CuO/CeO2-ZrO2/SiC整体催化剂催化甲醇水蒸气重整制氢的研究

doi:10.6023/A20120562

摘要/Abstract

采用溶胶凝胶法制备了CeO₂-ZrO₂固溶体载体涂层, 再经浸渍法制备了高空速下性能较好的甲醇水蒸气重整制氢xCuO/CeO₂-ZrO₂/SiC整体催化剂. 采用X射线衍射(XRD)、比表面积测试(BET)、H₂程序升温还原(H₂-TPR)和X射线光电子能谱(XPS)等手段对催化剂进行了表征, 结果表明, 催化剂活性主要与Cu比表面积、活性组分与载体之间相互作用以及氧空穴量有关. 其中5%CuO/CeO₂-ZrO₂/SiC整体催化剂的Cu比表面积较大, 活性组分CuO与CeO₂-ZrO₂固溶体氧化物之间相互作用较强, 氧空穴量较多, 因此表现出较好的催化性能. 在反应温度为360 ℃、水醇物质的量比为1.2、甲醇水蒸气气体空速为4840 h^–1的条件下, 甲醇转化率为89.9%, 产氢速率为1556 L•m^–3•s^–1. 与传统颗粒催化剂相比, SiC基整体催化剂的产氢速率更高, 更适用于高空速下的甲醇水蒸气重整制氢反应, 有利于小型化制氢反应器的集成.

关键词: 甲醇水蒸气重整, 氢气, 一氧化碳, 固溶体, 整体催化剂

Hydrogen proton exchange membrane fuel cell is considered as the most cleanest way with high energy efficiency of hydrogen energy utilization. However, the high storage and transportation cost of hydrogen can always be the important factors hindering its development. Fortunately, on-site hydrogen production from methanol steam reforming can effectively solve this problem, which has low reforming temperature and CO content in reforming gas. Monolithic catalyst, a kind of catalytic material, on which the active components loaded on the formed support are generally honeycombed structures with multiple parallel channels. Therefore, compared to the traditional beaded catalytic materials, the monolithic catalytic material has lower pressure drop and higher mass transfer efficiency, which means that the monolithic catalysts have a certain practical application prospect. Ceria-zirconia solid solution was prepared by the sol-gel method, then a series xCuO/CeO₂-ZrO₂/SiC catalysts were prepared by incipient-wetness impregnation method, and demonstrated considerable catalytic activity at high velocity reaction conditions. The catalyst samples were characterized by X-ray diffraction (XRD), BET specific surface area test, H₂-temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) techniques. According to the results, we proposed that the catalytic performances are mainly effected by the surface area of Cu, the interaction between active component and support, and the amount of oxygen vacancy. Among those catalysts, 5%CuO/CeO₂-ZrO₂/SiC had relatively higher copper specific surface area, stronger interaction between CuO and support, more oxygen vacancies, thus showing better catalytic activity. When the reaction temperature reached 360 ℃, with a water/methanol molar ratio of 1.2, methanol and water total gas hourly space velocity of 4840 h^–1, the methanol conversion reached 89.9%, and the H₂ production rate was 1556 L•m^–3•s^–1. When compared with the traditional bead catalyst, monolithic catalyst seems to be more suitable for high space velocity methanol steam reforming reaction, also the SiC support is chemical stable and has favorable thermal conductivity, which avoiding the device volume increase caused by the additional heating device, thus facilitating the integration of minitype reactors for hydrogen generation.

Key words: methanol steam reforming, hydrogen, carbon monoxide, solid solution, monolithic catalyst

引用此文

焦桐, 许雪莲, 张磊, 翁幼云, 翁玉冰, 高志贤. CuO/CeO₂-ZrO₂/SiC整体催化剂催化甲醇水蒸气重整制氢的研究[J]. 化学学报, 2021, 79(4): 513-519.

Tong Jiao, Xue-lian Xu, Lei Zhang, You-yun Weng, Yu-bing Weng, Zhi-xian Gao. Research on CuO/CeO₂-ZrO₂/SiC Monolithic Catalysts for Hydrogen Production by Methanol Steam Reforming[J]. Acta Chimica Sinica, 2021, 79(4): 513-519.

