介孔磷酸铌一锅法催化葡萄糖制备5-羟甲基糠醛
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摘要
水热法制得介孔磷酸铌(m-NbP)固体酸催化剂,并用X-射线衍射(XRD)、氮气吸脱附、扫描电镜(SEM)、透射电镜(TEM)、氨气程序升温脱附(NH_3-TPD)、吡啶吸附红外光谱(Py-FTIR)等手段对m-NbP进行了结构和酸性质表征。将m-NbP用于催化水-DMSO两相体系葡萄糖一锅法合成5-羟甲基糠醛(5-HMF),考察了催化剂用量、水与DMSO体积比、反应温度、反应时间及催化剂循环利用次数对5-HMF收率的影响,并与其他三种催化剂(Amberlyst-15、Nb_2O_5及m-NbP-F127)比较催化性能。结果表明,m-NbP具有介孔结构和大量表面强酸性位,因而催化性能突出;当m(葡萄糖)∶m(m-NbP)=2∶1、V(水)∶V(DMSO)=1∶1、170℃反应1.5 h时,5-HMF的收率高达47.0%,且m-NbP经烧焦再生可重复利用5次而无明显失活。因此,m-NbP固体酸催化性能突出,能够高效催化葡萄糖一锅法制备5-HMF。
A kind of mesoporous niobium phosphate( m-NbP) solid acid catalyst was successfully synthesized via convenient hydrothermal method. The obtained catalyst was characterized by X-ray diffraction( XRD),nitrogen adsorption-desorption,scanning electron microscopy( SEM),transmission electron microscopy( TEM),temperature-programmed desorption of ammonia( NH_3-TPD) and Fourier transform infrared spectra of pyridine adsorption( Py-FTIR). Then,the one-pot conversion of glucose to5-hydroxymethylfurural( 5-HMF) in a biphasic water/DMSO medium was investigated on the m-NbP catalyst. The factors affecting the yield of 5-HMF such as catalyst dosage,volume ratio of water to DMSO,reaction temperature,reaction time,and catalyst recyclability were studied. Moreover,the catalytic performance of m-NbP was compared with other three catalysts( Amberlyst-15,Nb_2O_5 and m-NbPF127). The results indicated that the m-NbP catalyst exhibited a promising catalytic performance for the preparation of 5-HMF due to its porous structure and adequate strong acid sites. The yield of 5-HMF could be as high as 47. 0% at 170 ℃ within 1. 5 h when the mass ratio of glucose to m-NbP was 2∶1 and the volume ratio of water to DMSO was 1∶1. Noticeably,the m-NbP catalyst could be recycled to reuse,after recycled five times,it showed no obvious deactivation after high-temperature calcination-regeneration. Therefore,the as-prepared m-NbP is an efficient catalyst for one-pot preparation of 5-HMF.
A kind of mesoporous niobium phosphate( m-NbP) solid acid catalyst was successfully synthesized via convenient hydrothermal method. The obtained catalyst was characterized by X-ray diffraction( XRD),nitrogen adsorption-desorption,scanning electron microscopy( SEM),transmission electron microscopy( TEM),temperature-programmed desorption of ammonia( NH_3-TPD) and Fourier transform infrared spectra of pyridine adsorption( Py-FTIR). Then,the one-pot conversion of glucose to5-hydroxymethylfurural( 5-HMF) in a biphasic water/DMSO medium was investigated on the m-NbP catalyst. The factors affecting the yield of 5-HMF such as catalyst dosage,volume ratio of water to DMSO,reaction temperature,reaction time,and catalyst recyclability were studied. Moreover,the catalytic performance of m-NbP was compared with other three catalysts( Amberlyst-15,Nb_2O_5 and m-NbPF127). The results indicated that the m-NbP catalyst exhibited a promising catalytic performance for the preparation of 5-HMF due to its porous structure and adequate strong acid sites. The yield of 5-HMF could be as high as 47. 0% at 170 ℃ within 1. 5 h when the mass ratio of glucose to m-NbP was 2∶1 and the volume ratio of water to DMSO was 1∶1. Noticeably,the m-NbP catalyst could be recycled to reuse,after recycled five times,it showed no obvious deactivation after high-temperature calcination-regeneration. Therefore,the as-prepared m-NbP is an efficient catalyst for one-pot preparation of 5-HMF.
