钇和柠檬酸对非负载磷化镍催化剂加氢脱硫性能的影响  

Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide

作　　者：宋华[1,2] 于祺[1] 徐晓伟[1,3] 宋华林[4] 姜楠[1] 李锋[1] 陈彦广[1] 

机构地区：[1]东北石油大学化学化工学院 [2]东北石油大学石油与天然气化工省重点实验室,大庆163318 [3]山东玉皇化工有限公司技术与研发中心,菏泽274500 [4]牡丹江医学院黑龙江省高校肿瘤疾病防治重点实验室,牡丹江157011

出　　处：《高等学校化学学报》2016年第8期1528-1534,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21276048);黑龙江省教育厅面上项目(批准号:12541060);东北石油大学研究生创新科研项目(批准号:YJSCX2016-019NEPU)资助~~

摘　　要：采用传统程序升温(TPR)法制备了稀土金属钇(Y)或柠檬酸(CA)改性及Y和CA同时改性的非负载型Ni2P催化剂;采用X射线衍射(XRD)分析、N2吸附比表面积(BET)测定、CO化学吸附分析、X射线光电子能谱(XPS)和透射电子显微镜(TEM)对催化剂的结构和性质进行了表征;并考察了Y和CA对催化剂上进行的二苯并噻吩(DBT)加氢脱硫(HDS)反应性能的影响.结果表明,Y和CA均可促使非晶相NixPyOz向磷化镍活性相的转化,抑制Ni_5P_4杂晶相的形成,从而促进Ni2P活性相的生成;同时能够丰富催化剂的孔道,抑制催化剂表面磷的富集,得到更好的孔结构、更高的活性相分散度.Y或CA以及两者同时改性后的催化剂DBT转化率均明显高于Ni-P催化剂.各催化剂的HDS活性大小顺序为Y-Ni-P-CA>Ni-P-CA>Y-Ni-P>Ni-P.在340℃,3.0 MPa,氢油体积比700,质量空速(WHSV)1.5 h-1的条件下,Y-Ni-P-CA催化剂的DBT转化率为97%,比Ni-P催化剂提高了约35%.The Yttrium（ Y）,citric acid（ CA） and combined Y and CA modified bulk nickel phosphide（ Ni-P） catalysts were prepared by temperature programmed reduction（ TPR） method. The catalysts were characterized by means of X-ray diffraction（ XRD）,N2-adsorption specific surface area measurements（ BET）,CO chemisorption uptake measurements,X-ray photoelectron spectroscopy（ XPS） and transmission electron microscopy（ TEM）. The effects of Y and CA on catalyst activity for dibenzothiophene（ DBT） hydrodesulfurization（ HDS） were studied. The results indicated that both Y and CA can promote the transformation from NixPy Ozamorphous phase to nickel phosphide active phase,suppress the formation of Ni_5P_4 phase and therefore promote the formation of Ni2 P active phase. Addition of Y or CA can increase the surface area and suppress the enrichment of phosphorus on surface,leading to a smaller and highly dispersed active phase particles. The Y,CA and combined Y and CA modified nickel phosphide catalysts were proved to possess higher HDS activity than Ni-P sample. The DBT conversions of catalysts followed the order： Y-Ni-P-CA Ni-P-CA Y-Ni-P Ni-P. At the conditions of 340 ℃,3. 0 MPa,WHSV of 1. 5 h-1and H2/oil volume ratio of 700,the DBT conversion of the Y-Ni-P-CA catalyst reached 97%,which is an increase of 35% when compared with that found for bulk Ni-P sample.

关 键 词：加氢脱硫 磷化镍 钇 柠檬酸 二苯并噻吩 

分 类 号：O643.361[理学—物理化学] TQ426.95[理学—化学]