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图/表 14

材料	导热系数/(W•m^–1•K^–1)
SiC	490
纯铜	401
纯金	317
纯铝	237

表1. 导热系数对比表

Table 1. Comparison table of thermal conductivity

图1. xCuO/CeO2-ZrO2催化剂的XRD谱图

Figure 1. XRD spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) CeO2-ZrO2; (b) 2%CuO/CeO2-ZrO2/SiC; (c) 5%CuO/CeO2-ZrO2/SiC; (d) 10%CuO/CeO2-ZrO2/SiC; (e) 20%CuO/CeO2-ZrO2/SiC

催化剂^a	比表面积/ (m²•g^–1)	孔容/ (cm³•g^–1)	Cu比表面积^b/ (m²•g^–1)	产氢速率^c/ (L•m^–3•s^–1)
a	98.3	0.32	—	—
b	98.3	0.31	4.8	631
c	94.6	0.30	5.8	1556
d	69.5	0.26	5.6	1418
e	63.2	0.21	5.1	1407

表2. 催化剂的物化性质和产氢速率

Table 2. Physicochemical and hydrogen production rate of catalysts

图2. xCuO/CeO2-ZrO2/SiC整体催化剂的H2-TPR谱图

Figure 2. H2-TPR spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

催化剂	峰位置/℃	面积占比/%
催化剂	α峰	β峰	α峰	β峰
2%CuO/CeO₂-ZrO₂/SiC	137	192	30.2%	69.8%
5%CuO/CeO₂-ZrO₂/SiC	137	194	24.6%	75.4%
10%CuO/CeO₂-ZrO₂/SiC	138	197	14.3%	85.7%
20%CuO/CeO₂-ZrO₂/SiC	138	208	9.0%	91.0%

表3. CuO还原峰位置及峰面积占比

Table 3. Reduction peak positions and area content of CuO

图3. xCuO/CeO2-ZrO2/SiC整体催化剂Ce 3d XPS谱图

Figure 3. Ce 3d XPS spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

催化剂	Ce³⁺含量占比/%	Cu⁺含量占比/%
2%CuO/CeO₂-ZrO₂/SiC	9.9	67.1
5%CuO/CeO₂-ZrO₂/SiC	14.5	70.5
10%CuO/CeO₂-ZrO₂/SiC	12.3	67.3
20%CuO/CeO₂-ZrO₂/SiC	11.2	59.2

表4. 催化剂Ce和Cu的XPS曲线拟合结果

Table 4. Fitting results of Cu and Ce XPS curves of catalysts

图4. xCuO/CeO2-ZrO2/SiC整体催化剂Cu 2p XPS谱图

Figure 4. Cu 2p XPS spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

图5. xCuO/CeO2-ZrO2/SiC整体催化剂Cu LMM谱图

Figure 5. Cu LMM spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

图6. xCuO/CeO2-ZrO2/SiC整体催化剂Zr 3d XPS谱图

Figure 6. Zr 3d XPS spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

图7. xCuO/CeO2-ZrO2/SiC整体催化剂O 1s XPS谱图

Figure 7. O 1s XPS spectra of xCuO/CeO2-ZrO2/SiC catalysts (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC

图8. 反应温度与催化剂性能的关系

Figure 8. Correlation between reaction temperature and catalyst performance (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC; (e) equilibrium. Reaction condition: H2O/CH3OH=1.2, GHSV=4840 h–1

图9. 反应温度与重整尾气中CO摩尔含量的关系

Figure 9. Correlation between reaction temperature and CO molar content (a) 2%CuO/CeO2-ZrO2/SiC; (b) 5%CuO/CeO2-ZrO2/SiC; (c) 10%CuO/ CeO2-ZrO2/SiC; (d) 20%CuO/CeO2-ZrO2/SiC; (e) equilibrium. Reaction condition: H2O/CH3OH=1.2, GHSV=4840 h–1

催化剂	T/℃	H₂O/CH₃OH	GHSV/ h^–1	产氢速率/ (L•m^–3•s^–1)
5%CuO/CeO₂-ZrO₂/SiC	360	1.2:1	4840	1556
10%Cu/γ-Al@MMO^[24]	300	1.2:1	1760	721
CuO/CeO₂-R^[26]	240	1.2:1	1760	631
CuZnCeZr^[32]	240	1.2:1	2640	1020
Zn₁Ce₁Zr₉O_x^[33]	400	1.4:1	2955	1135
Zn₅Ce₁Zr₉O_x^[33]	400	1.4:1	2955	476

