磷钨酸/SBA-15催化氧化-萃取柴油脱硫

doi:10.16085/j.issn.1000-6613.2016.09.022

化工进展 ›› 2016, Vol. 35 ›› Issue (09): 2790-2795.DOI: 10.16085/j.issn.1000-6613.2016.09.022

磷钨酸/SBA-15催化氧化-萃取柴油脱硫

李瑞丽, 吕本震, 蒋善良, 李晶晶

中国石油大学(北京)重质油国家重点实验室, 北京 102249

收稿日期:2015-11-09 修回日期:2016-03-23 出版日期:2016-09-05 发布日期:2016-09-05
通讯作者: 李瑞丽(1965-),女,硕士,副研究员,从事清洁油品生产的教学与研究工作。E-mail:lrl4806@163.com。
作者简介:李瑞丽(1965-),女,硕士,副研究员,从事清洁油品生产的教学与研究工作。E-mail:lrl4806@163.com。

Diesel desulfurization by phosphotungstic acid/SBA-15 catalytic oxidation-extraction

LI Ruili, LV Benzhen, JIANG Shanliang, LI Jingjing

State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China

Received:2015-11-09 Revised:2016-03-23 Online:2016-09-05 Published:2016-09-05

摘要/Abstract

摘要： 以自制的SBA-15为载体，磷钨酸为活性组分，用过量浸渍法制备了HPW/SBA-15催化剂，并采用SEM、BET和TG-DTA对催化剂进行表征分析。H₂O₂为氧化剂，十六烷基三甲基溴化铵（CTAB）为相转移剂，以二苯并噻吩（DBT）的模型化合物（DBT为溶质、正辛烷为溶剂）进行氧化脱除为探针反应，考察了磷钨酸负载量和HPW/SBA-15的焙烧温度对催化剂活性的影响，同时考察了氧化-萃取工艺条件对真实柴油脱硫效果的影响。实验结果表明，磷钨酸最佳负载量为30%，HPW/SBA-15在250℃焙烧处理时活性最高；在n(H₂O₂)：n(S)=6、HPW/SBA-15用量为2.5%（基于柴油质量）、CTAB用量为0.4%（基于柴油质量）、萃取级数为4、温度60℃反应1.5h的条件下，柴油硫含量从1317mg/L降到39mg/L，脱硫率达到97.0%、收率不低于85.0%。气相色谱结果显示，该催化氧化脱硫体系容易脱除柴油中加氢难以脱除的二苯并噻吩及其衍生物。

关键词: SBA-15, 载体, 磷钨酸, 催化剂, 催化氧化, 萃取, 柴油, 脱硫

Abstract: A series of HPW/SBA-15 were prepared by supersaturated impregnation method with phosphotungstic acid loaded on SBA-15. The catalysts were characterized by means of BET,SEM and TG-DTA. The effects of HPW loading amount and calcination temperature on the desulfurization were investigated by studying the DBT desulfurization performance on the HPW/SBA-15 with H₂O₂ as oxidation and CTAB as phase transfer catalyst. Meanwhile,the effects of different oxidation-extraction conditions on diesel desulfurization were investigated. The results showed that the best mass percentage of HPW was 30% and HPW/SBA-15 showed the highest activity at 250℃. The sulfur content in the diesel oil decreased from 1317mg/L to 39mg/L and the sulfur removal rate reached 97.0% under the best condition of n(H₂O₂):n(S)=6,the mass percentage of HPW/SBA-15 of 2.5% that of CTAB of 0.4%(both based on the diesel oil),extraction stage of 4,reaction temperature of 60℃ and reaction time of 1.5h. According to GC analysis,the HPW/SBA-15 catalytic oxidation-extraction method could easily remove dibenzothiophene and its derivatives,which were quite inert in diesel during its hydrodesulfurization.

Key words: SBA-15, support, phosphotungstic acid, catalyst, catalytic oxidation, extraction, diesel, desulfurization

中图分类号:

TE626

李瑞丽, 吕本震, 蒋善良, 李晶晶. 磷钨酸/SBA-15催化氧化-萃取柴油脱硫[J]. 化工进展, 2016, 35(09): 2790-2795.

