质子化钛酸纳米管催化果糖制备5-羟甲基糠醛
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摘要
利用XRD,SEM,TEM,BET表征手段对其进行物相结构、微观形貌、比表面积分析,以此为催化剂并将其应用于催化果糖脱水制备5-羟甲基糠醛(5-HMF).研究了反应温度、反应时间、催化剂用量等对5-HMF收率的影响,从而得到最佳反应条件.研究结果表明:以二甲基亚砜(DMSO)为溶剂,反应温度130℃、反应时间5 h、催化剂用量为果糖用量5%时,5-HMF收率达到56. 6%;催化剂具有较高的重复使用性能,经重复使用3次后,5-HMF收率只下降2. 7%.
The method of hydrothermal synthesis was adopted to prepare titanate nanotubes using P25 TiO2 powder as raw material,and then protonated titanate nanotubes were obtained after pickling with hydrochloric acid. XRD,SEM,TEM,and BET were used to analyze the phase structure,microstructure,and specific surface area. The protonated titanate nanotubes were applied to catalyze the dehydration of fructose to prepare 5-hydroxymethylfurfural(5-HMF). The effects of reaction temperature,reaction time and catalyst amount on the yield of 5-HMF were studied,and the reaction conditions were optimized. The results showed that the yield of 5-HMF reached56. 6% when dimethyl sulfoxide(DMSO) was used as the solvent,the reaction temperature was 130 ℃,the reaction time was 5 h,and the amount of catalyst was 5% fructose in mass fraction. After the catalyst was reused for three times,the yield decreased only by2. 7%,indicating that the catalyst had better reusability.
The method of hydrothermal synthesis was adopted to prepare titanate nanotubes using P25 TiO2 powder as raw material,and then protonated titanate nanotubes were obtained after pickling with hydrochloric acid. XRD,SEM,TEM,and BET were used to analyze the phase structure,microstructure,and specific surface area. The protonated titanate nanotubes were applied to catalyze the dehydration of fructose to prepare 5-hydroxymethylfurfural(5-HMF). The effects of reaction temperature,reaction time and catalyst amount on the yield of 5-HMF were studied,and the reaction conditions were optimized. The results showed that the yield of 5-HMF reached56. 6% when dimethyl sulfoxide(DMSO) was used as the solvent,the reaction temperature was 130 ℃,the reaction time was 5 h,and the amount of catalyst was 5% fructose in mass fraction. After the catalyst was reused for three times,the yield decreased only by2. 7%,indicating that the catalyst had better reusability.
引文
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[19] Li J,Zhang M,Li Q,et al. Enhanced visible light activity on direct contact Z-scheme g-C3N4-TiO2photocatalyst[J]. Applied Surface Science,2016,391:184-193.
[20]刘彦丽,王福余,王崇,等.固体酸WO3/Zr O2催化果糖脱水合成5-羟甲基糠醛[J].化工进展,2014,33(1):105-109.
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[22] Zhang X,Wang M,Wang Y,et al. Nanocoating of magnetic cores with sulfonic acid functionalized shells for the catalytic dehydration of fructose to 5-hydroxymethylfurfural[J]. Chinese Journal of Catalysis,2014,35(5):703-708.
[23] Qi X H,Guo H X,Li L Y,et al. Acid-catalyzed dehydration of fructose into 5-hydroxymethyfufural by cellulose-derived amorphous carbon[J]. Chemsuschem,2012,5(11):2215-2220.
[24]李黎峰,沈忠权,厉岑怡,等.新型磺化碳基材料催化果糖制备5-羟甲基糠醛[J].高校化学工程学报,2016,30(6):1341-1347.
[2] Zhang Y,Wang J,Li X,et al. Efficient conversion of glucose to HMF using organo catalysts with dual acidic and basic functionalities-A mechanistic and experimental study[J]. Fuel,2017,162:30-36.
[3]张文芊.新型离子液体中葡萄糖催化水解制五羟甲基糠醛研究[D].北京:北京化工大学,2015.
[4] Kumari P K,Rao B S,Padmakar D,et al. Lewis acidity induced heteropoly tungustate catalysts for the synthesis of5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural[J]. Molecular Catalysis,2018,448:108-115.
