Effects of Hydrothermal Reaction Time on the Performance of CuO/CeO2 Catalyst for Hydrogen Production from Steam Reforming Methanol

doi:10.12422/j.issn.1006-396X.2023.02.008

Abstract

Abstract:

CeO₂?X (X is the hydrothermal synthesis time, X=3, 6, 12, 24 h) carriers were prepared by varying the hydrothermal synthesis time using Ce(NO₃)₃·6H₂O and urea as raw materials, and CuO/CeO₂?X catalysts were obtained by isovolumetric impregnation with active component Cu, which were applied to methanol steam reforming (MSR) reaction. The effects of hydrothermal synthesis time on the structure and physicochemical properties of the prepared CeO₂?X carriers and CuO/CeO₂?X catalysts were explored by XRD, BET, H₂?TPR.The performances of the CuO/CeO₂?X catalyst samples were evaluated in methanol steam reforming(MSR) reaction.The results show that the CuO/CeO₂?6 has good catalytic activity. At the reaction temperature of 280 °C, when the molar ratio of water to methanol was 1.2, and the space velocity of methanol vapor (GHSV) was 800 h^-1, the methanol conversion rate could reach 92.8%.

Key words: Hydrothermal method, Cu?Ce catalyst, Methanol steam reforming, Cerium oxide, Hydrogen

摘要：

以六水合硝酸铈和尿素为原料，通过改变水热时间制备了CeO₂?X（X为水热时间，X=3、6、12、24 h）载体，对其进行等体积浸渍法负载活性组分Cu获得CuO/CeO₂?X催化剂，将其应用于甲醇水蒸气重整制氢(MSR)反应中。通过XRD、BET、H₂?TPR等表征手段，探索水热时间对CeO₂?X载体、CuO/CeO₂?X催化剂的结构和物化性质的影响，并考察了CuO/CeO₂?X催化剂在MSR反应中的催化性能。结果表明，CuO/CeO₂?6催化剂在MSR反应中展现出较好的催化活性；在反应温度为280 ℃、水醇物质的量比为1.2、甲醇气体体积空速（GHSV）为800 h^-1的条件下，甲醇转化率可达92.8%。

关键词: 水热法, Cu?Ce催化剂, 甲醇水蒸气重整, 氧化铈, 氢气

CLC Number:

TQ426

Xinyu Yang, Shu Sun, Yan Shi, Xu Feng, Jiao Han, Caishun Zhang, Lei Zhang, Zhixian Gao. Effects of Hydrothermal Reaction Time on the Performance of CuO/CeO₂ Catalyst for Hydrogen Production from Steam Reforming Methanol[J]. Journal of Petrochemical Universities, 2023, 36(2): 63-69.

杨昕毓, 孙舒, 石岩, 冯旭, 韩蛟, 张财顺, 张磊, 高志贤. 水热时间对CuO/CeO₂催化甲醇水蒸气重整制氢的影响[J]. 石油化工高等学校学报, 2023, 36(2): 63-69.

