Ni晶粒粒径对Ni/SiO<sub>2</sub>催化月桂酸甲酯脱氧制烃性能的影响

韩蒙蒙; 代吉才; 陈吉祥

Ni晶粒粒径对Ni/SiO₂催化月桂酸甲酯脱氧制烃性能的影响

1.
天津大学化工学院催化科学与工程系天津市应用催化科学与工程重点实验室, 天津 300072;
2.
河北泊头职业学院, 河北泊头 062150

基金项目: 国家自然科学基金（21176177）；天津市自然科学基金（12JCYBJC13200）。

详细信息

通讯作者:
陈吉祥，Tel：（022）27890865，Fax：（022）87894301，E-mail：jxchen@tju.edu.cn。

中图分类号: O643
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出版历程
- 收稿日期: 2014-01-10
- 修回日期: 2014-05-01
- 刊出日期: 2014-08-30

Influence of Ni crystallite size on deoxygenation of methyl laurate to hydrocarbons over Ni/SiO₂ catalyst

1.
Tianjin Key Laboratory of Applied Catalysis Science and Technology, Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2.
Hebei Botou Vocational College, Botou 062150, China

摘要

摘要: 采用等体积浸渍-干燥-还原法及等体积浸渍-干燥-焙烧-还原法制备了3种具有不同Ni晶粒粒径的Ni/SiO₂催化剂，利用H₂-TPR、XRD、TEM、H₂-TPR、NH₃-TPD及TGA技术对其及前驱体进行了表征，并在固定床反应器上评价了其催化月桂酸甲酯脱氧制十一烷（C₁₁）和十二烷（C₁₂）的性能，分析了Ni晶粒粒径对其脱氧性能的影响。结果表明，采用等体积浸渍-干燥-还原法制备的催化剂中Ni晶粒粒径较小，提高还原温度可以促进Ni晶粒长大。随Ni晶粒粒径增大，月桂酸甲酯的转换频率提高，而C₁₁和C₁₂总选择性、C₁₁/C₁₂物质的量比及裂解产物选择性降低，Ni/SiO₂催化剂上月桂酸甲酯脱氧为结构敏感反应。此外，还考察了重时空速对Ni/SiO₂催化剂脱氧性能的影响，随重时空速提高，月桂酸甲酯转化率、C₁₁和C₁₂总选择性、C₁₁/C₁₂物质的量比及裂化产物选择性降低。月桂酸甲酯通过脱羰/脱羧反应路径生成的CO/CO₂几乎全部加氢转化为CH₄，表明Ni/SiO₂催化剂具有很高的甲烷化活性。研究还发现，较小Ni晶粒烧结、有机物种吸附及积炭会导致催化剂失活。
- Ni晶粒粒径 /
- 月桂酸甲酯 /
- 加氢脱氧 /
- 脱羰/脱羧 /
- 结构敏感
Abstract: Three Ni/SiO₂ catalysts with different Ni crystallite sizes were prepared by the incipient wetness impregnation-drying-reduction and incipient wetness impregnation-drying-calcination-reduction methods. The catalysts were characterized by H₂-TPR, XRD, TEM, H₂ chemisorption, NH₃-TPD and TGA techniques. Their catalytic performances in the deoxygenation of methyl laurate to undecane (C₁₁) and dodecane (C₁₂) were evaluated in a fixed bed reactor. The effects of Ni crystallite size on the catalyst structure and performance were investigated. It was found that the impregnation-drying-reduction method gave smaller Ni crystallite size, and the high reduction temperature promoted the growth of Ni crystallite. With the increase of the Ni crystallite size, the turnover frequency of methyl laurate increased, while the total selectivity to C₁₁ and C₁₂ (s_C₁1+C₁₂), C₁₁/C₁₂ mol ratio and the selectivity to cracking products decreased. We suggest that the deoxygenation of methyl laurate on Ni/SiO₂ is structurally sensitive. The effects of weight hourly space velocity (WHSV) on performance of Ni/SiO₂ were also investigated. As WHSV increased, the methyl laruate conversion, s_C₁1+C₁₂, C₁₁/C₁₂ mol ratio and the selectivity to cracking products decreased. In addition, CO and CO₂ generated from the decarbonylation/decarboxylation pathway were converted to CH₄, indicating that Ni/SiO₂ had high activity for methanation. It was also found that the sintering of small Ni crystallites, the adsorption of organic compounds and carbon deposit led to catalyst deactivation.
- Ni crystallite size /
- methyl laurate /
- hydrodeoxygenation /
- decarbonylation/decarboxylation /
- structure sensitivity

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