摘要
以廉价的三苯基膦(PPh3)为磷源,以三正辛胺(TOA)为液相反应体系,溶剂热法制备了负载型Ni2P/M CM-41催化剂,并采用XRD、BET、CO吸附、XPS和TEM等手段对制备得到的催化剂进行了表征。该方法的合成温度为330℃,反应在常压下进行,比程序升温还原法(H2-TPR)所需的还原温度至少低300℃,比传统的溶剂热法合成原料更廉价。以二苯并噻吩(DBT)为模型化合物,比较了所制备的Ni2P/M CM-41催化剂与H2-TPR法制备的催化剂结构以及加氢脱硫(HDS)性能。结果表明,溶剂热法能够降低催化剂表面上P物种的集聚,从而得到较大比表面积的Ni2P催化剂(690 m2/g);促进小尺寸、高度分散的Ni2P活性相的生成;制得的催化剂的HDS活性明显高于H2-TPR法催化剂,在反应温度340℃,质量空速2.0 h-1,H2/油=500(体积比),3.0 MPa的条件下,Ni2P/M41-R催化剂DBT转化率达到96.8%,较H2-TPR法高10.6%。
The supported Ni2 P / MCM-41 catalyst was prepared by a solvothermal method using triphenylphosphine（TPP） as a cheap phosphorus material and tri-n-octylamine（TOA） as the coordinating liquid reaction system. The catalysts were characterized by X-ray diffraction（XRD）,N2-adsorption,CO uptake,X-ray photoelectronspectroscopy（XPS） and transmission electron microscopy（TEM）. The solvothermal synthesis was performed at atmospheric pressure and 330 ℃,at least 300 ℃ lower than the temperature for preparing the corresponding catalysts by temperature-programmed reduction（H2-TPR） method. The structure and hydrodesulfurization（HDS） performance of the as-prepared Ni2 P / MCM-41 catalyst are compared with those prepared by H2-TPR,with dibenzothiophene（DBT）as a model compound. The results showed that the solvothermal method can decrease the aggregation of P species on the catalyst surface so as to achieve a Ni2 P catalyst with high surface area（690 m2/ g） and then promote the formation of small and highly dispersed Ni2 P active phase. The catalyst from solvothermal synthesis exhibits distinctly a superior HDS performance to that prepared by H2-TPR method. Under the conditions of 340 ℃,3. 0 MPa,a H2/oil volume ratio of 500（ volume ratio）,and a weight hourly space velocity（ WHSV） of 2. 0 h-1,the conversion of DBT reaches 96. 8% over the catalyst from solvothermal synthesis,which is 10. 6% higher than that over the catalyst prepared via H2-TPR.
出处
《燃料化学学报》
EI
CAS
CSCD
北大核心
2015年第6期714-719,共6页
Journal of Fuel Chemistry and Technology
基金
国家自然科学基金(21276048)
黑龙江省自然科学基金(ZD201201)
黑龙江省教育厅项目(12541060)