LI Ruili, LV Benzhen, JIANG Shanliang, LI Jingjing. Diesel desulfurization by phosphotungstic acid/SBA-15 catalytic oxidation-extraction[J]. Chemical Industry and Engineering Progree, 2016, 35(09): 2790-2795.

参考文献

[1] JOSE N,SENGUPTA S,BASU J K. Optimization of oxidative desulfurization of thiophene using Cu/titanium silicate-1 by boxbehnken design[J]. Fuel,2011,90:626-632.
[2] ALI M F,AL-MALKI A,EL-ALI B,et al. Dee desulphurization of gasoline and diesel fuels using non-hydrogen consuming techniques[J]. Fuel,2006,85:1354-1363.
[3] SATORU M,KAZUTAKA M,Kidena K,et al. A novel oxidative desulfurization system for diesel fuels with molecular oxygen in the presence of cobalt catalysts and aldehydes[J]. Energy Fuels,2004, 18:116-121
[4] 牟明仁,姜莉,张代华,等.车用柴油新标准的硫含量修订及其影响[J]. 沈阳师范大学学报(自然科学版),2013,31(4):523-526.
[5] MARKO M,KATICA S B,ZORAN G,et al. Study of diesel fuel desulfurization by adsorption[J]. Chem. Eng. Res. Des,2010,88:487-495.
[6] 张姝妍,曹祖宾,赵德智,等. 室温离子液体对FCC汽油络合萃取脱硫的研究[J]. 炼油技术与工程,2005,35(5):35-38.
[7] TANG X D,ZHANG Y F, LI J J, et al. Deep extractive desulfurization with areniumlon deep eutecticsolvents (DESs)[J]. Industrial & Engineering Chemistry Research,2015,54(16):4625-4632
[8] 张海燕,代跃利,蔡蕾. 杂多酸催化剂催化氧化脱硫研究进展[J]. 化工进展,2013,32(4):809-815
[9] 马荣华,刘春涛. 杂多配合物异构体[M]. 哈尔滨:哈尔滨工程大学出版社,2007:199-219.
[10] 李瑞丽,李波,张平. 磷钨酸/氧化锆催化剂催化氧化柴油脱硫[J]. 石油化工,2014,43(9):1024-1030
[11] LUO G Q,KANG L H,ZHU M Y, et al. Highly active phosphotungstic acid immobilized on amino functionalized MCM-41 for the oxidesulfurization of dibenzothiophene[J]. Fuel Process Technol.,2014,118:20-27
[12] 李秀萍,赵荣祥,苏建勋,等. 磷钨酸功能化氮化碳的制备及其氧化脱硫研究[J]. 燃料化学学报,2015,43(7):870-875.
[13] 齐晶瑶,强亮生,杜茂松,等. AL-SBA-15介孔分子筛的制备及表征[J]. 稀有金属材料与工程,2007,36(1):534-538.
[14] 陈维林,王恩波. 多酸化学[M]. 北京:科学出版社,2013:47-59.
[15] 何奕工,李奋,王蓬,等. 杂多酸催化剂的吸附酸性和物化性质[J]. 石油炼制与化工,1996,27(8):12-16
[16] 李宇慧,冯丽娟,王景刚,等. MoO₃/介孔Al₂O₃-H₂O₂体系用于柴油催化氧化脱硫[J]. 化工进展,2010,29(s1):659-661
[17] MEI H,MEI B W,YEN T F. A new method for obtaining ultra-low sulfur diesel fuel via ultrasound assisted oxidative desulfurization[J]. Fuel,2003,82:405-414.
[18] 刘帅,冯丽娟,候影飞,等. 汽柴油氧化-萃取脱硫技术中萃取过程研究进展[J]. 精细石油化工进展,2008,9(9):28-31
[19] ZHANG C,PAN X Y,WANG F,et al. Extraction-oxidation desulfurization by pyridinium-based task-specific ionic liquids[J]. Fuel,2012,102:580-586.

磷钨酸/SBA-15催化氧化-萃取柴油脱硫

Diesel desulfurization by phosphotungstic acid/SBA-15 catalytic oxidation-extraction

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