Effect of Si-doped Cu/ZrO2 on the performance of catalysts for CO2 hydrogenation to methanol

doi:10.11949/0438-1157.20220614

Abstract

Abstract:

In order to improve the catalytic activity of Cu/ZrO₂catalysts in carbon dioxide hydrogenation to methanol, a series of Si-ZrO₂ supports with different Si/Zr were prepared and loaded 5% Cu to obtain the Cu/Si-ZrO₂ catalysts. The prepared catalysts were characterized by X-ray diffraction (XRD), N₂ physisorption measurements (BET), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of CO₂(CO₂-TPD) and high-resolution transmission electron microscopy (HRTEM). The results showed that the doping of Si promoted Cu/ZrO₂ system to obtain stable crystal phase, abundant specific surface area and more basic sites, especially medium and strong basic sites. At the same time, higher oxygen vacancy concentration was generated, which promoted the adsorption and activation of CO₂, and thus the catalyst with Si/Zr molar ratio 0.2 which possessed higher activity with 4.6% CO₂ conversion and 85% CH₃OH selectivity was obtained at 220℃ under 3.0 MPa with WHSV=6000 ml·g^-1·h^-1, H₂/CO₂ volume ratio 3/1.

Key words: activation, carbon dioxide, catalyst, methanol synthesis, silica, modified zirconia

摘要：

为了提高Cu/ZrO₂催化剂在二氧化碳加氢制甲醇中的催化活性，制备了一系列不同Si/Zr的Si-ZrO₂载体并负载5%（质量分数）Cu得到了Cu/Si-ZrO₂催化剂。对所制备的催化剂进行了X射线衍射（XRD）、N₂物理吸脱附（BET）、X射线光电子能谱（XPS）、氢气程序升温还原（H₂-TPR）、二氧化碳程序升温脱附（CO₂-TPD）及高分辨透射电子显微镜（HRTEM）的表征。结果表明，Si的掺杂使得Cu/ZrO₂体系获得了稳定的晶相，大的比表面积和更多的碱性位点，尤其是中强碱性位点，同时产生了更多的氧空位，促进了CO₂的吸附和转化，因此得到了更高活性的催化剂。当Si与Zr的摩尔比为0.2时，在质量空速为6000 ml·g^-1·h^-1，温度为220℃、压力为3.0 MPa，V（H₂）∶V（CO₂）=3∶1（体积比）条件下，催化剂的CO₂转化率为4.6%，CH₃OH选择性为85%。

关键词: 活化, 二氧化碳, 催化剂, 甲醇合成, 二氧化硅, 改性二氧化锆

CLC Number:

TQ 546.4

Wenhua DAI, Zhong XIN. Effect of Si-doped Cu/ZrO₂on the performance of catalysts for CO₂ hydrogenation to methanol[J]. CIESC Journal, 2022, 73(8): 3586-3596.

戴文华, 辛忠. Si掺杂对Cu/ZrO₂催化CO₂加氢制甲醇性能的影响[J]. 化工学报, 2022, 73(8): 3586-3596.

Figures/Tables 15

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催化剂	比表面积^①/(m²·g^-1)	孔容^②/(cm³·g^-1)	平均孔径/ nm	铜比表面积^③/(m²·g^-1)
Cu/ZrO₂	43	0.17	15.5	2.02
Cu/0.1Si-ZrO₂	162	0.43	10.7	6.31
Cu/0.2Si-ZrO₂	188	0.37	7.8	8.89
Cu/0.3Si-ZrO₂	252	0.30	4.8	6.19
Cu/0.4Si-ZrO₂	272	0.41	7.2	6.12

催化剂	比表面积^①/(m²·g^-1)	孔容^②/(cm³·g^-1)	平均孔径/ nm	铜比表面积^③/(m²·g^-1)
Cu/ZrO₂	43	0.17	15.5	2.02
Cu/0.1Si-ZrO₂	162	0.43	10.7	6.31
Cu/0.2Si-ZrO₂	188	0.37	7.8	8.89
Cu/0.3Si-ZrO₂	252	0.30	4.8	6.19
Cu/0.4Si-ZrO₂	272	0.41	7.2	6.12

催化剂	Cu物种/%
催化剂	CuO	Cu-Si-Zr氧化物
Cu/ZrO₂	71.7	28.3
Cu/0.1Si-ZrO₂	59.4	40.6
Cu/0.2Si-ZrO₂	35.1	64.9

催化剂	Cu物种/%
催化剂	CuO	Cu-Si-Zr氧化物
Cu/ZrO₂	71.7	28.3
Cu/0.1Si-ZrO₂	59.4	40.6
Cu/0.2Si-ZrO₂	35.1	64.9

催化剂	O物种/%
催化剂	晶格氧	缺陷氧
Cu/ZrO₂	77.7	22.3
Cu/0.1Si-ZrO₂	70.9	29.1
Cu/0.2Si-ZrO₂	59.3	40.7
Cu/0.3Si-ZrO₂	60.6	39.4
Cu/0.4Si-ZrO₂	64.8	35.2

Effect of Si-doped Cu/ZrO₂on the performance of catalysts for CO₂ hydrogenation to methanol

Si掺杂对Cu/ZrO₂催化CO₂加氢制甲醇性能的影响

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Figures/Tables 15

References 49

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催化剂	总碱性位点/(µmol·g^-1)	弱碱性位点/ (µmol·g^-1)	中强碱性位点/ (µmol·g^-1)	中强碱密度/(µmol·m^-2)
Cu/ZrO₂	35.6	18.4	17.2	0.40
Cu/0.1Si-ZrO₂	229.5	190.6	38.9	0.24
Cu/0.2Si-ZrO₂	230.5	19.1	211.4	1.12
Cu/0.3Si-ZrO₂	207.4	14.0	193.4	0.77
Cu/0.4Si-ZrO₂	187.4	2.9	184.5	0.68

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