磷钨酸离子液体负载γ-Al2O3催化氧化-萃取脱硫

doi:10.16085/j.issn.1000-6613.2016-1995

化工进展 ›› 2017, Vol. 36 ›› Issue (S1): 267-273.DOI: 10.16085/j.issn.1000-6613.2016-1995

磷钨酸离子液体负载γ-Al₂O₃催化氧化-萃取脱硫

李瑞丽, 蒋善良, 李晶晶, 丁力实

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:2016-11-01 修回日期:2017-02-12 出版日期:2017-12-31 发布日期:2017-12-13
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。
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。

Phosphotungstic acid ionic liquids/γ-Al₂O₃ catalytic oxidation-extraction desulfurization

LI Ruili, JIANG Shanliang, LI Jingjing, DING Lishi

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

Received:2016-11-01 Revised:2017-02-12 Online:2017-12-31 Published:2017-12-13

摘要/Abstract

摘要： 以γ-Al₂O₃为载体、磷钨酸离子液体为活性组分，用共沉淀法制备了[C₁imCH₂CH₂COOH]₃PW₁₂O₄₀/γ-Al₂O₃（IL-HPW/γ-Al₂O₃）催化剂，并采用BET、TGA、FTIR、XRD以及SEM表征技术对催化剂进行表征分析。以质量分数为30%的H₂O₂为氧化剂，以N-甲基吡咯烷酮（NMP）为萃取剂，以含二苯并噻吩（DBT）的模拟油品进行氧化萃取脱硫反应，考察了氧化-萃取工艺条件对模拟油脱硫效果的影响。实验结果表明，在催化剂用量质量分数为0.7%（基于模拟油质量），反应时间为60min，n（H₂O₂）∶n（S）=2.5，反应温度为50℃，萃取一次的最佳条件下，其最佳脱硫率为99.2%。该催化剂在直馏柴油中也表现出较高的脱硫活性，在一定的反应条件下，使用N-甲基吡咯烷酮萃取剂萃取4次后，柴油硫含量从477mg/L降到24.4mg/L，脱硫率高达94.88%。

关键词: 磷钨酸离子液体, 共沉淀法, 催化剂, 脱硫率

Abstract: In the experiment,[C₁imCH₂CH₂COOH]₃PW₁₂O₄₀/γ-Al₂O₃(IL-HPW/γ-Al₂O₃)was made as a kind of catalyst by co-precipitation in the experiment using γ-Al₂O₃ as the carrier and phosphotungstic acid ionic liquids as the active component, characterized by BET,TGA,FTIR,XRD and SEM.The technology conditions of oxidation-extraction were investigated by oxidative desulfurization.During the process, with 30% H₂O₂ as the oxidant, and N-methyl-2-pyrrolidone (NMP) as the extraction agent, model oil which contained dibenzothiophene(DBT) experienced extraction and oxidation desulfurization.The results showed that under an optimum condition when the dosage of the catalyst is 0.7% (based on the mass of model oil), the reaction time was 60min,n(H₂O₂):n(S)=2.5;when the reaction temperature was 50℃ with only one-time extraction, the optimal sulfur removal was 99.2%.The catalyst showed high desulfurization activity in straight run diesel oil as well.The sulfur content dropped from 477mg/L to 24.4mg/L after extracting it four times with NMP at the given reaction condition.The sulfur removal was as high as 94.88%.

Key words: phosphotungstic acid ionic liquids, co-precipitation, catalyst, desulfurization

中图分类号:

TE626

李瑞丽, 蒋善良, 李晶晶, 丁力实. 磷钨酸离子液体负载γ-Al₂O₃催化氧化-萃取脱硫[J]. 化工进展, 2017, 36(S1): 267-273.

LI Ruili, JIANG Shanliang, LI Jingjing, DING Lishi. Phosphotungstic acid ionic liquids/γ-Al₂O₃ catalytic oxidation-extraction desulfurization[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 267-273.

