高比表面积等级孔γ-Al2O3的金属醇酯一步水解法制备及性能

doi:10.7503/cjcu20200076

摘要/Abstract

摘要：

采用金属醇酯一步水解法, 在不同含水有机溶剂反应介质中在常温条件下制备了具有特殊形貌及等级孔道结构的超高比表面积γ-Al₂O₃材料. X射线衍射(XRD)、 N₂吸附-脱附、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征结果证明, 通过调节反应介质中水含量和溶剂类型可以精确控制仲丁醇铝的水解缩合反应过程和副产物醇分子的扩散行为, 进而优化产物的孔道结构. 研究结果表明, 在水/乙腈体系下制备的γ-Al₂O₃材料整体呈现出由大孔直孔道和三维介孔孔道构成的等级孔道结构, 且随着水含量的增加, 大孔孔壁依次出现光滑状、片状和褶皱状的特定形貌; 在饱和水的丁醇溶液体系下制备的材料则展现出由厚度约为10 nm的片状γ-Al₂O₃堆积而成的三维介孔结构, 比表面积高达517 m ²/g. 选取水含量为3 mL的水/乙腈体系下的大孔-介孔γ-Al₂O₃材料作为载体制备负载型Pt基催化剂. 负载后载体等级孔结构基本保持完好, 金属Pt纳米颗粒均匀分散在载体上, 该催化剂在渣油脱金属催化反应中的脱金属性能比商用薄水铝石为载体制备Pt基催化剂更加优异. 脱Ni率和脱V率分别提高11.62%和10.83%.

关键词: 金属醇酯一步水解, 等级孔结构, 催化剂, 渣油加氢, 脱金属

Abstract:

Ultrahigh-surface-area γ-Al₂O₃ materials with special morphologies and hierarchically porous structures were prepared at room temperature by one-step hydrolysis of metal alkoxide under different aqueous organic solvents systems. With the aid of X-ray diffraction(XRD), N₂ adsorption-desorption, scanning electronic microscopy(SEM) and transmission electron microscope(TEM), it was proved that the hydrolysis and condensation process of aluminum tri-sec-butoxide and the diffusion behavior of by-product alcohol molecules could be precisely controlled by the water content and the type of solvent, thereby the product structure were optimized in return. The results show that the γ-Al₂O₃ material with straight macroporous wall and 3D-mesporous was obtained under the water/acetonitrile system, meanwhile, the smooth, flaky and wrinkled morphologies appeared in the macroporous wall in turn as the water content increased. However, only 3D-mesporous structure stacked with 10 nm-thick flaky γ-Al₂O₃ could be observed for the material prepared under the saturated butanol solution system with the specific surface area of up to 517 m ²/g. Besides, the macro-mesoporous γ-Al₂O₃ material prepared under the 3 mL water content in the water/acetonitrile system was selected as the carrier for Pt-based catalyst. The carrier structure basically remained intact after the loading process and metal Pt nanoparticles were uniformly dispersed on the carrier. The hierarchical γ-Al₂O₃ supported Pt-based catalyst showed better hydrodemetallization performance than the commercial boehmite supported catalyst, and the Ni and V removal rate increased by 11.62% and 10.83%, respectively.

Key words: One-step hydrolysis of metal alkoxide, Hierarchically porous structure, Catalyst, Residual oil hydrogenation, Demetallization

中图分类号:

O643
O611

TrendMD:

刘思明, 汪建南, 余申, 刘湛, 王朝, 李小云, 陈丽华, 苏宝连. 高比表面积等级孔γ-Al₂O₃的金属醇酯一步水解法制备及性能. 高等学校化学学报, 2020, 41(6): 1208.

LIU Siming, WANG Jiannan, YU Shen, LIU Zhan, WANG Zhao, LI Xiaoyun, CHEN Lihua, SU Baolian. Preparation of High-surface-area Hierarchically Porous γ-Al₂O₃ by One-step Hydrolysis of Metal Alkoxide and Performance ^†. Chem. J. Chinese Universities, 2020, 41(6): 1208.

图/表 12

Fig.1 XRD patterns of precursor materials prepared under different water content in the H2O/C2H3N(A) and H2O/C4H9OH(B) systems

Fig.2 SEM images of precursor materials prepared under different water content in the H2O/C2H3N systems (A) 0—1 mL H2O; (B) 2 mL H2O; (C) 3—4 mL H2O; (D) >4 mL H2O.

Fig.3 SEM images of precursor materials prepared in C4H9OH(A, B) and H2O/C4H9OH(C, D) systems

Fig.4 XRD patterns of calcined materials prepared in the H2O/C2H3N(A) and H2O/C4H9OH(B) systems with optimal water content

Fig.5 SEM(A, B, D, E) and TEM(C, F) images of calcined samples prepared under H2O/C2H3N(A, B, C) and H2O/C4H9OH(D, E, F) systems Insets of (C) and (F) are HRTEM.

Fig.6 N2 adsorption-desorption isotherms(A—D) and pore size distributions(insets) of calcined samples prepared under different systems (A) C2H2N; (B) H2O/CH2N; (C) C4H9OH; (D) H2O/C4H9OH.

Table 1 Textual properties of samples under different systems

System	S_BET/(m²·g^-1)	Mesopore size/nm	Total pore volume/(cm³·g^-1)
C₂H₃N	462	——	0.05
H₂O/C₂H₃N	381	9	0.75
C₄H₁₀O	305	——	0.11
H₂O/C₄H₉OH	517	12	1.66
SB-C	213	6	0.68

Fig.7 XRD patterns of γ-Al2O3 and supported Pt/γ-Al2O3 materials

Fig.8 SEM images(A—C), STEM-HAADF image(D) and corresponding EDX elemental maps of Al(E), O(F) and Pt(G) and metal particle size distributions(H) of Pt/γ-Al2O3

Fig.9 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of Pt/γ-Al2O3 material

Table 2 Textual properties of Pt/γ-Al2O3 samples before and after loaded

Sample	S_BET/( m²·g^-1)	Mesopore size/nm	Total pore volume/(cm³·g^-1)
γ-Al₂O₃	381	9	0.75
1.0% Pt/γ-Al₂O₃	309	6	0.50

Table 3 Comparison of properties between Pt/γ-Al2O3 and Pt/SB-C

Sample	Ni removal rate(%)	V removal rate(%)
1.0% Pt/SB-C	24.65	71.48
1.0% Pt/γ-Al₂O₃	36.27	82.31

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高比表面积等级孔γ-Al₂O₃的金属醇酯一步水解法制备及性能

Preparation of High-surface-area Hierarchically Porous γ-Al₂O₃ by One-step Hydrolysis of Metal Alkoxide and Performance ^†

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