活性炭负载磷钨酸催化剂的制备及其催化氧化脱硫性能  

Preparation and performance of phosphotungstic acid/activated carbon catalyst for catalytic oxidative desulfurization

作　　者：侯影飞[1] 李力军 蒋驰 郭宁[1,2] 牛青山 HOU Yingfei;LI Lijun;JIANG Chi;GUO Ning;NIU Qingshan(State Key Laboratory of Heavy Oil Processing,College of Chemical Engineering,China University of Petroleum (East China),Qingdao 266580,Shandong,China;College of Chemistry and Chemical Engineering,Ocean University of China,Qingdao 266100,Shandong,China)

机构地区：[1]中国石油大学(华东)化学工程学院,重质油国家重点实验室,山东青岛266580 [2]中国海洋大学化学化工学院,山东青岛266100

出　　处：《化工进展》2017年第11期4072-4079,共8页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(51173203);中央高校基本科研业务费专项资金(15CX05014A);山东省自然科学基金(ZR2012BL15)

摘　　要：以活性炭(AC)为载体,磷钨酸(HPW)为活性组分,通过等体积浸渍法制备HPW/AC催化剂,并以二苯并噻吩(DBT)的正十二烷溶液为模拟油(硫含量为800μg/g),H_2O_2为氧化剂,探究催化剂的催化氧化脱硫性能。采用BET、SEM和XRD表征手段对催化剂的结构进行分析。考察了反应温度、反应时间、H_2O_2用量、催化剂用量、乳化剂用量以及模拟油的组成对催化剂催化氧化脱硫效果的影响,最后考察了催化剂的循环使用性能。结果表明,AC经质量分数45%硝酸溶液80℃下活化2h,活性组分HPW的负载质量分数为30%时,所制备的HPW/AC催化剂的氧化脱硫性能最好;最佳反应条件为反应温度80℃,反应时间80min,氧化剂/硫摩尔比n(H_2O_2)/n(S)=12,催化剂用量0.05g/m L,乳化剂用量0.004g/m L。该反应条件下DBT被氧化为二苯并噻吩砜(DBTO_2),用N-甲基吡咯烷酮(NMP)进行萃取,萃取比为1,模拟油的氧化脱硫率达到90.4%。芳香族化合物和烯烃对氧化脱硫效果起到抑制作用,烯烃的影响最为显著,并且催化剂具有良好的稳定性。The HPW/AC catalyst was prepared by the incipient wetness impregnation method with activated carbon and phosphotungstic acid(HPW)as the support and active component respectively.The model fuel was prepared by dissolving dibenzothiophene(DBT)into n-dodecane yielding a sulfur concentration of800μg/g,for which HPW/AC was investigated with hydrogen peroxide(H2O2)as oxidant.HPW/AC was characterized by the means of BET,SEM and XRD.The effects of oxidative temperature,reaction time,the mount of H2O2,the dosage of catalyst and CTAB on the performance of HPW/AC for the oxidative desulfurization(ODS)were also investigated.The reusability of HPW/AC was explored as well.The results showed that HPW/AC with activation of45%HNO3at HPW loading amount of30%had the best performance in the ODS.The optimum reaction conditions were determined as oxidative temperature at80℃,the molar ratio of oxidant to sulfur of12,and the dosage of catalyst and CTAB of0.05g/mL and0.004g/mL in the model fuel,under which DBT was substantially converted to dibenzothiophene sulfone(DBTO2).After extracted by N-methyl pyrrolidone(NMP)with a volumetric ratio of1,the model fuel could achieve a sulfur removal rate as high as90.4%.The presence of aromatic compounds and alkenes inhibited the ODS of DBT,and the inhibiting effect caused by alkenes was more significant.The catalyst could be regenerated as well.

关 键 词：模拟油 HPW/AC催化剂 氧化脱硫 过氧化氢 

分 类 号：TE624[石油与天然气工程—油气加工工程]