Pd-Cu/ZrO2催化CO2加氢制甲醇的性能

doi:10.11944/j.issn.1000-0518.2020.02.190211

摘要/Abstract

摘要：

采用溶胶-凝胶法制备了n(Cu):n(Zr)=1:1、1:2、1:4和1:8的Cu/ZrO₂催化剂。实验结果表明,当n(Cu):n(Zr)=1:4时,催化剂表现出较高的CO₂转化率(8.0%)和甲醇选择性(59.5%),为了增加CO₂的转化率,提高甲醇选择性,在n(Cu):n(Zr)=1:4的催化剂中添加质量分数1%的Pd,采用浸渍法制备了Pd-Cu/ZrO₂催化剂。在250 ℃、2 MPa、12000 mL/(g·h)和V(H₂):V(CO₂)=3:1的反应条件下,CO₂转化率和CH₃OH收率相比Cu/ZrO₂催化剂(n(Cu):n(Zr)=1:4)分别提高了40.0%和80.9%。通过X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)、N₂吸附-脱附(BET)、X射线光电子能谱仪(XPS)和程序升温还原化学吸附仪(H₂-TPR)等仪器表征证明Pd的添加提高了催化剂的分散性和比表面积。催化剂中Pd和Cu之间强相互作用,使Cu2p轨道结合能向低处偏移,还原温度的降低,说明Pd-Cu/ZrO₂催化剂还原能力增强,使得CO₂加氢活性提高。

关键词: 溶胶-凝胶法, 浸渍法, CO₂加氢, 甲醇

Abstract:

Cu/ZrO₂ catalysts with the Cu/Zr molar ratio of 1:1, 1:2, 1:4 and 1:8 were prepared by the sol-gel method. When n(Cu):n(Zr)=1:4, a high CO₂ conversion (8.0%) with methanol selectivity of 59.5% was achieved. To increase CO₂ conversion and CH₃OH selectivity, Pd-Cu/ZrO₂ catalyst with the Cu/Zr molar ratio of 1:4 and 1 % mass fraction of Pd was synthesized by the impregnation method. The results showed that CO₂ conversion and CH₃OH yield over the Pd-Cu/ZrO₂ catalyst were 40.0% and 80.9% higher than that over the Cu/ZrO₂ catalyst at 250 ℃, 2 MPa, 12000 mL/(g·h) and V(H₂):V(CO₂)=3:1. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy analysis (FT-IR), N₂ adsorption-desorption (BET), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction of H₂(H₂-TPR) results indicated that addition of Pd improved the dispersion and surface area of the catalyst. The strong interaction between Pd and Cu species leads to the shift of Cu2p to low binding energies and decreases the catalyst reduction temperature, which exhibits high catalytic performance for hydrogenation of CO₂.

Key words: sol-gel method, impregnation method, carbon dioxide hydrogenation, methanol

高佳, 宋夫交, 程文强, 葛艳, 许琦. Pd-Cu/ZrO₂催化CO₂加氢制甲醇的性能[J]. 应用化学, 2020, 37(2): 160-167.

GAO Jia, SONG Fujiao, CHENG Wenqiang, GE Yan, XU Qi. Catalytic Performance of Pd-Cu/ZrO₂ Catalyst for Hydrogenation of Carbon Dioxide to Methanol[J]. Chinese Journal of Applied Chemistry, 2020, 37(2): 160-167.

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Pd-Cu/ZrO₂催化CO₂加氢制甲醇的性能

Catalytic Performance of Pd-Cu/ZrO₂ Catalyst for Hydrogenation of Carbon Dioxide to Methanol

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