活性炭负载磷钨酸催化剂的制备及其催化氧化脱硫性能

doi:10.16085/j.issn.1000-6613.2017-0356

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

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. 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 Ning^1,2, NIU Qingshan¹

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/Abstract

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

中图分类号:

TE624

侯影飞, 李力军, 蒋驰, 郭宁, 牛青山. 活性炭负载磷钨酸催化剂的制备及其催化氧化脱硫性能[J]. 化工进展, 2017, 36(11): 4072-4079.

HOU Yingfei, LI Lijun, JIANG Chi, GUO Ning, NIU Qingshan. Preparation and performance of phosphotungstic acid/activated carbon catalyst for catalytic oxidative desulfurization[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4072-4079.

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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

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