Figures/Tables 11

References 24

1	殷伊琳. 我国氢能产业发展现状及展望［J］.化学工业与工程， 2021， 38（4）： 78⁃83.
	Yin Y L. Present situation and prospect of hydrogen energy industry［J］. Chemical Industry and Engineering， 2021， 38（4）： 78⁃83.
2	Ma Y F， Guan G Q， Phanthong P， et al. Steam reforming of methanol for hydrogen production over nanostructured wire⁃like molybdenum carbide catalyst［J］. International Journal of Hydrogen Energy， 2014， 39（33）： 18803⁃18811．
3	Kawamura Y， Ogura N， Igarashi A. Hydrogen production by methanol steam reforming using microreactor［J］. Journal of the Japan Petroleum Institute， 2013， 56（5）： 288⁃297.
4	Iulianelli A， Ribeirinha P， Mendes A， et al. Methanol steam reforming for hydrogen generation via conventional and membrane reactors： A review［J］. Renewable and Sustainable Energy Reviews， 2014， 29（1）： 355⁃368.
5	孙晓明，沙琪昊，王陈伟，等. 用于甲醇重整制氢的铜基催化剂研究进展［J］. 化工学报， 2021， 72（12）： 5975⁃6001.
	Sun X M， Sha Q H， Wang C W，et al. Application of copper⁃based catalysts for hydrogen production in methanol steam reforming［J］. Journal of Chemical Industry and Engineering， 2021， 72（12）： 5975⁃6001 .
6	Mierczynski P， Mosinska M， Maniukiewicz W， et al. Oxy⁃steam reforming of methanol on copper catalysts［J］. Reaction Kinetics Mechanisms and Catalysis， 2019， 127（2）： 857⁃874.
7	Liu Y Y， Hayakawa T， Tsunoda T， et al. Steam reforming of methanol over Cu/CeO₂ catalysts studied in comparison with Cu/ZnO and Cu/Zn（Al）O catalysts［J］. Topics in Catalysis， 2003， 22（3⁃4）： 205⁃213.
8	Landi G， Barbato P S， Benedetto A D， et al. Optimization of the preparation method of CuO/CeO₂， structured catalytic monolith for CO preferential oxidation in H₂⁃rich streams［J］. Applied Catalysis B⁃Environmental， 2016， 181（8）： 727⁃737.
9	Liu X， Men Y， Wang J G， et al. Remarkable support effect on the reactivity of Pt/In₂O₃/MOx catalysts for methanol steam reforming［J］. Journal of Power Sources， 2017， 364（29）： 341⁃350.
10	Guo X L， Zhou R X. Identification of the nano/micro structure of CeO₂（rod） and the essential role of interfacial copper⁃ceria interaction in CuCe（rod） for selective oxidation of CO in H₂⁃rich streams［J］. Journal of Power Sources， 2017， 361（25）： 39⁃53.
11	刘玉娟，许骥，佟宇飞，等. 氧化铈纳米材料合成方法的研究进展［J］. 辽宁石油化工大学学报， 2017， 37（5）： 8⁃12.
	Liu Y J， Xu J， Tong Y F， et al. Progress in research of the synthesis methods of nanometer ceria［J］. Journal of Liaoning Shihua University， 2017， 37（5）： 8⁃12.
12	王东哲，田志强，张宣娇，等. 制备方法对甲醇水蒸气重整制氢CuO/CeO₂催化剂的影响［J］. 石油化工， 2019， 48（4）： 335⁃341.
	Wang D Z， Tian Z Q， Zhang X J， et al. Effect of preparation methods on performance of CuO/CeO₂ catalyst for hydrogen production from methanol steam reforming［J］. Petrochemical Technology， 2019， 48（4）： 335⁃341 .
13	Lykaki M， Pachatouridou E， Iliopoulou E. Impact of synthesis parameters on the solid state properties and the CO oxidation performance of ceria nanoparticles［J］. RSC Advances， 2017， 7（10）： 6160⁃6169.
14	Niu X. Hydrothermal synthesis and optical properties of the monodisperse spindle⁃shaped CeO₂ microstructures［J］. Russian Journal of Physical Chemistry， 2018， 92（4）： 768⁃771.
15	Meng F， Wu H， Gao C. Hydrothermal synthesis of monocrystalline CeO₂ polymeric nano⁃balls and their optical properties［J］. Russian Journal of Physical Chemistry A， 2021， 95（4）： 754⁃761.
16	王金果，陈菲菲，曹锋雷，等.多孔单晶CeO₂空壳球的制备及其CO催化氧化性能研究［J］.上海师范大学学报（自然科学版）， 2013， 42（3）： 288⁃292.
	Wang J G， Chen F F， Cao F L， et al. Synthesis of mesocrystal CeO₂ hollow spheres and their catalytic performance on CO oxidation［J］. Journal of Shanghai Normal University （Natural Sciences）， 2013， 42（3）： 288⁃292 .
17	赵艳娜，姬定西. 纳米CeO₂/水性聚氨酯复合材料的制备及性能［J］. 化工进展， 2017， 36（12）： 4501⁃4507.
	Zhao Y N， Ji D X. Preparation and properties of nano CeO₂/waterborne polyurethane composites［J］. Chemical Industry and Engineering Progress， 2017， 36（12）： 4501⁃4507.
18	贺建平，张磊，陈琳，等. CeO₂改性Cu/Zn⁃Al水滑石衍生催化剂对甲醇水蒸气重整制氢性能的影响［J］. 高等学校化学学报， 2017， 38（10）： 1822⁃1828.
	He J P， Zhang L， Chen L， et al. Effect of CeO₂ modified Cu/Zn⁃Al water derived catalyst on hydrogen production performance of methanol water vapor reforming［J］. Chemical Journal of Chinese University， 2017， 38（10）： 1822⁃1828.
19	Jung W Y， Hong S S. Complete oxidation of benzene over CuO⁃CeO₂ catalysts prepared using different process［J］. Journal of Nanosci Nanotechnol， 2016， 16（5）： 4576⁃4579.
20	Zhang L， Pan L W， Ni C J， et al. CeO₂⁃ZrO₂⁃promoted CuO/ZnO catalyst for methanol steam reforming［J］. International Journal of Hydrogen Energy， 2013， 38（11）： 4397⁃4406.
21	Yang S Q， Zhou F， Liu Y J， et al. Morphology effect of ceria on the performance of CuO/CeO₂ catalysts for hydrogen production by methanol steam reforming［J］. International Journal of Hydrogen Energy， 2019， 44（14）： 7252⁃7261.
22	Zhang F， Liu Y， Xu X Y， et al. Effect of Al⁃containing precursors on Cu/ZnO/Al₂O₃ catalyst for methanol production［J］. Fuel Processing Technology， 2018， 178（9）： 148⁃155.
23	邢月，杨劭杰，曹利星，等.甲醇水蒸气重整制氢CuO⁃ZnO/CeO₂催化剂的制备及性能［J］.石油化工， 2022， 51（9）： 1011⁃1016.
	Xing Y， Yang S J， Cao L X， et al. Preparation and performance of CuO⁃ZnO/CeO₂ catalyst for producing hydrogen via methanol steam reforming［J］. Petrochemical Technology， 2022， 51（9）： 1011⁃1016.
24	冯旭，林宇，张财顺，等. 水热合成温度对CuO/CeO₂催化甲醇水蒸气重整制氢性能的影响［J］. 燃料化学学报， 2022， 50（7）： 832⁃840.
	Feng X， Lin Y， Zhang C S， et al. Effects of hydrothermal reaction temperatures on the performance of CuO/CeO₂ catalyst for hydrogen production from steam reforming methanol［J］. Journal of Fuel Chemistry and Technology， 2022， 50（7）： 832⁃840.

