Effect of CeO2 on Cu/Zn-Al Catalysts Derived from Hydrotalcite Precursor for Methanol Steam Reforming†

doi:10.7503/cjcu20170158

Abstract

Abstract:

ZnAl-LDHs was synthesized on γ-Al₂O₃ by in situ synthesis method. Moreover, the Ce/Cu/Zn-Al catalysts were prepared by ordinal wet impregnation method and applied to methanol steam reforming. The effect of cerium content on Cu/Zn-Al catalysts was discussed for methanol steam reforming. The catalysts were studied by XRD, SEM, H₂-TPR, N₂ adsorption techniques and chemisorption N₂O. The results showed that the addition of CeO₂ improved the copper dispersion, copper surface area and catalyst reducibility. The catalytic activity and hydrogen production rate was also promoted thereby. When the Ce content was 4%, the catalyst exhibited the best catalytic activity, that was, the methanol conversion was 100% and the molar fraction of CO was 0.39% at 250 ℃ in hydrogen production by methanol steam reforming. Compared to the Cu/ZnAl catalyst, the methanol conversion increased by almost 40%.

Key words: CeO₂, Methanol steam reforming, Hydrotalcite, Hydrogen

CLC Number:

O643

TrendMD:

HE Jianping, ZHANG Lei, CHEN Lin, YANG Zhanxu, TONG Yufei. Effect of CeO₂ on Cu/Zn-Al Catalysts Derived from Hydrotalcite Precursor for Methanol Steam Reforming^†[J]. Chem. J. Chinese Universities, 2017, 38(10): 1822.

Figures/Tables 8

Fig.1 XRD patterns of γ-Al2O3(a) and ZnAl-LDHs/γ-Al2O3(b)

Fig.2 XRD patterns of the prepared catalysts with different cerium contentsa. CZA; b. 2%Ce/CZA; c. 4%Ce/CZA;d. 6%Ce/CZA; e. 8%Ce/CZA.

Fig.3 SEM images of γ-Al2O3 (A) and ZnAl-LDHs/γ-Al2O3 (B)

Table 1 Component contents of different catalysts

Catalyst	Content of element(%)
Catalyst	Cu	Zn	Al	Ce	O
CZA	9.66	14.60	36.90		38.84
2%Ce/CZA	9.43	14.28	36.11	1.79	38.39
4%Ce/CZA	9.19	13.88	35.42	3.50	38.01
6%Ce/CZA	9.03	13.24	34.73	5.37	37.63
8%Ce/CZA	8.87	13.00	33.99	6.92	37.22

Table 2 Physical characteristics of the prepared catalysts and hydrogen production rate in methanol steam reforminga

Catalyst	S_BET/(m²·g^-1)	Pore volume/ (cm³·g^-1)	d_CuO/nm	Cu dispersion^b(%)	Cu surface area^c/ (m²·g^-1)	$Y H 2$ / (mL³·k $g cat - 1$ ·s^-1)
CZA	147.0	0.47	34.0	10.32	5.90	446.2
2%Ce/CZA	114.1	0.42	24.4	10.96	6.17	786.6
4%Ce/CZA	109.6	0.41	22.8	11.49	6.32	810.7
6%Ce/CZA	106.7	0.38	26.4	11.44	6.16	691.2
8%Ce/CZA	105.3	0.37	26.7	11.78	6.18	648.0

Table 2 Physical characteristics of the prepared catalysts and hydrogen production rate in methanol steam reforminga

Catalyst	S_BET/(m²·g^-1)	Pore volume/ (cm³·g^-1)	d_CuO/nm	Cu dispersion^b(%)	Cu surface area^c/ (m²·g^-1)	$Y H 2$ / (mL³·k $g cat - 1$ ·s^-1)
CZA	147.0	0.47	34.0	10.32	5.90	446.2
2%Ce/CZA	114.1	0.42	24.4	10.96	6.17	786.6
4%Ce/CZA	109.6	0.41	22.8	11.49	6.32	810.7
6%Ce/CZA	106.7	0.38	26.4	11.44	6.16	691.2
8%Ce/CZA	105.3	0.37	26.7	11.78	6.18	648.0

Fig.4 H2-TPR profiles of the prepared catalystsa. CZA; b. 2%Ce/CZA; c. 4%Ce/CZA; d. 6%Ce/CZA; e. 8%Ce/CZA.

Fig.5 Profiles of the catalyst activity as a function of the reaction temperatureReaction conditions: n(water)/n(methanol)=1.2:1, GHSV=800 h-1, no carrier gas.

Fig.6 Profiles of the CO molar fraction as a function of the reaction temperatureReaction conditions: n(water)/n(methanol)=1.2:1, GHSV=800 h-1, no carrier gas.

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Effect of CeO₂ on Cu/Zn-Al Catalysts Derived from Hydrotalcite Precursor for Methanol Steam Reforming^†

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