TiO2-Al2O3复合载体的制备及Co-Mo/TiO2-Al2O3催化剂加氢脱硫性能的研究

王广建; 李佳佳; 吴春泽; 王芳

TiO₂-Al₂O₃复合载体的制备及Co-Mo/TiO₂-Al₂O₃催化剂加氢脱硫性能的研究

青岛科技大学化工学院, 山东青岛 266042

基金项目:

国家自然科学基金 2127613007，21506107

山东省自然科学基金 ZR2014BP009

详细信息

中图分类号: O643
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出版历程
- 收稿日期: 2016-07-01
- 修回日期: 2016-08-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-12-10

Study on the preparation of TiO₂-Al₂O₃ composite support and its application in Co-Mo/TiO₂-Al₂O₃ catalyst for hydro-desulfurization

Chemical Engineering Institute, Qingdao University of Science & Technology, Qingdao 266042, China

More Information

Corresponding author: Tel: 0532-85883839， guangjianwang@126.com

摘要

摘要: 通过改进的溶胶-凝胶法（SG）、共沉淀法（CP）、表面沉淀法（PR）及混捏法（ME）制备TiO₂-Al₂O₃复合载体，考察了不同制备方法对复合载体物理性质的影响。采用浸渍法制备Co-Mo/TiO₂-Al₂O₃-X加氢脱硫催化剂，研究了Co-Mo/TiO₂-Al₂O₃-X加氢脱硫催化剂的脱硫性能。利用XRD、BET、SEM等表征手段对复合载体及催化剂进行表征分析。结果表明，SG法制备的复合载体粒径均一，具有较大的比表面积、孔径和孔体积；CP法制备复合载体时TiO₂以单层或亚单层的分散状态高度分散于γ-Al₂O₃中。在氢气压力3.0 MPa、反应温度280℃、反应时间4 h、液时空速1.4 h^-1和氢油比600的条件下，SG法制备的Co-Mo/TiO₂-Al₂O₃催化剂具有较高加氢脱硫活性，噻吩转化率达到96.6%。
- TiO₂-Al₂O₃复合载体 /
- 加氢脱硫 /
- 溶胶-凝胶法 /
- Co-Mo催化剂
Abstract: A variety of TiO₂-Al₂O₃ composite support were prepared using improved sol-gel method (SG), co-precipitation method (CP), surface precipitation (PR) and mechanical kneading method (ME), and the influence of preparation methods on their physical properties were investigated. The hydro-desulfurization activity of Co-Mo/TiO₂-Al₂O₃-X catalysts prepared by impregnation method was studied. XRD, BET and SEM were used to characterize the composite support and the catalysts. Results show that the composite support prepared by SG method has uniform morphology with larger surface area, pore size and pore volume. And the monolayer or sub-monolayer of TiO₂ existed in the γ-Al₂O₃. Under the reaction conditions of 3.0 MPa of hydrogen pressure, 280℃ of reaction temperature, 4 h of reaction time, 1.4 h^-1 of the liquid space velocity and 600 of hydrogen to oil ratio, Co-Mo/TiO₂-Al₂O₃ prepared by SG method has highest hydro-desulfurization activity, and the thiophene conversion rate reached 96.6%.
- TiO₂-Al₂O₃composite support /
- hydro-desulfurization /
- sol-gel method /
- Co-Mo catalyst

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图 1 载体的XRD谱图

Figure 1 XRD patterns of TA support

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图 2 催化剂的XRD谱图

Figure 2 XRD spectra of TA catalysts

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图 3 不同复合载体的N₂吸附-脱附等温线

Figure 3 N₂ adsorption-desorption isotherms of TiO₂-Al₂O₃ composite support prepared with different mothods

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图 4 不同复合载体的BJH孔径分布

Figure 4 BJH pore distributions of TiO₂-Al₂O₃ composite support prepared with different mothods

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图 5 复合载体的SEM照片

Figure 5 SEM images of TiO₂-Al₂O₃ composite support

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表 1 复合载体的物理性质

Table 1 Physical properties of TA support

Sample	A_BET/ (m²·g^-1)	BJH pore volume v/ (cm³·g^-1)	Average pore size d/nm
Al₂O₃	296	0.80	8.01
TiO₂	145	0.38	4.40
TA-ME	169	0.63	11.34
TA-SG	242	0.88	12.24
TA-PR	180	0.71	11.89
TA-CP	291	0.26	3.08

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表 2 载体制备方法对Co-Mo/TiO₂-Al₂O₃催化剂HDS活性的影响

Table 2 Effect of preparation methods of the support on the activity of the Co-Mo/TiO₂-Al₂O₃ catalyst for HDS

Catalyst	TiO₂ w/%	Thiophene conversion x/%
Co-Mo/TiO₂-Al₂O₃-SG	30	96.6
Co-Mo/TiO₂-Al₂O₃-CP	30	94.4
Co-Mo/TiO₂-Al₂O₃-PR	30	90.4
Co-Mo/TiO₂-Al₂O₃-ME	30	83.5

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