铁基低共熔剂在柴油氧化脱硫中的研究
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摘要
近年来,不同类型的低共熔剂在柴油脱硫中的应用日益广泛。本文首次采用己内酰胺(CPL)和氯化铁为原料合成了铁基低共熔剂(CPL/FeCl_3),并将其应用于氧化脱硫过程中。研究发现:以分子氧为氧化剂,铁基低共熔剂(CPL/FeCl_3)作为催化剂具有很好的氧化脱硫活性。首先,CPL/FeCl_(3 )低共熔剂(DES)的组成及配比均与氧化脱硫活性有关。其次,随着温度的升高,脱硫率逐渐增大,当温度在60℃时,氧化脱硫率达到100%。另外,探究了不同溶剂对脱硫反应的影响。经过系统的研究影响脱硫效率的反应参数,得到最优反应条件如下:反应温度为60℃,氧气流量是60 mL·min~(-1),V_(DES/model oil )=1/10,n(CPL:FeCl_3·6H_2O)=1∶1,此时铁基低共熔剂(CPL/FeCl_3)作为催化剂可以达到100%的脱硫率。
In recent years,different types of deep eutectic solvents(DESs)have been increasingly used in desulfurization process.In this work,Fe based deep eutectic solvents(CPL/FeCl_3)was firstly designed and synthesized by mixing caprolactam(CPL)and FeCl_3·6 H_2O for the oxidative desulfurization process.It is found that the CPL/FeCl_3 as a catalyst possess excellent oxidative desulfurization activity with molecular oxygen as an oxidant.First,the composition and molar ratio of CPL/FeCl_3 are related to the oxidative desulfurization activity.Secondly,the sulfur removal gradually increases with reaction temperature.CPL/FeCl_(3 )exhibited best catalytic performance with 100%desulfurization efficiency at 60 °C.In addition,effects of different solvents on the desulfurization reaction were investigated.The desulfurization efficiency of the Fe‐based DES reached as high as 100%under optimal conditions(the reaction temperature at 60 ℃,the oxygen flow rate with 60 mL·min~(-1),V_(DES/model oil)=1/10,and n(CPL)∶n(FeCl_3·6 H_2O)=1:1).
In recent years,different types of deep eutectic solvents(DESs)have been increasingly used in desulfurization process.In this work,Fe based deep eutectic solvents(CPL/FeCl_3)was firstly designed and synthesized by mixing caprolactam(CPL)and FeCl_3·6 H_2O for the oxidative desulfurization process.It is found that the CPL/FeCl_3 as a catalyst possess excellent oxidative desulfurization activity with molecular oxygen as an oxidant.First,the composition and molar ratio of CPL/FeCl_3 are related to the oxidative desulfurization activity.Secondly,the sulfur removal gradually increases with reaction temperature.CPL/FeCl_(3 )exhibited best catalytic performance with 100%desulfurization efficiency at 60 °C.In addition,effects of different solvents on the desulfurization reaction were investigated.The desulfurization efficiency of the Fe‐based DES reached as high as 100%under optimal conditions(the reaction temperature at 60 ℃,the oxygen flow rate with 60 mL·min~(-1),V_(DES/model oil)=1/10,and n(CPL)∶n(FeCl_3·6 H_2O)=1:1).
引文
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[2]Li F,Liu R,Wen J,et al.Desulfurization of dibenzothiophene by chemical oxidation and solvent extraction with Me3NCH2C6H5Cl·2ZnCl2 ionic liquid[J].Green Chemistry,2009,11(6):883-888.
[3]Ayala M,Robledo N R,Lopez-Munguia A,et al.Substrate specificity and ionization potential in chloroperoxidase-catalyzed oxidation of diesel fuel[J].Environmental Science Technology,2000,34(13):2804-2809.
[4]Yang R T,Hernández-Maldonado A J,Yang F H.Desulfurization of transportation fuels with zeolites under ambient conditions[J].Chem inform,2003,301(5629):79-81.
[5]Tam P S,Kittrell J R,Eldridge J W.Desulfurization of fuel oil by oxidation and extraction.1.Enhancement of extraction oil yield[J].Industrial&Engineering Chemistry Research,1990,29(3):321-324.
[6]Li C,Jiang Z,Gao J,et al.Ultra-deep desulfurization of diesel:oxidation with a recoverable catalyst assembled in emulsion.[J].Chemistry-A European Journal,2010,10(9):2277-2280.
[7]葛建华,周钰明,高良敏,等.酸性离子液体中八聚钼酸盐相转移催化氧化脱硫的研究[J].化学研究与应用,2013,25(6):804-811.
[8]王孟平,王强,封瑞江,等.添加磷钨酸的离子液体萃取催化氧化脱硫研究[J].化学研究与应用,2017(03):49-57.
[9]Jiang Z,Lv H,Zhang Y,et al.Oxidative desulfurization of fuel Oils[J].Chinese Journal of Catalysis,2011,32(5):707-715.
