANG Yan, LEI Jun-teng, GUI Jian-zhou, LIU Dan, LIU Dao-sheng, PAN Li-wei. Thermodynamic simulation of hydrogen production process from kilowatt PEMFC methanol steam reforming[J]. J Petrochem College,2015,28(2):21−25.
[16]	杨淑倩, 贺建平, 张娜, 隋晓伟, 张磊, 杨占旭. 稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响[J]. 燃料化学学报,2018,46(2):179−188. doi: 10.3969/j.issn.0253-2409.2018.02.007 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. doi: 10.3969/j.issn.0253-2409.2018.02.007
[17]	刘玉娟, 王东哲, 张磊, 王宏浩, 陈琳, 刘道胜, 韩蛟, 张财顺. 载体焙烧气氛对甲醇水蒸气重整制氢CuO/CeO₂催化剂的影响[J]. 燃料化学学报,2018,46(8):992−999. doi: 10.3969/j.issn.0253-2409.2018.08.011 LIU Yu-juan, WANG Dong-zhe, ZHANG Lei, WANG Hong-hao, CHEN Lin, LIU Dao-sheng, HAN Jiao, ZHANG Cai-shun. Effect of carrier roasting atmosphere on CuO/CeO₂ catalyst for methanol steam reforming[J]. J Fuel Chem Technol,2018,46(8):992−999. doi: 10.3969/j.issn.0253-2409.2018.08.011
[18]	ZHANG L, PAN L W, NI C J, SUN T J, ZHAO S S, WANG S D, WANG A J, HU Y K. CeO₂-ZrO₂-promoted CuO/ZnO catalyst for methanol steam reforming[J]. Int J Hydrogen Energy,2013,38(11):4397−4406. doi: 10.1016/j.ijhydene.2013.01.053
[19]	SONG Q L, MEN Y, WANG J G, LIU S, CHAI S S, AN W, WANG K, LI Y Y, TANG Y H. Methanol steam reforming for hydrogen production over ternary composite Zn_yCe₁Zr₉O_x catalysts[J]. Int J Hydrogen Energy,2020,45(16):9592−9602. doi: 10.1016/j.ijhydene.2020.01.175