CeO₂⁃X	CeO₂晶胞边长/ nm	比表面积/（m²·g^-1）	孔容 /(cm³·g^-1)
CeO₂⁃3	0.540 3	84.5	0.07
CeO₂⁃6	0.540 8	86.8	0.07
CeO₂⁃12	0.540 4	87.1	0.07
CeO₂⁃24	0.540 8	76.6	0.07

CeO₂⁃X	CeO₂晶胞边长/ nm	比表面积/（m²·g^-1）	孔容 /(cm³·g^-1)
CeO₂⁃3	0.540 3	84.5	0.07
CeO₂⁃6	0.540 8	86.8	0.07
CeO₂⁃12	0.540 4	87.1	0.07
CeO₂⁃24	0.540 8	76.6	0.07

CuO/CeO₂⁃X	CeO₂晶胞边长/nm	比表面积/（m²·g^-1）	孔容/(cm³·g^-1)
CuO/CeO₂⁃3	0.540 1	36.7	0.05
CuO/CeO₂⁃6	0.540 7	37.3	0.05
CuO/CeO₂⁃12	0.540 3	40.3	0.06
CuO/CeO₂⁃24	0.540 4	38.2	0.05

CuO/CeO₂⁃X	CeO₂晶胞边长/nm	比表面积/（m²·g^-1）	孔容/(cm³·g^-1)
CuO/CeO₂⁃3	0.540 1	36.7	0.05
CuO/CeO₂⁃6	0.540 7	37.3	0.05
CuO/CeO₂⁃12	0.540 3	40.3	0.06
CuO/CeO₂⁃24	0.540 4	38.2	0.05

CuO/CeO₂⁃X	t_peak/℃			x_Cu/%
CuO/CeO₂⁃X	α峰	β峰	γ峰	α峰	β峰	γ峰
CuO/CeO₂-3	158	189	237	39	54	7
CuO/CeO₂-6	149	183	220	42	56	2
CuO/CeO₂-12	157	189	225	37	60	3
CuO/CeO₂-24	158	189	229	35	64	1

Effects of Hydrothermal Reaction Time on the Performance of CuO/CeO₂ Catalyst for Hydrogen Production from Steam Reforming Methanol

水热时间对CuO/CeO₂催化甲醇水蒸气重整制氢的影响

HTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 24

Related Articles 15

Recommended Articles

Metrics

催化剂	制备方法	反应温度/℃	α/％	参考文献
CuO⁃ZnO/CeO₂	球磨法	280	91.4	[23]
CuO/CeO₂	水热法	300	93.0	[12]
CuO/CeO₂	水热法	280	91.0	[24]
CuO/CeO₂	水热法	280	92.8	本文

