化工进展 ›› 2017, Vol. 36 ›› Issue (11): 4072-4079.DOI: 10.16085/j.issn.1000-6613.2017-0356

• 工业催化 • 上一篇    下一篇

活性炭负载磷钨酸催化剂的制备及其催化氧化脱硫性能

侯影飞1, 李力军1, 蒋驰1, 郭宁1,2, 牛青山1   

  1. 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
  • 收稿日期:2017-03-07 修回日期:2017-06-17 出版日期:2017-11-05 发布日期:2017-11-05
  • 通讯作者: 侯影飞(1977-),男,博士,副教授,从事石油与天然气加工、膜分离、油田化学品等研究。
  • 作者简介:侯影飞(1977-),男,博士,副教授,从事石油与天然气加工、膜分离、油田化学品等研究。E-mail:houyf@upc.edu.cn。
  • 基金资助:
    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)及山东省自然科学基金(ZR2012BL15)项目。

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

HOU Yingfei1, LI Lijun1, JIANG Chi1, GUO Ning1,2, NIU Qingshan1   

  1. 1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum(East China), Qingdao 266580, Shandong, China;
    2. College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, Shandong, China
  • Received:2017-03-07 Revised:2017-06-17 Online:2017-11-05 Published:2017-11-05

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),H2O2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、H2O2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(H2O2)/n(S)=12,催化剂用量0.05g/mL,乳化剂用量0.004g/mL。该反应条件下DBT被氧化为二苯并噻吩砜(DBTO2),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。

关键词: 模拟油, HPW/AC催化剂, 氧化脱硫, 过氧化氢

Abstract: 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 of 800μg/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 of 45% HNO3 at HPW loading amount of 30% had the best performance in the ODS. The optimum reaction conditions were determined as oxidative temperature at 80℃,the molar ratio of oxidant to sulfur of 12,and the dosage of catalyst and CTAB of 0.05g/mL and 0.004g/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 of 1,the model fuel could achieve a sulfur removal rate as high as 90.4%. 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.

Key words: model fuel, phosphotungstic acid/activated carbon catalyst, oxidative desulfurization, hydrogen peroxide

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