表5. 催化剂的产氢速率对比

Table 5. Hydrogen production rate of catalysts

参考文献 33

[1]	Jung, C.; Nagel, L.; Schindler, D.; Grau, L. Int. J. Hydrogen Energy 2018, 43,23161.
[2]	Muradov, N. Int. J. Hydrogen Energy 2017, 42,14058.
[3]	Uyar, T.S.; Besikci, D. Int. J. Hydrogen Energy 2017, 42,2453.
[4]	Xi, H.J.; Hou, X.N.; Liu, Y.J.; Qing, S.J.; Gao, Z.X. Angew. Chem., Int. Ed. 2014, 53,11886.
[5]	Chi, H.; Andolina, C.M.; Li, J.; Curnan, M.T.; Saidi, W.A.; Zhou, G.W.; Yang, J.C.; Veser, G. Appl. Catal., A 2018, 556,64.
[6]	Jampa, S.; Jamieson, A.M.; Chaisuwan, T.; Luengnaruemithai, A.; Wongkasemjit, S. Int. J. Hydrogen Energy 2017, 42,15073.
[7]	Kuc, J.; Neumann, M.; Armbruster, M.; Yoon, S.; Zhang, Y.C.; Erni, R.; Weidenkaff, A.; Matam, S.K. Catal. Sci. Technol. 2016, 6,43.
[8]	Ma, Y.F.; Guan, G.Q.; Phanthong, P.; Li, X.M.; Cao, J.; Hao, X.G.; Wang, Z.D.; Abudula, A. Int. J. Hydrogen Energy 2014, 39,18803.
[9]	Sa, S.; Silva, H.; Brandao, L.; Sousa, J.M.; Mendes, A. Appl. Catal., B 2010, 99,43.
[10]	Yao, C.Z.; Zhang, X.R.; Wang, L.C.; Cao, Y.; Dai, W.L.; Fan, K.N.; Wu, D.; Sun, Y.H. Acta Chim. Sinica 2006, 64,269. (in Chinese)
	( 姚成漳, 张新荣, 王路存, 曹勇, 戴维林, 范康年, 吴东, 孙予罕, 化学学报, 2006, 64,269.)
[11]	Kim, W.; Mohaideen, K.K.; Seo, D.J.; Yoon, W.L. Int. J. Hydrogen Energy 2017, 42,2081.
[12]	Zhou, J.J.; Zhang, Y.; Wu, G.S.; Mao, D.S.; Lu, G.Z. RSC Adv. 2016, 6,30176.
[13]	Das, D.; Llorca, J.; Dominguez, M.; Colussi, S.; Trovarelli, A.; Gayen, A. Int. J. Hydrogen Energy 2015, 40,10463.
[14]	Figueiredo, R.T.; Martinez-Arias, A.; Granados, M.L.; Fierro, J.L. G. J. Catal. 1998, 178,146.
[15]	Liu, Y.; Hayakawa, T.; Tsunoda, T.; Suzuki, K.; Hamakawa, S.; Murata, K.; Shiozaki, R.; Ishii, T.; Kumagai, M. Top. Catal. 2003, 22,205.
[16]	Khani, Y.; Bahadoran, F.; Safari, N.; Soltanali, S.; Taheri, S.A. Int. J. Hydrogen Energy 2019, 44,11824.
[17]	Zhou, S.L.; Yuan, Z.S.; Wang, S.D. Int. J. Hydrogen Energy 2006, 31,924.
[18]	Qi, A.D.; Wang, S.D.; Fu, G.Z.; Ni, C.J.; Wu, D.Y. Appl. Catal., A 2005, 281,233.
[19]	Suetsuna, T.; Suenaga, S.; Fukasawa, T. Appl. Catal., A 2004, 276,275.
[20]	Liu, N.; Yuan, Z.S.; Zhang, C.X.; Wang, S.J.; Li, D.Y.; Wang, S.D. Chin. J. Catal. 2005, 26,1078. (in Chinese)