[1]	Shujie ZHI, Haifeng XU, Luoqian LIU, Shilong XUE, Shiyao PENG, Xiaobin ZHANG. Small Hole Leakage and Diffusion Characteristics of Hydrogen⁃Blended Natural Gas High⁃Pressure Pipeline [J]. Journal of Petrochemical Universities, 2024, 37(4): 25-32.
[2]	Lele LI, Lisha SHEN, Zhiming TU, Zhuoxin LU, Hongyi TAN, Yi YANG, Changfeng YAN. Preparation of Cu⁃Doped WN Nanoarrays and Study on Their Hydrogen Evolution Performance [J]. Journal of Petrochemical Universities, 2024, 37(4): 57-65.
[3]	Zhe LI, Fangfang WANG, Changdong CHEN. Synthesis of Mn₃O₄/CuMnO₂ by One-Step Hydrothermal Method and Its Photo-Fenton Reaction Performance [J]. Journal of Petrochemical Universities, 2024, 37(3): 73-80.
[4]	Shijia LIU, Kai HE, Yanfeng BI, Lijuan SONG. A Review of the Morphological Regulation of γ⁃Al₂O₃ Spport and Its Effect on Propane Dehydrogenation Catalysts [J]. Journal of Petrochemical Universities, 2024, 37(2): 31-41.
[5]	Changhe LÜ, Dianqing WU, Kaiwen ZHANG, Dongbei YU, Caishun ZHANG, Jiao HAN, Zhixian GAO. Characteristics of Methanol Steam Reforming Catalyzed by Cu⁃Mn⁃Al Ternary Spinel [J]. Journal of Petrochemical Universities, 2024, 37(2): 50-57.
[6]	Honglin LI, Yuling YAN, Lihua LI. Performance Studies of Nano⁃GO⁃ZnO / CeO₂ Composite Particles in Water⁃Based Polyurethane Coatings [J]. Journal of Petrochemical Universities, 2024, 37(1): 66-73.
[7]	Jinming Kang, Jianhao Jiao, Yucai Qin, Ye Yang, Huan Wang, Lijuan Song. Effect of Sn Pt0.5⁃Snx/γ⁃Al₂O₃ Catalysts on the Performance of Propane Dehydrogenation [J]. Journal of Petrochemical Universities, 2023, 36(4): 34-39.
[8]	Jie Li, Zhiqiang Zhang, Yue Fu, Shujun Chen, Yao Xu, Haixu Fan. Numerical Simulation of Hydrogen Storage Process in MIL⁃101(Cr) with Different Thermal Conductivity [J]. Journal of Petrochemical Universities, 2023, 36(3): 31-36.
[9]	Lei Guan, Xian Chen, Bowen Fan, Yaxu Chen, Pengpeng Yin, Ying Wang. Hydrothermal Synthesis, Crystal Structure and Fluorescence Property of a Tb Coordination Complex [J]. Journal of Petrochemical Universities, 2023, 36(3): 60-65.
[10]	Mengshan Liu, Chao Meng, Han Hu, Mingbo Wu. Preparation of NiMoN Catalytic Electrode Material for Hydrogen Production via Seawater Electrolysis [J]. Journal of Petrochemical Universities, 2023, 36(2): 1-9.
[11]	Bo Yu, Jianghua Ling, Fuzhi Jia, Mei Liu. Separation and Recovery of Aluminum and Nickel from Alkali Leaching Residue of Spent Catalysts [J]. Journal of Petrochemical Universities, 2023, 36(2): 20-26.
[12]	Dong Li, Kunyan Wang, Yuqiao Wang. Effects of NiCoP with Different Dimension on Hydrogen Evolution Reaction [J]. Journal of Petrochemical Universities, 2023, 36(2): 70-77.
[13]	Mingyu Cui, Jianhao Jiao, Jinming Kang, Shijia Liu, Huimin Guan, Lijuan Song. Control of Propane Dehydrogenation Performance of Pt⁃Sn/γ⁃Al₂O₃ Catalysts by Support Surface Properties [J]. Journal of Petrochemical Universities, 2023, 36(1): 40-47.
[14]	Yujing Zhang, Baoshan Zhang, Jie Sun. Progress in Hydrogen Production by Water Electrolysis and Its Electrocatalysts [J]. Journal of Petrochemical Universities, 2022, 35(6): 19-27.
[15]	Xingsi Kang, Qiongyao Chen, Lin He. Recent Advances on MeOH Production via Homogeneous Catalytic CO₂ Hydrogenation [J]. Journal of Petrochemical Universities, 2022, 35(5): 25-35.