引文
[1]Vilcocq L,Castilho P C,Carvalheiro F,et al.Hydrolysis of oligosaccharides over solid acid catalysts:a review[J].Chem Sus Chem,2014,7(4):1010-1019.
[2]Dibenedetto A,Aresta M,Pastore C,et al.Conversion of fructose into 5-HMF:a study on the behaviour of heterogeneous ceriumbased catalysts and their stability in aqueous media under mild conditions[J].RSC Adv,2015,5(34):26941-26948.
[3]Bispo C,Oliveria Vigier K D,Sardo M,et al.Catalytic dehydration of fructose to HMF over sulfonic acid functionalized periodic mesoporous organosilicas:role of the acid density[J].Catal Sci Technol,2014,4(8):2235-2240.
[4]Zhang Y L,Pan J M,Yan Y S,et al.Synthesis and evaluation of stable polymeric solid acid based on halloysite nanotubes for conversion of one-pot cellulose to 5-hydroxymethylfurfural[J].RSC Adv,2014,4(45):23797-23806.
[5]Teimouria A,Mazaheria M,Chermahini A N,et al.Catalytic conversion of glucose to 5-hydroxymethylfurfural(HMF)using nano-POM/nano-Zr O2/nano-γ-Al2O3[J].J Taiwan Inst Chem E,2015,49:40-50.
[6]Liu J,Li H,Liu Y C,et al.Catalytic conversion of glucose to 5-hydroxymethylfurfural over nano-sized mesoporous Al2O3-B2O3solid acids[J].Catal Commun,2015,62:19-23.
[7]Gallo J M R,Alonso D M,Mellmer M A,et al.Production and upgrading of 5-hydroxymethyl-furfural using heterogeneous catalysts and biomass-derived solvents[J].Green Chem,2013,15(1):85-90.
[8]Ordomsky V V,van der Schaaf J,Schouten J C,et al.The effect of solvent addition on fructose dehydration to 5-hydroxymethylfurfural in biphasic system over zeolites[J].J Catal,2012,287(1):68-75.
[9]Karimi B,Mirzaei H M.The influence of hydrophobic/hydrophilic balance of the mesoporous solid acid catalysts in the selective dehydration of fructose into HMF[J].RSC Adv,2013,3(43):20655-20661.
[10]Yan H P,Yang Y,Tong D M,et al.Catalytic conversion of glucose to 5-hydroxymethyl-furfural over SO42-/Zr O2and SO42-/Zr O2-Al2O3solid acid catalysts[J].Catal Commun,2009,10(11):1558-1563.
[11]Kourieh R,Rakic V,Bennici S,et al.Relation between surface acidity and reactivity in fructose conversion into 5-HMF using tungstated zirconia catalysts[J].Catal Commun,2013,30(1):5-13.
[12]Carlini C,Patrono P,Raspolli Galletti A M,et al.Heterogeneous catalysts based on vanadyl phosphate for fructose dehydration to5-hydroxymethyl-2-furaldehyde[J].Appl Catal A-Gen,2004,275(1/2):111-118.
[13]Fan C Y,Guan H Y,Zhang H,et al.Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt[J].Biomass Bioenerg,2011,35(7):2659-2665.
[14]Nakajima K,Baba Y,Noma R,et al.Nb2O5·H2O as a heterogeneous catalyst with water-tolerant lewis acid sites[J].J Am Chem Soc,2011,133(12):4224-4227.
