助剂对ZnO/ZrO2物化性质及催化性能的影响

doi:10.19964/j.issn.1006-4990.2023-0333

摘要/Abstract

摘要：

CO₂加氢制甲醇是实现碳中和目标的有效途径。尽管已报道的ZnO/ZrO₂催化剂具有高活性和稳定性，但其催化性能仍有望进一步提高。采用浸渍法制备得到一系列不同元素掺杂的Ma-ZnO _x /ZrO₂催化剂，并通过评价发现只有Ga促进了ZnO/ZrO₂催化剂催化CO₂加氢制甲醇。其中，5%Ga-ZnO _x /ZrO₂催化剂表现出优异的催化性能，在反应条件：P=3 MPa、T=320 ℃、V（H₂）∶V（CO₂）=4∶1、气体质量空速（WHSV）=24 000 mL/（g∙h）时CO₂转化率为7.2%，甲醇选择性为81.0%，甲醇时空产率可达410 mg/（g∙h），是ZnO/ZrO₂的1.26倍，且在反应100 h内催化性能无明显衰减。X射线光电子能谱（XPS）和电子顺磁共振（EPR）表征发现，适量Ga助剂的掺入可以促进催化剂中氧空位的形成。H₂程序升温还原（H₂-TPR）、CO₂/H₂程序升温脱附（CO₂/H₂-TPD）结果表明，Ga助剂的掺入增强了ZnO/ZrO₂催化剂活性位点的活性，Ga-ZnO _x /ZrO₂催化剂表现出更强的CO₂和H₂吸附活化能力。原位漫反射傅里叶变换红外（in situ DRIFTS）结果表明，各催化剂合成甲醇均遵循甲酸盐-甲氧基路径，Ga助剂的掺入促进了甲醇中间体的形成，并且更有利于HCOO*物种向CH₃O*物种的转化，从而提高甲醇产率。

关键词: CO₂加氢, 甲醇, ZnO/ZrO₂, Ga助剂, 氧空位

Abstract:

CO₂ hydrogenation to methanol is an effective way to achieve the goal of carbon neutrality.Although the reported ZnO/ZrO₂ catalysts have high activity and stability，their catalytic performance are expected to be further improved.A series of Ma-ZnO _x /ZrO₂ catalysts with different elements doping were prepared by the impregnation method，and it was found by evaluation that only Ga promoted the catalytic CO₂ hydrogenation to methanol by ZnO/ZrO₂ catalyst.Among them，5%Ga-ZnO _x /ZrO₂ catalyst showed excellent catalytic performance.At the reaction conditions：P=3 MPa，T=320 ℃，V（H₂）∶V（CO₂）=4∶1 and gas weight hourly space velocity（WHSV）=24 000 mL/（g∙h），the CO₂ conversion of 5%Ga-ZnO _x /ZrO₂ catalyst was 7.2%，the methanol selectivity was 81.0% and the methanol space-time yield was up to 410 mg/（g∙h），which was 1.26 times higher than that of the ZnO/ZrO₂.And there was no significant decay in the catalytic performance within 100 h of reaction.X-ray photoelectron spectrometry（XPS） and electron paramagnetic resonance（EPR） characterization showed that doping with the appropriate amount of Ga promoter could promote the formation of oxygen vacancies in the catalyst.H₂ temperature programmed reduction（H₂-TPR），temperature-programmed desorption of the preabsorbed CO₂/H₂（CO₂/H₂-TPD） results showed that the doping of the Ga promoter enhanced the activity of the active sites of the ZnO/ZrO₂ catalyst，and the Ga-ZnO _x /ZrO₂ catalyst exhibited a stronger capacity for the adsorption and activation of CO₂ and H₂.The in situ diffuse reflectance infrared Fourier transform spectroscopy（in situ DRIFTS） results showed that the synthesis of methanol by each catalyst followed the formate-methoxy pathway，and the incorporation of Ga promoter facilitated the formation of methanol intermediates and was favorable for the conversion of HCOO* species to CH₃O* species，thus improving the methanol yield.

Key words: CO₂ hydrogenation, methanol, ZnO/ZrO₂, Ga promoter, oxygen vacancy

中图分类号:

TQ132.41

任启霞, 杨坤, 刘飞, 姚梦琴, 曹建新. 助剂对ZnO/ZrO₂物化性质及催化性能的影响[J]. 无机盐工业, 2024, 56(3): 144-154.

REN Qixia, YANG Kun, LIU Fei, YAO Mengqin, CAO Jianxin. Effect of promoter on physicochemical properties and catalytic performance of ZnO/ZrO₂[J]. Inorganic Chemicals Industry, 2024, 56(3): 144-154.

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催化剂	比表面积/（m²∙g^-1）	孔容/（cm³∙g^-1）
ZnO/ZrO₂	49.9	0.23
2.5%Ga-ZnO _x /ZrO₂	51.3	0.23
5%Ga-ZnO _x /ZrO₂	54.0	0.24
7.5%Ga-ZnO _x /ZrO₂	50.4	0.23
10%Ga-ZnO _x /ZrO₂	49.3	0.19

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助剂对ZnO/ZrO₂物化性质及催化性能的影响

Effect of promoter on physicochemical properties and catalytic performance of ZnO/ZrO₂

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