[5] Fachri B A,Abdilla R M,Bovenkamp H H,et al. Experimental and kinetic modeling studies on the sulfuric acid catalyzed conversion of D-fructose to 5-hydroxymethylfurfural and levulinic acid in water[J]. ACS Sustainable Chemistry&Engineering,2015,3(12):3024-3034.
[6]刘昕,吕秀阳,夏文莉,等.高温液态水中有机酸对果糖分解反应动力学的影响[J].化工学报,2006,57(1):52-56.
[7] Sta Hlberg T,Rodriguez-Rodriguez S,Fristrup P,et al.Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter[J].Chemistry-A European Journal,2011,17(5):1369-1369.
[8]仝新利,李梦然.酸性离子液体催化蔗糖转化合成5-羟甲基糠醛[J].工业催化,2011,19(1):68-71.
[9] Han H,Zhao H,Liu Y,et al. Efficient conversion of fructose into 5-hydroxymethylfurfural over WO3/reduced graphene oxide catalysts[J]. Rsc Advances,2017,7(7):3790-3795.
[10] Jin P,Zhang Y,Chen Y,et al. Facile synthesis of hierarchical porous catalysts for enhanced conversion of fructose to 5-hydroxymethylfurfural[J]. Journal of the Taiwan Institute of Chemical Engineers,2017,75:59-69.
[11] Maldonado C S,De La Rosa J R,Lucio-Ortiz C J,et al. Synthesis and characterization of functionalized alumina catalysts with thiol and sulfonic groups and their performance in producing 5-hydroxymethylfurfural from fructose[J]. Fuel,2017,198:134-144.
[12] Lv G,Deng L,Lu B,et al. Efficient dehydration of fructose into 5-hydroxymethyfufural in aqueous medium over silica-included heteropolyacids[J]. Journal of Cleaner Production,2017,142:2244-2251.
[13] Preda S,Rutar M,Umek P,et al. A study of thermal properties of sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method[J]. Materials Research Bulletin,2015,71:98-105.
[14] Guo L,Hu X,Hu G,et al. Tetraethylenepentamine modified protonated titanate nanotubes for CO2capture[J]. Fuel Processing Technology,2015,138:663-669.
[15] Camposeco R,Castillo S,Mejia-Centeno I,et al. Behavior of Lewis and Brnsted surface acidity featured by Ag,Au,Ce,La,Fe,Mn,Pd,Pt,V and W decorated on protonated titanate nanotubes[J]. Microporous&Mesoporous Materials,2016,236:235-243.
[16] Kitano M,Wada E,Nakajima K,et al. Protonated titanate nanotubes with Lewis and Brnsted acidity:Relationship between nanotube structure and catalytic activity[J]. Chemistry of Materials,2013,25(3):385-393.
[17] Li S,Li N,Li G,et al. Protonated titanate nanotubes as a highly active catalyst for the synthesis of renewable diesel and jet fuel range alkanes[J]. Applied Catalysis B Environmental,2015,170:124-134.
[18] Sluban M,Cojocaru B,Parvulescu V I,et al. Protonated titanate nanotubes as solid acid catalyst for aldol condensation[J]. Journal of Catalysis,2017,346:161-169.
[19] Li J,Zhang M,Li Q,et al. Enhanced visible light activity on direct contact Z-scheme g-C3N4-TiO2photocatalyst[J]. Applied Surface Science,2016,391:184-193.
[20]刘彦丽,王福余,王崇,等.固体酸WO3/Zr O2催化果糖脱水合成5-羟甲基糠醛[J].化工进展,2014,33(1):105-109.
[21]孙春蕾,刘仕伟,李露,等. Brnsted酸性离子液体催化果糖脱水制备5-羟甲基糠醛[J].青岛科技大学学报(自然科学版),2011,32(4):331-334.
[22] Zhang X,Wang M,Wang Y,et al. Nanocoating of magnetic cores with sulfonic acid functionalized shells for the catalytic dehydration of fructose to 5-hydroxymethylfurfural[J]. Chinese Journal of Catalysis,2014,35(5):703-708.
[23] Qi X H,Guo H X,Li L Y,et al. Acid-catalyzed dehydration of fructose into 5-hydroxymethyfufural by cellulose-derived amorphous carbon[J]. Chemsuschem,2012,5(11):2215-2220.
[24]李黎峰,沈忠权,厉岑怡,等.新型磺化碳基材料催化果糖制备5-羟甲基糠醛[J].高校化学工程学报,2016,30(6):1341-1347.