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

doi:10.6023/A20120562

Abstract

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

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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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Fig. & Tab. 14

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

Table 1. Comparison table of thermal conductivity

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

Table 2. Physicochemical and hydrogen production rate of catalysts

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%

Table 3. Reduction peak positions and area content of CuO

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

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

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

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

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

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

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

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

Table 5. Hydrogen production rate of catalysts

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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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Fig. & Tab. 14

References 33

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CuO/CeO2-ZrO2/SiC整体催化剂催化甲醇水蒸气重整制氢的研究