Study on Hydrogen Production Catalytic Materials for Perovskite Methanol Steam Reforming

doi:10.6023/A20080374

Abstract

As an important clean energy, hydrogen energy has the advantages of light weight, high calorific value, and environmental protection. If hydrogen energy can be well developed and stored, it will play more and more important roles in the human production and life. Methanol steam reforming (MSR) hydrogen production technology, which has been used in industry for many years, is the best choice for methanol hydrogen production because of its high hydrogen content in reforming tail gas and mature technology. ABO₃ perovskite oxide is a new type of material. Compared with other materials, due to its unique electronic structure, it has various properties such as electricity, magnetism, optics and chemistry. It have shown great application prospects in many fields. The perovskite composite oxide was synthesized by the sol-gel method. After loading copper oxide, a perovskite-supported catalytic material was obtained. The catalytic material was characterized by XRD (X-ray diffraction), BET (Brunner-Emmet-Teller), H₂-TPR (H₂-temperature programmed reduction) and XPS (X-ray photo- electron spectra). The effect of the structure and properties of perovskite-loaded nano-copper catalytic materials on the performance of methanol steam reforming for hydrogen production were investigated. The results showed that the catalytic activity of the perovskite-loaded nano-copper catalytic material is mainly related to the copper surface area, the catalytic and reductive properties, the oxygen lattice deficiency on the surface of the catalyst, and the interaction between the active component and the carrier. Among them, because the CuO/LaCrO₃ perovskite-supported catalytic materials have the larger copper surface area, the lower reduction temperature, the more oxygen vacancies on the surface, and the stronger interaction between the active component, the catalytic activity of methanol steam reforming for hydrogen production is better than that of the CuO/LaNiO₃, CuO/LaFeO₃ and CuO/La₂Zr₂O₇. When the reaction temperature was 360 ℃, the CuO/LaCrO₃ perovskite catalyst did not show significant deactivation, the methanol conversion rate was 98.6%, and the hydrogen production rate was 694.9 mL•kg_cat ^–1•s ^–1.

Key words: perovskite, CuO, catalyst, steam reforming of methanol, hydrogen

Cite this article

Guopeng Xiao, Weijun Qiao, Lei Zhang, Shaojun Qing, Caishun Zhang, Zhixian Gao. Study on Hydrogen Production Catalytic Materials for Perovskite Methanol Steam Reforming[J]. Acta Chimica Sinica, 2021, 79(1): 100-107.

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Fig. & Tab. 15

Figure 1. XRD patterns of perovskite catalytic material a—LaCrO3; b—LaNiO3; c—LaFeO3; d—La2Zr2O7

Figure 2. XRD patterns of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	比表面积/ (m ²•g ^–1)	孔容/ (cm ³•g ^–1)	孔径/nm
LaCrO ₃	10.6	0.02	3.06
LaNiO ₃	7.4	0.02	3.06
LaFeO ₃	10.8	0.02	3.41
La ₂Zr ₂O ₇	4.0	0.01	3.31

Table 1. The physical and chemical properties of the carrier

催化剂	比表面积/ (m ²•g ^–1)	孔容/ (cm ³•g ^–1)	孔径/nm	铜比表面积/ (m ²•g _cat ^–1)	产氢速率 ^a / (mL•kg _cat ^–1• s ^–1)
CuO/ LaCrO ₃	12.1	0.03	3.06	2.1	665.5
CuO/ LaNiO ₃	7.5	0.02	3.03	1.2	427.7
CuO/ LaFeO ₃	11.5	0.03	3.86	1.1	276.6
CuO/ La ₂Zr ₂O ₇	4.1	0.01	3.48	1.1	304.3

Table 2. The catalyst physicochemical properties and hydrogen production rate in the MSR reaction

Figure 3. H2-TPR profiles of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 4. XPS spectra of La 3d for CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 5. XPS spectra of Cu 2p for CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 6. Cu Auger spectra of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	Cu ⁺/(Cu ⁺+Cu ²⁺) (at%)
CuO/LaCrO ₃	56
CuO/LaNiO ₃	51
CuO/LaFeO ₃	48
CuO/La ₂Zr ₂O ₇	48

Table 3. Cu LMM XPS curve fitting results of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts

Figure 7. XPS spectra of O 1s of CuO/LaBO3(B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	O _ads/(O _latt+O _ads+O _H2O) (at%)
CuO/LaCrO ₃	34
CuO/LaNiO ₃	31
CuO/LaFeO ₃	28
CuO/La ₂Zr ₂O ₇	27

Table 4. Curve fitting results of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts and O 1s XPS curves

Figure 8. The influence of the reaction temperature on the catalytic activity Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 9. The influence of the reaction temperature on the CO molar content Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 10. The influence of the reaction temperature on the Hydrogen selectivity Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

Figure 11. Stability test of the CuO/LaCrO3 catalyst Reaction conditions: atmospheric,T=320 ℃, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas

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