硫化行为对Ni_2P/SBA-15催化剂结构和加氢脱硫性能的影响  

Influence of Sulfurization Behavior on Structure and Hydrodesulfurization Performance of Ni_2P/SBA-15 Catalysts

作　　者：高丽丽[1] 吴平易[1,2] 兰玲 关月明[1] 季生福[1] 

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]中国石油石油化工研究院,北京100195

出　　处：《石油学报（石油加工）》2013年第2期198-204,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展计划(2006CB202503);中国石油科技创新基金(2010D-5006-0401)项目资助

摘　　要：以介孔分子筛SBA-15为载体、硝酸镍为镍源、磷酸氢二铵为磷源,等体积浸渍法制备了Ni2P/SBA-15催化剂前驱体,然后在H2流中程序升温还原,得到Ni2P/SBA-15催化剂,再用CS2溶液对催化剂进行了硫化处理,制备出了硫化态xCS2-Ni2P/SBA-15催化剂。采用XRD、N2吸附-脱附、XPS对催化剂的结构进行了表征,对催化剂的二苯并噻吩加氢脱硫活性进行了评价,考察了硫化条件对催化剂结构和二苯并噻吩加氢脱硫催化活性的影响。结果表明,xCS2-Ni2P/SBA-15催化剂的物相有Ni2P、Ni12P5、Ni3S2,催化剂的比表面积随硫化溶液中CS2质量分数的增加有一定程度的增加,催化剂表面的Ni以Niδ+和Ni 2+形式存在,P以Pδ-和P5+形式存在。采用5%CS2硫化溶液硫化的催化剂对二苯并噻吩加氢脱硫具有最高的催化活性,380℃时二苯并噻吩的转化率可达99.3%。硫化过程形成的Ni3S2活性物相对二苯并噻吩的转化和直接脱硫都有利。A series of xCS2-Ni2P/SBA-15 catalysts were prepared with Ni（NO3）2 as Ni source, （NH4）2HPO4 as P source, SBA-15 as a support and CS2 as a sulfurization reagent. The structures of the catalysts were characterized by XRD, N2 adsorption-desorption and XPS. The hydrodesulfurization （HDS） activities of the catalysts were evaluated by using dibenzothiophene （DBT） as a model compound. The effects of the sulfurization condition on the structure and catalytic activity of the catalyst were investigated. The results indicated that the phases of Ni2P, Ni12P5 and Ni3S2 existed in xCS2-Ni2P/SBA-15 catalysts. BET surface area of xCS2-Ni2P/SBA-15 catalysts increased with the CS2 mass fraction in sulfurization solution. Ni existed in the Niδ＋ and Ni2＋ species and P existed in the P δ- and P 5＋ species on the catalyst surface. xCS2-Ni2P/SBA-15 catalyst sulfided with the solution of 5%CS2 exhibited the best catalytic performance for DBT HDS reaction, in which the conversion of DBT reached 99.3% at 380℃. Ni3S2 phase played an important role on DBT conversion and direct desulfurization.

关 键 词：NI2P SBA-15 CS2 二苯并噻吩 加氢脱硫 

分 类 号：O643.36[理学—物理化学]