[15]Ordomsky V V,Sushkevich V L,Schouten J C,et al.Glucose dehydration to 5-hydroxymethylfurfural over phosphate catalysts[J].J Catal,2013,300(3):37-46.
[16]Wang Y H,Tong X L,Yan Y T,et al.Efficient and selective conversion of hexose to 5-hydroxymethylfurfural with tinzirconium-containing heterogeneous catalysts[J].Catal Commun,2014,50(18):38-43.
[17]Nowak I,Ziolek M.Niobium compounds:preparation,characterization,and application in heterogeneous catalysis[J].Chem Rev,1999,99(12):3603-3624.
[18]Ordomsky V V,van der Schaaf J,Schouten J C,et al.Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system[J].Chem Sus Chem,2012,5(9):1812-1819.
[19]Dunn E F,Liu D J,Chen E Y X.Role of N-heterocyclic carbenes in glucose conversion into HMF by Cr catalysts in ionic liquids[J].Appl Catal A-Gen,2013,460-461(11):1-7.
[20]Sun P,Long X D,He H,et al.Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate[J].Chem Sus Chem,2013,6(11):2190-2197.
[21]Cranston R W,Inkley F A.The determination of pore structures from nitrogen adsorption isotherms[J].Adv Catal,1957,9:143-154.
[22]Corma A.Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions[J].Chem Rev,1995,95(3):559-614.
[23]Jain A,Shore A M,Jonnalagadda S C,et al.Conversion of fructose,glucose and sucrose to 5-hydroxymethyl-2-furfural over mesoporous zirconium phosphate catalyst[J].Appl Catal A-Gen,2015,489:72-76.
[24]Rocha A S,Forrester A M S,de la Cruz M H C,et al.Comparative performance of niobium phosphates in liquid phase anisole benzylation with benzyl alcohol[J].Catal Commun,2008,9(10):1959-1965.
[24]Faungnawakij K,Kikuchi R,Matsui T,et al.A comparative study of solid acids in hydrolysis and steam reforming of dimethyl ether[J].Appl Catal A,2007,333(1):114-121.
[25]Jia S Y,Xu Z W,Zhang Z C.Catalytic conversion of glucose in dimethylsulfoxide/water binary mix with chromium trichloride:role of water on the product distribution[J].Chem Eng J,2014,254(1):333-339.
[2]Dibenedetto A,Aresta M,Pastore C,et al.Conversion of fructose into 5-HMF:a study on the behaviour of heterogeneous ceriumbased catalysts and their stability in aqueous media under mild conditions[J].RSC Adv,2015,5(34):26941-26948.
[3]Bispo C,Oliveria Vigier K D,Sardo M,et al.Catalytic dehydration of fructose to HMF over sulfonic acid functionalized periodic mesoporous organosilicas:role of the acid density[J].Catal Sci Technol,2014,4(8):2235-2240.
[4]Zhang Y L,Pan J M,Yan Y S,et al.Synthesis and evaluation of stable polymeric solid acid based on halloysite nanotubes for conversion of one-pot cellulose to 5-hydroxymethylfurfural[J].RSC Adv,2014,4(45):23797-23806.
[5]Teimouria A,Mazaheria M,Chermahini A N,et al.Catalytic conversion of glucose to 5-hydroxymethylfurfural(HMF)using nano-POM/nano-Zr O2/nano-γ-Al2O3[J].J Taiwan Inst Chem E,2015,49:40-50.
[6]Liu J,Li H,Liu Y C,et al.Catalytic conversion of glucose to 5-hydroxymethylfurfural over nano-sized mesoporous Al2O3-B2O3solid acids[J].Catal Commun,2015,62:19-23.
[7]Gallo J M R,Alonso D M,Mellmer M A,et al.Production and upgrading of 5-hydroxymethyl-furfural using heterogeneous catalysts and biomass-derived solvents[J].Green Chem,2013,15(1):85-90.