[10]Tian Y,Wang G,Long J,et al.Ultra-deep oxidative desulfurization of fuel with H2O2,catalyzed by phosphomolybdic acid supported on silica[J].Chinese Journal of Catalysis,2016,37(12):2098-2105.
[11]Granadeiro C M,Ribeiro S O,Karmaoui M,et al.Production of ultra-deep sulfur-free diesels using a sustainable catalytic system based on UiO-66(Zr)[J].Chemical Communications,2015,51(72):13818-13821.
[12]Baudoux J,Judeinstein P,Cahard D,et al.Design and synthesis of novel ionic liquid/liquid crystals(IL2Cs)with axial chirality[J].Tetrahedron Letters,2005,46(7):1137-1140.
[13]Martínezpalou R,Luque R.Applications of ionic liquids in the removal of contaminants from refinery feedstocks:an industrial perspective[J].Energy&Environmental Science,2014,7(8):2414-2447.
[14]Ebben C J,Shrestha M,Martinez I S,et al.Organic constituents on the surfaces of aerosol particles from southern finland,amazonia,and california studied by vibrational sum frequency generation[J].Journal of Physical Chemistry A,2012,116(32):8271-8290.
[15]Hayashi S,Hamaguchi H O.Discovery of a magnetic ionic liquid[bmim]FeCl4[J].Chem inform,2005,36(18):1590-1591.
[16]何义,余江,陈灵波.铁基离子液体湿法氧化硫化氢的反应性能[J].化工学报,2010,61(4):963-968.
[17]Li H,Zhu W,Wang Y,et al.Deep oxidative desulfurization of fuels in redox ionic liquids based on iron chloride[J].Green Chemistry,2009,11(6):810-815.
[18]Pham T P T,Cho C W,Yun Y S.Environmental fate and toxicity of ionic liquids:A review[J].WATER RESEARCH,2010,44(2):352-372.
[19]Docherty K M,Kulpa C F.Toxicity and antimicrobial activity of imidazolium and pyridinium ionic liquids[J].Green Chemistry,2005,7(4):185-189.
[20]Deetlefs M,Seddon K R.Assessing the greenness of some typical laboratory ionic liquid preparations[J].Green Chemistry,2010,12(1):17-30.
[21]Abbott A P,Capper G,Davies D L,et al.Novel solvent properties of choline chloride/urea mixtures[J].Chemical Communications,2002,9(1):70-71.
[22]Lindberg D,De l F R M,Widersten M.Deep eutectic solvents(DESs)are viable cosolvents for enzyme-catalyzed epoxide hydrolysis[J].Journal of Biotechnology,2010,147(3):169-171.
[23]Davey R J,Garside J,Hilton A M,et al.Purification of molecular mixtures below the eutectic by emulsioncrystallization[J].Nature,1995,375(6533):664-666.
[24]Nkuku C A,Lesuer R J.Electrochemistry in deep eutectic solvents[J].Journal of Physical Chemistry B,2007,111(46):13271-13277.
[25]Zhao X,Kang.Ionothermal synthesis of FeAlPO-16 molecular sieve by microwave irradiation in eutectic mixture[J].Journal of Porous Materials,2011,18(5):615-621.
[26]Durand E,Lecomte J,Baréa B,et al.Evaluation of deep eutectic solvent-water binary mixtures for lipase-catalyzed lipophilization of phenolic acids[J].Green Chemistry,2013,15(8):2275-2282.
[27]Abbott A P,Barron J C,Ryder K S,et al.Eutectic-based ionic liquids with metal-containing anions and cations[J].Chemistry,2007,13(22):6495-6501.
[28]Bagh F S G,Hadj-Kali M K O,Mjalli F S,et al.Solubility of sodium chloride in phosphonium-based deep eutectic solvents[J].Journal of Molecular Liquids,2014,199:344-351.
[29]Li C,Zhang J,Li Z,et al.Extraction desulfurization of fuels with“metal ions”based deep eutectic solvents(MDESs)[J].Green Chemistry,2016,18(13):3789-3795.
[30]郭智慧,张婷婷,顾佳佳,等.铁基离子液的水相合成工艺[J].化工学报,2013,64(S1):198-202.
[31]Zhu W,Wang C,Li H,et al.One-pot extraction combined with metal-free photochemical aerobic oxidative desulfurization in deep eutectic solvent[J].Green Chemistry,2015,17(4):2464-2472.
[32]Hao L,Su T,Hao D,et al.Oxidative desulfurization of diesel fuel with caprolactam-based acidic deep eutectic solvents:Tailoring the reactivity of DESs by adjusting the composition[J].Chinese Journal of Catalysis,2018,39(9):1552-1559.
[33]姚润生,余江.氯化咪唑铁基离子液体的物化性能及脱硫机理[J].煤炭学报,2011,36(01):135-139.