Si掺杂对Cu/ZrO2催化CO2加氢制甲醇性能的影响

doi:10.11949/0438-1157.20220614

摘要/Abstract

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

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

中图分类号:

TQ 546.4

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.

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.

图/表 15

图1 催化剂的XRD谱图

Fig.1 XRD patterns of catalysts

图2 由N2物理吸附脱附仪测得的催化剂的孔道结构

Fig.2 Pore structures of catalysts tested by N2-physical adsorption-desorption

表1 催化剂的理化性质

Table 1 Physical and chemical properties of catalysts

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

图3 载体xSi-ZrO2的XPS谱图

Fig.3 XPS spectra of the xSi-ZrO2 supports

图4 催化剂Cu/xSi-ZrO2的XPS谱图

Fig.4 XPS spectra of the Cu/xSi-ZrO2 catalysts

表2 Cu/xSi-ZrO2催化剂中Cu的化学价态

Table 2 Cu valence of Cu/xSi-ZrO2 catalysts

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

图5 催化剂O 1s的XPS谱图

Fig.5 XPS spectra of O 1s of catalysts

表3 Cu/xSi-ZrO2催化剂中O的化学价态

Table 3 O valence of Cu/xSi-ZrO2 catalysts

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

图6 催化剂的H2-TPR

Fig.6 H2-TPR profiles of catalysts

图7 催化剂的CO2-TPD

Fig.7 CO2-TPD profiles of catalysts

表4 催化剂表面碱性位点密度

Table 4 The basic sites density of catalysts

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

图8 催化剂的TEM图

Fig.8 TEM images of catalysts

图9 Cu/xSi-ZrO2催化剂的催化性能

Fig.9 Catalytic performance of Cu/xSi-ZrO2 catalysts

图10 Cu/ZrO2, Cu/0.1Si-ZrO2和Cu/0.2Si-ZrO2催化剂甲醇生成的TOF和Arrhenius图

Fig.10 TOF and Arrhenius plots of TOF for the formation of methanol of Cu/ZrO2, Cu/0.1Si-ZrO2 and Cu/0.2Si-ZrO2 catalysts

图11 Cu/xSi-ZrO2催化剂性能提高的原因示意图

Fig.11 Schematic diagram of the improvement of Cu/xSi-ZrO2 catalysts performance

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Si掺杂对Cu/ZrO₂催化CO₂加氢制甲醇性能的影响

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

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