还原温度对低温还原法制备的Ni2 P/Ti-MCM-41催化剂加氢脱硫性能的影响  

Effect of reduction temperature on the performance of Ni_2P/Ti-MCM-41 catalyst in hydrodesulfurization

作　　者：于祺[1] 宋华[1,2] 宋华林[3] 王健[1] 姜楠[1] 李锋[1,2] 陈彦广[1,2] 

机构地区：[1]东北石油大学化学化工学院,黑龙江大庆163318 [2]东北石油大学石油与天然气化工省重点实验室,黑龙江大庆163318 [3]牡丹江医学院医学影像学院,黑龙江牡丹江157011

出　　处：《燃料化学学报》2016年第8期970-976,共7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);黑龙江省教育厅面上项目(12541060);东北石油大学研究生创新科研项目(YJSCX2016-019NEPU)资助~~

摘　　要：以氯化镍(Ni Cl_2·6H_2O)为镍源、次磷酸铵(NH_4H_2PO_2)为磷源、Ti-MCM-41为载体,通过程序升温还原法制备了Ni_2P/Ti-M CM-41催化剂,并采用H_2-TPR、XRD、BET、XPS、TEM等手段对其结构和性质进行了表征。以二苯并噻吩(DBT)为模型化合物,考察了还原温度对Ni_2P/Ti-M CM-41催化剂的加氢脱硫(HDS)性能的影响。结果表明,程序升温还原法制备的Ni_2P/Ti-M CM-41催化剂前驱体的还原温度为318℃,比传统程序升温还原制备的Ni_2P低200℃。在350-500℃下还原得到的催化剂活性相为单一的Ni_2P相,较低的还原温度有利于形成更小粒径的磷化镍晶粒。还原温度为400℃时,制得的Ni_2P/Ti-M CM-41催化剂比表面积高、分散性最好、表面P富集少,具有最高的HDS活性;在340℃、3.0 M Pa、H_2/油体积比500、质量空速(WHSV)为2.0 h^(-1)的条件下,二苯并噻吩HDS转化率达到99.4%。The supported Ni2 P/Ti-MCM-41 catalyst is prepared by temperature-programmed reduction method with nickel chloride （NiCl2·6H2O） as the nickel precursor, ammonium hypophosphite （NH4H2PO2） as the phosphorus precursor and Ti-MCM-41 as the support. The Ni2 P/Ti-MCM-41 catalyst was characterized by H2-TPR, XRD, BET, XPS, and TEM; the effect of reduction temperature on its catalytic performance in hydrodesulfurization （HDS） was investigated by using dibenzothiophene （DBT） as a model compound. The results show that the precursors on the catalyst prepared in this way can be reduced at 318℃, which is at least 200℃ lower than that prepared by traditional methods. Pure Ni2 P phase can be obtained by reduction at 350-500℃;the low reduction temperature is in favor of forming small Ni2 P crystallite size. The Ni2 P/Ti-MCM-41 catalyst obtained at a reduction temperature of 400 ℃ exhibits the highest surface area, the best dispersion of Ni2 P crystallite size, the lowest surface phosphorus content and the highest HDS activity; under 340 ℃, 3. 0 MPa, a H2/oil ratio of 500 （ volume ratio） and a weight hourly space velocity （ WHSV） of 2. 0 h-1 , the conversion of DBT for HDS reaches 99 . 4%.

关 键 词：加氢脱硫 磷化镍 还原温度 TI-MCM-41 二苯并噻吩 

分 类 号：O643.361[理学—物理化学]