Synthesis of P/W-coupled polyionic liquids for oxidative desulfurization of model oil
-
摘要: 合成了新型的聚合离子液体磷钨酸盐(聚1-丁基-3-乙烯基咪唑磷钨酸盐)(PBVImPW), 采用FT-IR、XRD和TG进行表征, 通过CHN元素和ICP分析确定其结构。催化剂用于过氧化氢为氧化剂的模拟油品氧化脱硫反应。考察反应温度、氧硫比、催化剂用量等对脱硫率的影响。结果表明, 当反应温度为50 ℃, n(H2O2)/n(S) 为8, n (PBVImPW (P))/n (BT) 为0.4:1.0, 反应时间150 min时, 苯并噻吩(BT) 的转化率可以达到99.4%。催化剂可回收重复使用四次, 催化活性无明显下降。Abstract: A novel PW-coupled polyionic liquid (1-n-butyl-3-vinylimidazolium phosphotungstate) (PBVImPW) was successfully synthesized and characterized by FT-IR, XRD, TG, ICP and CHN analysis. The prepared catalyst was applied in oxidative desulfurization processes of the model oil in the presence of H2O2. Several parameters including temperature, time, the amount of hydrogen peroxide and catalyst were investigated. PBVImPW is proved to be a highly efficient catalyst, and 99.4% benzothiophene conversion is achieved at reaction temperature of 50 ℃, n(H2O2)/n(S) ratio of 8, n(PBVImPW (P))/n(BT) ratio of 0.4 and reaction time of 150 min. There is not a significant decrease in the activity of the catalyst after being recycled four times.
-
图 1 不同样品的红外光谱谱图
Figure 1 FT-IR spectra of various samples
a: 1-Vim; b: PBVImPW; c: HPW
图 5 反应温度对脱硫效果的影响
Figure 5 Influence of reaction temperature on sulfur removal reaction conditions: BT model oil 5 mL, n (H2O2) /n(S)=6:1, n(PBVImPW) /n(S)=0.4
图 6 n(H2O2) /n(S) 对催化剂脱硫效果的影响
Figure 6 Influence of the H2O2/sulfur molar ratio on sulfur removal reaction conditions: BT model oil 5 mL, n(PBVImPW) /n(S)=0.4, 50 ℃
图 7 催化剂用量对脱硫效果的影响
Figure 7 Influence of the amount of (PBVImPW (P)) catalyst on sulfur removal reaction conditions: BT model oil 5 mL, 30% H2O2 (0.048 mL), 50 ℃, 150 min
图 8 氧化反应后模拟油的GC-FPD谱图和FT-IR谱图
Figure 8 GC-FPD chromatograms (a) and FT-IR spectra of model oil after oxidation (b)
表 1 其他油品氧化脱硫
Table 1 Oxidative desulfurization results
Conversion of BT x/% 4, 6-DMDBT DBT TP 98.5 95.8 54.9 model oil (sulfur content is 500 mg/L) 5 mL, 30% H2O2(0.048 mL) 
下载: 导出CSV
表 2 催化剂PBVImPW的氧化BT的循环使用
Table 2 Reusability of PBVImPW catalyst for BT ODS
Run number 1 2 3 4 Conversion of BT x/% 99.0 98.8 97.6 95.3 reaction condition: 30% H2O2 (0.048 mL), model oil (5 mL), 50 ℃, 150 min
下载: 导出CSV
-
[1] BABICH I V, MOULIJN J A. Science and technology of novel processes for deep desulfurization of oil refinery streams: A review[J]. Fuel, 2003, 82(6): 607-631. doi: 10.1016/S0016-2361(02)00324-1 [2] EPA. Heavy-duty engine and vehicle standards and highway diesel fuel sulfur control requirements[R]. US Environmental Protection Agency, Air and Radiation, EPA420-F-00-057, 2000. [3] MA X L, VELU S, KIM J H, SONG C S. Deep desulfurization of gasoline by selective adsorption over solid adsorbents and impact of analytical methods on ppm-level sulfur quantification for fuel cell applications[J]. Appl Catal B: Environ, 2005, 56(1): 137-147. https://www.researchgate.net/publication/222211079_Deep_desulfurization_of_gasoline_by_selective_adsorption_over_solid_adsorbents_and_impact_of_analytical_methods_on_ppm-level_sulfur_quantification_for_fuel_cell_applications [4] ROGERS R D, SEDDON K R. Ionic liquids-Solvents of the future?[J]. Science, 2003, 302(5646): 792-793. doi: 10.1126/science.1090313 [5] 张恒, 周志彬, 聂进.离子液体聚合物的研究进展[J].