介孔g-C_3N_4的制备及其对航空煤油的吸附脱硫性能
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摘要
采用硬模板法制备了介孔类石墨相氮化碳(g-C_3N_4),在500、550、600℃下焙烧分别得到CN-500、CN-550、CN-600。采用XRD、TEM、FT-IR、FPD和N_2吸脱附等分析手段对制备的介孔材料进行表征,考察了其对航空煤油(航煤)吸附脱硫的性能。结果表明:该介孔材料对噻吩有较好的吸附能力,550℃煅烧的样品CN-550吸附容量最大,为24mg(S)/g;其对真实航煤的脱硫吸附容量可达10.46mg(S)/g。g-C_3N_4介孔材料在用NaOH消除抗氧化剂后的航煤中对硫的吸附容量提升约50%。由于分子尺寸及位阻效应等影响,介孔g-C_3N_4对噻吩的吸附容量远大于对苯并噻吩吸附的吸附容量,对苯并噻吩及其衍生物的吸附能力较低是介孔g-C_3N_4对航煤脱硫性能下降的主要原因。
Mesoporous g-C_3N_4 was prepared by SiO_2 by a hard template method.Then the prepared mesoporous g-C_3N_4 was calcined at 500,550 or 600℃ and its final products are assigned as CN-500,CN-550 and CN-600,respectively.The above calcined mesoporous absorbents were further characterized by XRD,TEM,FT-IR,FPD and N_2 absorption-desorption,and their desulfurization performance for simulated fuel and jet fuel were investigated as well.Experimental results indicate that CN-550 has the best absorption capacity for thiophene,i.e.,24mg(S)/g in simulated fuel.For jet fuels,the absorption capacity of CN-550 can be 10.46mg(S)/g.After jet fuels were treated by NaOH,which eliminated the effect of antioxidant from fuel,the absorption capacity could increase 50%.The gas chromatogram analytical results for sulfur compounds suggest that the prepared absorbents have better absorption capacity for thiophene than benzothiophene due to size and steric effects.This is the main reason of their poor desulfurization performance for jet fuels.
Mesoporous g-C_3N_4 was prepared by SiO_2 by a hard template method.Then the prepared mesoporous g-C_3N_4 was calcined at 500,550 or 600℃ and its final products are assigned as CN-500,CN-550 and CN-600,respectively.The above calcined mesoporous absorbents were further characterized by XRD,TEM,FT-IR,FPD and N_2 absorption-desorption,and their desulfurization performance for simulated fuel and jet fuel were investigated as well.Experimental results indicate that CN-550 has the best absorption capacity for thiophene,i.e.,24mg(S)/g in simulated fuel.For jet fuels,the absorption capacity of CN-550 can be 10.46mg(S)/g.After jet fuels were treated by NaOH,which eliminated the effect of antioxidant from fuel,the absorption capacity could increase 50%.The gas chromatogram analytical results for sulfur compounds suggest that the prepared absorbents have better absorption capacity for thiophene than benzothiophene due to size and steric effects.This is the main reason of their poor desulfurization performance for jet fuels.
引文
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[2]邱国欢,孟祥瑞,王玉和.航空煤油在不同价态金属离子交换介孔材料上的深度吸附脱硫[J].化学工程师,2013,27(1):1-4.(QIU Guohuan,MENG Xiangrui,WANG Yuhe.Deep desulfurization of jet fuel by adsorption over mesoporous materials exchanged with different metal cations chemical engineer[J].Chemical Engineer,2013,27(1):1-4.)
[3]WANG Y H,YANG R T,HEINZEL J M.Desulfurization of jet fuel byπ-complexation adsorption with metal halides supported on MCM-41and SBA-15mesoporous materials[J].Chemical Engineering Science,2008,63(2):356-365.
[4]CHEN H,WANG Y H,YANG F H,et al.Desulfurization of high-sulfur jet fuel by mesoporousπ-complexation adsorbents[J].Chemical Engineering Science,2009,64(24):5240-5246.
[5]WANG Y H,YANG F H,YANG R T.Desulfurization of high-sulfur jet fuel by π-complexation with copper and palladium halide sorbents[J].Ind Eng Chem Res,2006,45(22):7649-7655.
[6]FONTAINE C,ROMERO Y,DAUDIN A,et al.Insight into sulphur compounds and promoter effects on molybdenum-based catalysts for selective HDS of FCCgasoline[J].Appl Catal A:General,2010,388(1):188-195.
[7]唐晓东,陈露,李晶晶,等.车用燃料油络合吸附脱硫剂的研究进展[J].现代化工,2015,35(12):39-42.(TANG Xiaodong,CHEN Lu,LI Jingjing,et al.Research advances in complexation adsorbents for adsorptive desulfurization of vehicle fuel oil[J].Modern Chemical Industry,2015,35(12):39-42.)
[8]李成岳,张金昌.汽油和柴油脱硫技术进展[J].石油技术与应用,2002,20(5):293-295.(LI Chengyue,ZHANG Jinchang.Progress of desulfurization technology for gasoline and diesel oil[J].Petrochemical Technology&Application,2002,20(5):293-295.)
[9]DONG F,WANG Z Y,SUN Y J,et al.Engineering the nanoarchitecture and texture of polymeric carbon nitride semiconductor for enhanced visible light photocatalytic activity[J].Journal of Colloid and Interface Science,2013,401(1):70-79.
[10]范乾靖,刘建军,于迎春,等.新型非金属光催化剂石墨型氮化碳的研究进展[J].化工进展,2014,33(5):1185-1194.(FAN Qianjing,LIU Jianjun,YUYingchun,et al.Research progress in a new metal-free photocatalyst-graphitic carbon nitride[J].Chemical Industry and Engineering Progress,2014,33(5):1185-1194.)
[11]ZHANG J S,CHEN X F,TAKANABE K,et al.Synthesis of a carbon nitride structure for visible-light catalysis by copolymerization[J].Angew Chem Int Ed,2010,49(2):441-444.
[12]ZHONG Y J,WANG Z Q,FENG J Y,et al.Improvement in photocatalytic H2evolution over g-C3N4prepared from protonated melamine[J].Applied Surface Science,2014,295(10):253-259.
[13]XU J,WU H T,WANG X,et al.A new and environmentally benign precursor for the synthesis of mesoporous g-C3N4 with tunable surface area[J].Physical Chemistry Chemical Physics,2013,15(13):4510-4517.