[8]Ordomsky V V,van der Schaaf J,Schouten J C,et al.The effect of solvent addition on fructose dehydration to 5-hydroxymethylfurfural in biphasic system over zeolites[J].J Catal,2012,287(1):68-75.
[9]Karimi B,Mirzaei H M.The influence of hydrophobic/hydrophilic balance of the mesoporous solid acid catalysts in the selective dehydration of fructose into HMF[J].RSC Adv,2013,3(43):20655-20661.
[10]Yan H P,Yang Y,Tong D M,et al.Catalytic conversion of glucose to 5-hydroxymethyl-furfural over SO42-/Zr O2and SO42-/Zr O2-Al2O3solid acid catalysts[J].Catal Commun,2009,10(11):1558-1563.
[11]Kourieh R,Rakic V,Bennici S,et al.Relation between surface acidity and reactivity in fructose conversion into 5-HMF using tungstated zirconia catalysts[J].Catal Commun,2013,30(1):5-13.
[12]Carlini C,Patrono P,Raspolli Galletti A M,et al.Heterogeneous catalysts based on vanadyl phosphate for fructose dehydration to5-hydroxymethyl-2-furaldehyde[J].Appl Catal A-Gen,2004,275(1/2):111-118.
[13]Fan C Y,Guan H Y,Zhang H,et al.Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt[J].Biomass Bioenerg,2011,35(7):2659-2665.
[14]Nakajima K,Baba Y,Noma R,et al.Nb2O5·H2O as a heterogeneous catalyst with water-tolerant lewis acid sites[J].J Am Chem Soc,2011,133(12):4224-4227.
[15]Ordomsky V V,Sushkevich V L,Schouten J C,et al.Glucose dehydration to 5-hydroxymethylfurfural over phosphate catalysts[J].J Catal,2013,300(3):37-46.
[16]Wang Y H,Tong X L,Yan Y T,et al.Efficient and selective conversion of hexose to 5-hydroxymethylfurfural with tinzirconium-containing heterogeneous catalysts[J].Catal Commun,2014,50(18):38-43.
[17]Nowak I,Ziolek M.Niobium compounds:preparation,characterization,and application in heterogeneous catalysis[J].Chem Rev,1999,99(12):3603-3624.
[18]Ordomsky V V,van der Schaaf J,Schouten J C,et al.Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system[J].Chem Sus Chem,2012,5(9):1812-1819.
[19]Dunn E F,Liu D J,Chen E Y X.Role of N-heterocyclic carbenes in glucose conversion into HMF by Cr catalysts in ionic liquids[J].Appl Catal A-Gen,2013,460-461(11):1-7.
[20]Sun P,Long X D,He H,et al.Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate[J].Chem Sus Chem,2013,6(11):2190-2197.
[21]Cranston R W,Inkley F A.The determination of pore structures from nitrogen adsorption isotherms[J].Adv Catal,1957,9:143-154.
[22]Corma A.Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions[J].Chem Rev,1995,95(3):559-614.
[23]Jain A,Shore A M,Jonnalagadda S C,et al.Conversion of fructose,glucose and sucrose to 5-hydroxymethyl-2-furfural over mesoporous zirconium phosphate catalyst[J].Appl Catal A-Gen,2015,489:72-76.
[24]Rocha A S,Forrester A M S,de la Cruz M H C,et al.Comparative performance of niobium phosphates in liquid phase anisole benzylation with benzyl alcohol[J].Catal Commun,2008,9(10):1959-1965.
[24]Faungnawakij K,Kikuchi R,Matsui T,et al.A comparative study of solid acids in hydrolysis and steam reforming of dimethyl ether[J].Appl Catal A,2007,333(1):114-121.
[25]Jia S Y,Xu Z W,Zhang Z C.Catalytic conversion of glucose in dimethylsulfoxide/water binary mix with chromium trichloride:role of water on the product distribution[J].Chem Eng J,2014,254(1):333-339.