化学进展, 2013, 25(5): 761-774. http://www.cnki.com.cn/Article/CJFDTOTAL-HXJZ201305014.htmZHANG Heng, ZHOU Zhi-bin, NIE Jin. Recent advances of polymeric ionic liquid[J]. Prog Chem, 2013, 25(5): 761-774. http://www.cnki.com.cn/Article/CJFDTOTAL-HXJZ201305014.htm [6] SHU C H, SUN T H, ZHANG H B, JIA J P, LOU Z Y.A novel process for gasoline esulfurization based on extraction with ionic liquids and reduction by sodium borohydride[J]. Fuel, 2014, 121: 72-78. doi: 10.1016/j.fuel.2013.12.037 [7] MALIKA A, EASTON E B. Hybrid material based on 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and Dawson polyoxoanion [P2Mo18O62]6-. Part II: further characterizations and catalytic oxidation of the NADH coenzyme[J]. J Solid State Electr, 2013, 17(1): 137-143. doi: 10.1007/s10008-012-1869-2 [8] ABIA J A, OZER R. Development of polyoxometalate-ionic liquid compounds for processing cellulosic biomass[J]. Bioresources, 2013, 8(2): 2924-2933. https://www.researchgate.net/publication/236381390_Development_of_Polyoxometalate-Ionic_Liquid_Compounds_for_Processing_Cellulosic_Biomass [9] LENG Y, LIU J, JIANG P P, WANG J. Organometallic-polyoxometalate hybrid based on V-Schiff base and phosphovanadomolybdate as a highly effective heterogenous catalyst forhydroxylation of benzene[J]. Chem Eng J, 2014, 239: 1-7. doi: 10.1016/j.cej.2013.10.092 [10] CHEN G J, ZHOU Y, LONG Z Y, WANG X C, LI J, WANG J. Mesoporous polyoxometalate-based ionic hybrid as a triphasic catalyst for oxidation of benzyl alcohol with H2O2 on water[J]. Appl Mater Inter, 2014, 6(6): 4438-4446. doi: 10.1021/am5001757 [11] LI J, ZHOU Y, MAO D, CHEN G J, WANG X C, YANG X N, WANG M, PENG L M, WANG J. Heteropolyanion-based ionic liquid-functionalized mesoporous copolymer catalyst for Friedel-Crafts benzylation of arenes with benzyl alcohol[J]. Chem Eng J, 2014, 254: 54-62. doi: 10.1016/j.cej.2014.05.124 [12] PEKEL N, RZAEV Z M O, GÜVEN O. Synthesis and characterization of poly (N -vinylimidazole-co -acrylonitrile) and determination of monomer reactivity ratios[J]. Macromol Chem Phys, 2004, 205(8): 1088-1095. doi: 10.1002/(ISSN)1521-3935 [13] HUANG W, ZHU W, LI H, SHI H, ZHU G, LIU H, CHEN G Y, Heteropolyanion-based ionic liquid for deep desulfurization of fuels in ionic liquids[J]. Ind Eng Chem Res, 2010, 49(19): 8998-9003. doi: 10.1021/ie100234d [14] OTSUKI S, NONAKA T, TAKASHIMA N, QIAN W, ISHIHARA A, IMAI T, KABE T. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction energy[J]. Fuels, 2000, 14(6): 1232-1239. doi: 10.1021/ef000096i [15] ZHU W, HUANG W, LI H. Polyoxometalate-based ionic liquids as catalysts for deep desulfurization of fuels[J]. Fuel Process Technol, 2011, 92(10): 1842-1848. doi: 10.1016/j.fuproc.2011.04.030 [16] CHEN X, SONG D, ASUMANA C, YU G. Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids based on 1-n-butyl-3-methylimidazolium metal chloride[J]. J Mol Catal A: Chem, 2012, 359: 8-13. doi: 10.1016/j.molcata.2012.03.014 [17] ZHU W S, LI H M, JIANG X, YAN Y S, LU J D, XIA J X. Oxidative desulfurization of fuels catalyzed by peroxotungsten and peroxomolybdenum complexes in ionic liquids [J].Energy Fuels, 2007, 21(5): 2514-2516. doi: 10.1021/ef700310r [18] LI C, JIANG Z X, GAO J B, YANG Y X, WANG S J, TIAN F P, SUN F X, SUN X P, YING P L, HAN C R. Ultra-deep desulfurization of diesel: Oxidation with a recoverable catalyst assembled in emulsion[J]. Chem Eur J, 2004, 10(9): 2277-2280. doi: 10.1002/(ISSN)1521-3765 [19] GAO H, LOU M, XING J, WU Y, LI Y, LI W, LIU Q, LIU H. Desulfurization of fuel by extraction with pyridinium-based ionic liquid[J]. Ind Eng Chem Res, 2008, 47(21): 8384-8388. doi: 10.1021/ie800739w [20] XU J H, ZHAO S, CHEN W, WANG M, SONG Y F. Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36·32H2O in [bmim]BF4 at room temperature[J]. Chem Eur J, 2012, 18(5): 4775-4781. [21] ZHANG M, ZHU W S, XUN S H, LI H M, GU Q Q, ZHAO Z, WANG Q. Deep oxidative desulfurization of dibenzothiophene with POM-based hybrid materials in ionic liquids[J]. Chem Eng J, 2013, 220: 328-336. doi: 10.1016/j.cej.2012.11.138 -
点击查看大图
计量
- 文章访问数: 92
- HTML全文浏览量: 37
- PDF下载量: 5
- 被引次数: 0
