Design,Preparation and Performance of CuO⁃SiO2⁃CeO2 Catalyst

doi:10.3969/j.issn.1006-396X.2022.01.005

Abstract

Abstract:

SiO₂?CeO₂ carriers were prepared by hydrothermal synthesis method,and CuO?SiO₂?CeO₂ catalysts were synthesized by impregnation method with active component CuO.The carriers and catalysts were characterized by XRD,BET and H₂?TPR methods.The effects of the addition amount of SiO₂ for the specific surface area of the catalyst and the catalytic performance of the catalysts in methanol steam reforming for hydrogen production were also investigated.The obtained results indicated that appropriate addition of SiO₂ can increase the specific surface area of the support and catalyst,reduce reduction temperature of the active component CuO,and increase the conversion rate of CH₃OH.When the amount of SiO₂ is 2.5%,the specific surface area of CuO5.0%?SiO₂2.5%?CeO₂ is 112.8 m²/g,and the conversion rate of CH₃OH is 75.1%.Both of the specific surface of the catalyst and the conversion rate of CH₃OH will decrease with the content of SiO₂ continue to improving in the catalyst.

Key words: Methanol steam reforming, CeO₂, Hydrothermal synthesis method, Catalyst preparation

摘要：

采用水热合成法制备了SiO₂?CeO₂载体，并利用浸渍法负载活性组分CuO得到CuO?SiO₂?CeO₂催化剂。通过XRD、BET和H₂?TPR等手段对载体和催化剂进行表征及性能测试，最后探究了SiO₂摩尔分数对催化剂的比表面积以及甲醇水蒸气重整制氢实验中催化性能的影响。研究发现，适量添加SiO₂可以增加载体和催化剂的比表面积，降低催化剂活性组分CuO的还原温度，提高CH₃OH的转化率。当SiO₂摩尔分数为2.5%时，催化剂CuO5.0%?SiO₂2.5%?CeO₂的比表面积为112.8 m²/g，CH₃OH转化率为75.1%。继续提高催化剂中SiO₂的摩尔分数，催化剂的比表面积减小，CH₃OH转化率降低。

关键词: 甲醇水蒸气重整, CeO₂, 水热合成法, 催化剂制备

CLC Number:

O643

Chang Lu, Caishun Zhang, Daosheng Liu, Lei Zhang, Zhixian Gao. Design,Preparation and Performance of CuO⁃SiO₂⁃CeO₂ Catalyst[J]. Journal of Petrochemical Universities, 2022, 35(1): 29-34.

卢畅, 张财顺, 刘道胜, 张磊, 高志贤. CuO⁃SiO₂⁃CeO₂催化剂的设计、制备及性能研究[J]. 石油化工高等学校学报, 2022, 35(1): 29-34.

Figures/Tables 9

Table 1 The raw material of supports

x（SiO₂）/%	m（Ce(NO₃)₃ $⋅$ 6H₂O）/g	m（TEOS）/ g	m（尿素）/ g
0	12.612	0	3.926
2.5	12.612	0.155	4.060
5.0	12.612	0.336	4.217
7.5	12.612	0.491	4.350
15.0	12.612	1.070	4.851

Table 1 The raw material of supports

x（SiO₂）/%	m（Ce(NO₃)₃ $⋅$ 6H₂O）/g	m（TEOS）/ g	m（尿素）/ g
0	12.612	0	3.926
2.5	12.612	0.155	4.060
5.0	12.612	0.336	4.217
7.5	12.612	0.491	4.350
15.0	12.612	1.070	4.851

Fig.1 XRD of carriers with different mole fractions of SiO2

Table 2 Cell parameters and average grain size of different SiO2 mole fraction carriers

x（SiO₂）/%	晶胞参数/nm	平均晶粒/nm
0	0.5406 20	13.77
2.5	0.5408 35	12.04
5.0	0.5407 75	12.79
7.5	0.5406 52	11.73
15.0	0.5408 57	12.37

Fig.2 XRD patterns of catalysts with different mole fractions of SiO2

Table 3 Specific surface area, pore volume and pore diameter of different mole fractions of SiO2

样品类型	比表面积/（m² $⋅$ g^-1）	孔体积/（mL $⋅$ g^-1）	孔径/nm
CeO₂	120.5	0.093 7	3.110 4
SiO₂2.5%⁃CeO₂	145.9	0.111 4	3.054 7
SiO₂5.0%⁃CeO₂	140.2	0.108 3	3.090 9
SiO₂7.5%⁃CeO₂	138.7	0.124 5	3.591 5
SiO₂15.0%⁃CeO₂	112.5	0.104 0	3.698 3

Table 3 Specific surface area, pore volume and pore diameter of different mole fractions of SiO2

样品类型	比表面积/（m² $⋅$ g^-1）	孔体积/（mL $⋅$ g^-1）	孔径/nm
CeO₂	120.5	0.093 7	3.110 4
SiO₂2.5%⁃CeO₂	145.9	0.111 4	3.054 7
SiO₂5.0%⁃CeO₂	140.2	0.108 3	3.090 9
SiO₂7.5%⁃CeO₂	138.7	0.124 5	3.591 5
SiO₂15.0%⁃CeO₂	112.5	0.104 0	3.698 3

Fig.3 Diagram of specific surface area of support and catalyst

Table 4 Specific surface area, pore volume and pore size of catalysts with different mole fractions of SiO2

样品类型	比表面积/（m²·g^-1）	孔体积/（mL·g^-1）	孔径/nm
CuO5.0%⁃CeO₂	79.3	0.071 0	3.583 3
CuO5.0%⁃SiO₂2.5%⁃CeO₂	112.8	0.089 1	3.159 1
CuO5.0%⁃SiO₂5.0%⁃CeO₂	102.3	0.088 1	3.446 0
CuO5.0%⁃SiO₂7.5%⁃CeO₂	100.8	0.103 7	4.113 4
CuO5.0%⁃SiO₂15.0%⁃CeO₂	97.7	0.106 1	4.343 4

Fig.4 Catalysts with different mole fractions of SiO2

Fig.5 Relationship between catalytic activity and reforming temperature。

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Design,Preparation and Performance of CuO⁃SiO₂⁃CeO₂ Catalyst

CuO⁃SiO₂⁃CeO₂催化剂的设计、制备及性能研究

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