多级孔Co/Al-SiO2催化剂制备及其费-托合成催化性能

doi:10.15541/jim20190500

无机材料学报 ›› 2020, Vol. 35 ›› Issue (9): 999-1004.DOI: 10.15541/jim20190500 CSTR: 32189.14.10.15541/jim20190500

所属专题：环境材料论文精选(2020)；【虚拟专辑】化学反应催化剂(2020~2021)

多级孔Co/Al-SiO₂催化剂制备及其费-托合成催化性能

王举汉(),文雄,刘成超,张煜华,赵燕熹,李金林()

中南民族大学催化转化与能源材料化学教育部重点实验室, 催化材料科学湖北省重点实验室, 武汉430074

收稿日期:2019-09-29 修回日期:2019-12-17 出版日期:2020-09-20 网络出版日期:2020-03-03
作者简介:王举汉(1994-), 男, 硕士研究生. E-mail: 834767117@qq.com
WANG Juhan(1994-), Male, Master candidate. E-mail:834767117@qq.com
基金资助:
国家自然科学基金(21972170);国家自然科学基金(21902187);湖北省自然科学基金(2018CFB365)

Preparation and Fischer-Tropsch Synthesis Performance of Hierarchical Co/Al-SiO₂ Catalyst

WANG Juhan(),WEN Xiong,LIU Chengchao,ZHANG Yuhua,ZHAO Yanxi,LI Jinlin()

Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central University for Nationalities, Wuhan 430074, China

Received:2019-09-29 Revised:2019-12-17 Published:2020-09-20 Online:2020-03-03
Supported by:
National Natural Science Foundation of China(21972170);National Natural Science Foundation of China(21902187);Natural Science Foundation of Hubei Province of China(2018CFB365)

摘要/Abstract

摘要：

多级孔硅铝材料因优异的性能而成为金属催化剂的重要载体。研究采用水热法以硝酸铝为铝源、正硅酸乙酯(TEOS)为硅源合成了Al掺杂SiO₂(Al-SiO₂)的多级孔材料, 然后采用等体积浸渍法负载钴, 制备了具有多级孔结构的 Co/Al-SiO₂催化剂。对Al-SiO₂材料的表征结果表明: 以四丙基氢氧化铵(TPAOH)为结构导向剂, 经80 ℃水热处理可以合成多级孔Al-SiO₂, 呈尺寸在30~40 nm范围的 “蠕虫状”大孔分布形态。将催化剂用于费-托合成反应, 与商业SiO₂负载的钴催化剂相比, Co/Al-SiO₂的CO转化率提高近一倍, CH₄选择性降低19.3wt%, C₂-C₄选择性降低13.3wt%, 汽油段产物(C₅-C₁₂)选择性达到53.3wt%。

关键词: 水热法, 多级孔材料, Al-SiO₂, 钴催化剂, 费-托合成

Abstract:

Hierarchically porous silica-aluminum is an important support material for metal-catalysts, because of its excellent properties. Herein, an efficient hydrothermal approach for the production of hierarchical aluminum- doped silica (Al-SiO₂) architectures was reported by employing aluminum nitrate as an aluminium source and TEOS as silicon source. Effects of the structure-oriented agent on the structure of Al-SiO₂ were investigated. Structural features of Al-SiO₂ were characterized by XRD, SEM and N₂-physisorption. The results showed that hierarchical Al-SiO₂ with "worm-like" porous of 30-40 nm can be synthesized by using TPAOH as the structure-oriented agent and hydrothermal treatment at 80 ℃. The cobalt catalysts were prepared by the wetness impregnation method. Compared with commercial SiO₂ supported cobalt catalysts, the Fischer-Tropsch synthesis performance of the catalyst Co/Al-SiO₂ is significantly enhanced, i.e., CO conversion nearly doubled, CH₄ selectivity reduced by 19.3wt%, C₂-C₄ selectivity reduced by 13.3wt%, and the selectivity of gasoline products (C₅-C₁₂) reached 53.3wt%.

Key words: hydrothermal method, hierarchical porous materials, Al-SiO₂, Cobalt catalyst, Fischer-Tropsch synthesis

中图分类号:

O643

王举汉,文雄,刘成超,张煜华,赵燕熹,李金林. 多级孔Co/Al-SiO₂催化剂制备及其费-托合成催化性能[J]. 无机材料学报, 2020, 35(9): 999-1004.

WANG Juhan,WEN Xiong,LIU Chengchao,ZHANG Yuhua,ZHAO Yanxi,LI Jinlin. Preparation and Fischer-Tropsch Synthesis Performance of Hierarchical Co/Al-SiO₂ Catalyst[J]. Journal of Inorganic Materials, 2020, 35(9): 999-1004.

图/表 7

图1 Al-SiO2样品的SEM照片(A)和XRD图谱(B)

Fig. 1 SEM images (A) and XRD patterns(B) of Al-SiO2

图2 Al-SiO2样品的SEM照片(A)和XRD图谱(B)

Fig. 2 SEM images (A) and XRD patterns (B) of Al-SiO2 samples

图3 Al-SiO2样品的N2吸附-脱附曲线及孔径分布图

Fig. 3 N2 adsorption-desorption curves and pore size distributions of Si-Al samples (a) Al-SiO2(t-80); (b) Al-SiO2(100); (c) Al-SiO2(120); (d) Al-SiO2(140)

表1 样品的孔结构参数

Table 1 Pore structure parameters of samples

Sample	S_BET/(m²·g^-1)	V_pore/(cm³·g^-1)	D*/nm
Al-SiO₂(t-80)	79.1	0.45	22.8
Al-SiO₂(100)	67.1	0.65	38.5
Al-SiO₂(120)	49.1	0.55	44.5
Al-SiO₂(140)	304.7	0.18	2.4

图4 催化剂的XRD图谱(A)和TEM图(B)

Fig. 4 XRD patterns (A) and TEM images (B) of different catalysts

图5 催化剂的H2-TPR图(A)和活性随时间的变化曲线(B)

Fig. 5 H2-TPR(A) and TOS(B) profiles of different catalyst

表2 催化剂的费-托合成反应活性和选择性数据

Table 2 Activity and selectivity data of catalysts for Fischer-Tropsch synthesis

Catalyst	Load/%^a	CO con./%	Sel/wt%
Catalyst	Load/%^a	CO con./%	CH₄	C₂-C₄	C₅-C₁₂	C₁₂₊
Co/SiO₂	14.1	10.1	15.0	16.5	49.5	19.0
Co/Al-SiO₂(t-80)	14.6	21.4	12.1	14.3	53.3	17.3

参考文献 21

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多级孔Co/Al-SiO₂催化剂制备及其费-托合成催化性能

Preparation and Fischer-Tropsch Synthesis Performance of Hierarchical Co/Al-SiO₂ Catalyst

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