参考文献

[1] ZHANG C,PAN X,WANG F,et al.Extraction-oxidation desulfurization by pyridinium-based task-specific ionic liquids[J].Fuel,2012,102:580-584.
[2] STANISLAUS A,MARAFI A,RANA M S.Recent advances in the science and technology of ultra low sulfur diesel(ULSD)production[J].Catalysis Today,2010,153(1):1-68.
[3] SONG C.An overview of new approaches to deep desulfurization for ultra-clean gasoline,diesel fuel and jet fuel[J].Catalysis Today,2003,86(1):211-263.
[4] QIU J,WANG G,ZHANG Y,et al.Direct synthesis of mesoporous H₃PMo₁₂O₄₀/SiO₂ and its catalytic performance in oxidative desulfurization of fuel oil[J].Fuel,2015,147:195-202.
[5] 王军民,房少华,廖启玲,等.催化裂化汽油溶剂萃取脱硫工艺的研究[J].炼油设计,2000,30(10):32-34. WANG J M,FANG S H,LIAO Q L,et al.Study on solvent extraction and desulfurization of FCC gasoline[J].Refining Design,2000,30(10):32-34.
[6] 唐晓东,赖先熔,李晓贞,等.直馏柴油络合萃取脱硫的实验研究[J].石油炼制与化工,2010,41(12):16-19. TANG X D,LAI X R,LI X Z,et al.Experimental study on desulfurization of straight-run diesel oil by complex extraction[J].Petroleum Processing and Petrochemicals,2010,41(12):16-19.
[7] 张晓静,秦如意,刘金龙.FCC汽油吸附脱硫工艺技术-LADS工艺[J].天然气与石油,2003,21(1):39-41. ZHANG X J,QING R Y,LIU J L.Adsorption desulfurization process technology of FCC gasoline-LADS process[J].Natural Gas and Petroleum,2003,21(1):39-41.
[8] 李瑞丽,吕本震,蒋善良,等.磷钨酸/SBA-15催化氧化-萃取柴油脱硫[J].化工进展,2016,35(9):2790-2795. LI R L,LV B Z,JIANG S L,et al.Catalytic oxidation-extraction of diesel oil by phosphotungstic/SBA-15[J].Chemical Industry and Engineering Progress,2016,35(9):2790-2795.
[9] 林燕,王芳,张志庆,等.离子液体绿色脱硫机理及应用进展[J].化工进展,2013,32(3):549-557. LIN Y,WANG F,ZHANG Z Q,et al.Green desulphurization mechanism and Application of Ionic Liquid[J].Chemical Industry and Engineering Progress,2013,32(3):549-557.
[10] 赵地顺,周二鹏,王建龙,等.离子液体脱除汽油中含硫化合物的研究[J].化学工程,2010,38(1):1-4. ZHAO D S,ZHOU E P,WANG J L,et al.Study on removal of sulfur compounds in gasoline by ionic liquid[J].Chemical Engineering,2010,38(1):1-4.
[11] ZHU W,HUANG W,LI H,et al.Polyoxometalate-based ionic liquids as catalysts for deep desulfurization of fuels[J].Fuel Processing Technology,2011,92(10):1842-1848.
[12] LI M,ZHANG M,WEI AM,et al.Facile synthesis of amphiphilic polyoxometalate-based ionic liquid supported silica induced efficient performance in oxidative desulfurization[J].Journal of Molecular Catalysis A:Chemical,2015,406:23-30.
[13] 王晓化.吴晓牧.寇元.功能化酸性离子液体的合成及表征[C]//第十二届全国催化学术会议,北京.2005. WANG X H,WU X M,KOU Y.Synthesis and Characterization of functionalized ionic liquids[C].2005.
[14] 陈维林,王恩波.多酸化学[M].北京:科学出版社,2016:52-59. CHEN W L,WANG E B.Chemistry of polyacids[M].Beijing:Science Press,2016:52-59.
[15] RAJKUMAR T,RAO G R.Investigation of hybrid molecular material prepared by ionic liquid and polyoxometalate anion[J].Journal of Chemical Sciences,2008,120(6):587-594.
[16] JIANG W,ZHU W,LI H,et al.Fast oxidative removal of refractory aromatic sulfur compounds by a magnetic ionic liquid[J].Chemical Engineering & Technology,2014,37(1):36-42.
[17] ZHANG Xia,LI Jing,CHEN Yang,et al.Heteropolyacid nanoreactor with double acid sites as a highly efficient and reusable catalyst for the transesterification of waste cooking oil[J].Energy Fuels,2009,23(9):4640-4646.

磷钨酸离子液体负载γ-Al₂O₃催化氧化-萃取脱硫

Phosphotungstic acid ionic liquids/γ-Al₂O₃ catalytic oxidation-extraction desulfurization

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