制备条件对CoMo/MCM-41-γ-Al_2O_3催化剂烯烃异构/加氢脱硫性能的影响  

Effect of preparation conditions on the performance of CoMo/MCM-41-γ-Al_2O_3 Catalysts for FCC Gasoline isomerization or hydrodesulfurization

作　　者：杨兰[1] 李竞周[1] 梁乃森[1] 段艳[1] 侯凯湖[1] 

机构地区：[1]河北工业大学绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《东北石油大学学报》2013年第4期67-74,122,共9页Journal of Northeast Petroleum University

基　　金：河北省自然科学基金项目(B2010000036)

摘　　要：采用静态混晶法制备MCM-41/γ-Al2O3复合载体,并利用XRD、BET及Py-IR等方法对复合载体进行表征;以模型石脑油为原料,在固定床反应装置上评价以MCM-41/γ-Al2O3为载体的CoMo负载型催化剂的烯烃异构和加氢脱硫活性,考察制备过程中γ-Al2O3水和温度、模板剂用量、晶化温度、晶化时间等对复合载体中MCM-41结晶度及催化剂性能的影响.结果表明:当γ-Al2O3水合温度为135℃、晶化温度为125℃、晶化时间为24h、投料摩尔比为n(γ-Al2O3)∶n(SiO2)∶n(NaOH)∶n(CTAB)(十六烷基三甲基溴化铵)∶n(H2O)=0.06∶1.0∶0.3∶0.15∶90时,所得MCM-41/γ-Al2O3复合载体具有规整有序的介孔孔道、较大的比表面积(750m2/g)和比孔容(0.55cm3/g)及较窄的孔径分布(2~3nm),对应的CoMo/MCM-41-γ-Al2O3催化剂具有较优异的催化性能.磷(P)改性可有效增加载体的酸量和调节载体的酸分布;载体1%P(质量分数)改性可改善催化剂的异构和加氢脱硫性能.在温度为265℃、压力为1.5MPa、氢油体积比为300、空速为2h-1时,模拟原料油的异构化率、脱硫率分别为76.5%、96.5%.The MCM-41/γ-Al2O3composite supporters were prepared by the static mixed crystallization method,and were characterized by means of XRD,BET and Py-IR.The isomerization and HDS performance of the CoMo catalysts supported on the synthesized composites were evaluated in a fixedbed reactor with modeling naphtha used as the feed.The effects of hydration temperature ofγ-Al2O3,template amount,crystallization temperature and time on crystallinity of MCM-41in the composite were examined.The results indicate that under the conditions ofγ-Al2O3hydration temperature 135℃,crystallization temperature 125℃,crystallization time 24hand the molar ratios of n(γ-Al2O3)∶n(SiO2)∶n(NaOH)∶n(CTAB)∶n(H2O)=0.06∶1.0∶0.3∶0.15∶90,the mixed crystal composite support MCM-41/γ-Al2O3has ordered mesoporous pores,a high specific surface area of 750m2/g,a high specific pore volume of 0.55cm3/g and a narrow pore distribution of 2~3nm.The support modification with phosphorus could effectively increase its acid amount,and adjust its acid distribution,and the isomerization and HDS performance of the catalyst supported the support modified with 1% p was improved.At the reaction conditions of 265 ℃,1.5MPa,LHSV 4h-1 and H2/Oil volume ratio 300,isomerization rate and desulfurization rate of the modeling feed were 76.5%and 96.5%.

关 键 词：MCM-41/γ-Al2O3复合材料 异构 加氢脱硫 催化剂 

分 类 号：TE55[石油与天然气工程—油气田开发工程]