	( 刘娜, 袁中山, 张纯希, 王淑娟, 李德意, 王树东, 催化学报, 2005, 26,1078.)
[21]	Liu, N.; Wang, S.D.; Yuan, Z.S.; Zhang, C.X.; Wang, S.J.; Li, D.Y.; Fu, G.Z. CIESC J. 2004, 55,90. (in Chinese)
	( 刘娜, 王树东, 袁中山, 张纯希, 王淑娟, 李德意, 付桂芝, 化工学报, 2004, 55,90.)
[22]	Liu, Y.J.; Wang, D.Z.; Zhang, L.; Bai, J.; Chen, L.; Liu, D.S. Fine Chem. 2018, 35,2045. (in Chinese)
	( 刘玉娟, 王东哲, 张磊, 白金, 陈琳, 刘道胜, 精细化工, 2018, 35,2045.)
[23]	Putna, E.S.; Bunluesin, T.; Fan, X.L.; Gorte, R.J.; Vohs, J.M.; Lakis, R.E.; Egami, T. Catal. Today 1999, 50,343.
[24]	He, J.P.; Yang, Z.X.; Zhang, L.; Li, Y.; Pan, L.W. Int. J. Hydrogen Energy 2017, 42,9930.
[25]	He, J.P.; Zhang, L.; Chen, L.; Yang, Z.X.; Tong, Y.F. Chem. J. Chinese U. 2017, 38,1822. (in Chinese)
	( 贺建平, 张磊, 陈琳, 杨占旭, 佟宇飞, 高等学校化学学报, 2017, 38,1822.)
[26]	Yang, S.Q.; Zhou, F.; Liu, Y.J.; Zhang, L.; Chen, Y.; Wang, H.H.; Tian, Y.; Zhang, C.S.; Liu, D.S. Int. J. Hydrogen Energy 2019, 44,7252.
[27]	She, W.; Qi, T.Q. J.; Cui, M.X.; Yan, P.F.; Weng, N.S. W.; Li, W.Z.; Li, G.M. ACS Appl. Mater. Interfaces 2018, 10,14698.
[28]	Wang, D.Z.; Feng, X.; Zhang, J.; Chen, L.; Zhang, L.; Wang, H.H.; Bai, J.; Zhang, C.S.; Zhang, Z.Y. J. Fuel Chem. Technol. 2019, 47,1251. (in Chinese)
	( 王东哲, 冯旭, 张健, 陈琳, 张磊, 王宏浩, 白金, 张财顺, 张政一, 燃料化学学报, 2019, 47,1251.)
[29]	Prusty, D.; Pathak, A.; Mukherjee, M.; Mukherjee, B.; Chowdhury, A. Mater. Charact. 2015, 10,31.
[30]	Bai, Y.X.; Wu, J.J.; Qiu, X.P.; Wang, J.S.; Zhu, W.T.; Chen, L.Q. Acta Chim. Sinica 2006, 64,527. (in Chinese)
	( 白玉霞, 吴建军, 邱新平, 王建设, 朱文涛, 陈立泉, 化学学报, 2006, 64,527.)
[31]	Wang, Z.H.; Shi, G.Y.; Xia, J.F.; Zhang, F.F.; Xia, Y.Z.; Li, Y.H.; Xia, L.H. Acta Chim. Sinica 2013, 71,1225. (in Chinese)
	( 王宗花, 史国玉, 夏建飞, 张菲菲, 夏延致, 李延辉, 夏临华, 化学学报, 2013, 71,1225.)
[32]	Zhang, L.; Pan, L.W.; Ni, C.J.; Sun, T.J.; Zhao, S.S.; Wang, S.D.; Wang, A.J.; Hu, Y.K. Int. J. Hydrogen Energy 2013, 38,4397.
[33]	Song, Q.L.; Men, Y.; Wang, J.G.; Liu, S.; Chai, S.S.; An, W.; Wang, K.; Li, Y.Y.; Tang, Y.H. Int. J. Hydrogen Energy 2020, 45,9592.

CuO/CeO₂-ZrO₂/SiC整体催化剂催化甲醇水蒸气重整制氢的研究

Research on CuO/CeO₂-ZrO₂/SiC Monolithic Catalysts for Hydrogen Production by Methanol Steam Reforming

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