Abstract
Biomass is an attractive source of carbohydrates that can be converted to fuels and fine chemicals. Acid-catalyzed alcoholysis of biomass derivatives provides alkyl levulinates, which are fuel bioadditives, intermediates in the synthesis of drugs and agrochemicals. In this work, we developed a one-pot route to obtain alkyl levulinates using Sn(II) exchanged Keggin heteropolyacids (i.e., H3PW12O40, H3PMo12O40, and H4SiW12O40) as catalysts, in alcoholysis reactions of various carbohydrates. All the catalysts were characterized by FT-IR, XRD, EDS/SEM, TG/DSC, and BET analysis. The tin(II) silicotungstate was the most active and selective catalyst. After 2 h of reaction carried out at 423 K, an almost complete conversion was achieved on the ethanolysis of the fructose, sucrose and inulin, which gave high yields of ethyl levulinate (ca. 78, 71 and 61 mol%, respectively). In all reactions, 5-ethoxymethylfurfural was always the secondary product. Maltose, galactose, and glucose were almost unreactive. The effects of main parameters of reaction, such as temperature, catalyst load, and type of alcohols were assessed. The Sn2SiW12O40 catalyst was easily recovered and successfully reused for 7 cycles, without loss activity.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alonso DM, Gallo JMR, Mellmer MA, Wettstein SG, Dumesic JA (2013) Direct conversion of cellulose to levulinic acid and gamma-valerolactone using solid acid catalysts. Catal Sci Technol 3(4):927–931. https://doi.org/10.1039/C2CY20689G
Avhad MR, Marchetti JM (2016) Innovation in solid heterogeneous catalysis for the generation of economically viable and ecofriendly biodiesel: a review. Catal Rev 58(2):157–208. https://doi.org/10.1080/01614940.2015.1103594
Bajuk-Bogdanovi D, Holclajtner-Antunonovi I, Todorovi M, Mio UB, Zakakrzewska J (2008) A study of 12-tungstosilicic and 12-molybdophosphoric acids in solution. J Serb Chem Soc 73(2):197. https://doi.org/10.2298/JSC0802197B
Chen H, Yu B, Jin S (2011) Production of levulinic acid from steam exploded rice straw via solid superacid, S2O8 2−/ZrO2–SiO2–Sm2O3. Bioresour Technol 102(3):3568–3570. https://doi.org/10.1016/j.biortech.2010.10.018
Chen X, Liu Y, Wang H, Yuan M, Wang X, Chen Y (2014) Effect of Cs content on CsxH5−xPMo10V2O40 properties and oxidative catalytic activity on starch oxidation by H2O2. RSC Adv 4(22):11232–11239. https://doi.org/10.1039/C3RA47122E
Coronel NC, Da Silva MJ (2018) Lacunar keggin heteropolyacid salts: soluble, solid and solid-supported catalysts. J Clust Sci 29(2):195–205. https://doi.org/10.1007/s10876-018-1343-0
Da Silva MJ, Chaves DM (2018) SnCl2-catalyzed synthesis of carbamates from renewable origin alcohols. Chem Pap 72(5):1169–1180. https://doi.org/10.1007/s11696-017-0349-7
Da Silva MJ, De Oliveira CM (2018) Catalysis by Keggin Heteropolyacid Salts. Curr Catal 7(1):26–34. https://doi.org/10.2174/2211544707666171219161414
Da Silva MJ, Liberto NA (2016) Soluble and solid supported Keggin heteropolyacids as catalysts in reactions for biodiesel production: challenges and recent advances. Curr Org Chem 20(12):1263–1283. https://doi.org/10.2174/1385272819666150907193100
Da Silva MJ, Teixeira MG (2017) An unexpected behavior of H3PMo12O40 heteropolyacid catalyst on the biphasic hydrolysis of vegetable oils. RSC Adv 7(14):8192–8199. https://doi.org/10.1039/C6RA27287H
Da Silva MJ, Rodrigues FA, Júlio AA (2017a) SnF2-catalyzed glycerol ketalization: a friendly environmentally process to synthesize solketal at room temperature over on solid and reusable Lewis acid. Chem Eng J 307:828–835. https://doi.org/10.1016/j.cej.2016.09.002
Da Silva MJ, Vilanculo CB, Teixeira MG, Júlio AA (2017b) Catalysis of vegetable oil transesterification by Sn (II)-exchanged Keggin heteropolyacids: bifunctional solid acid catalysts. React Kinet Mech Catal 122(2):1011–1030. https://doi.org/10.1007/s11144-017-1258-z
Démolis A, Essayem N, Rataboul F (2014) Synthesis and applications of alkyl levulinates. ACS Sustain Chem Eng 2(6):1338–1352. https://doi.org/10.1021/sc500082n
Dong X, Yu C, Wang D, Zhang Y, Wu P, Hu H, Xue G (2017) Cu and Fe-doped monolacunary tungstosilicate catalysts with efficient catalytic activity for benzyl alcohol oxidation and simulation gasoline desulfurization. Mater Res Bull 85:152–160. https://doi.org/10.1016/j.materresbull.2016.09.014
Ferreira AB, Cardoso AL, Da Silva MJ (2013) Novel and highly efficient SnBr 2-catalyzed esterification reactions of fatty acids: the notable anion ligand effect. Catal Lett 143(11):1240–1246. https://doi.org/10.1007/s10562-013-1089-0
Garcés D, Díaz E, Ordóñez S (2017) Aqueous phase conversion of hexoses into 5-hydroxymethylfurfural and levulinic acid in the presence of hydrochloric acid: mechanism and kinetics. Ind Eng Chem Res 56(18):5221–5230. https://doi.org/10.1021/acs.iecr.7b00952
Howard J, Rackemann DW, Bartley JP, Samori C, Doherty WOS (2018) Conversion of sugar cane molasses to 5-hydroxymethylfurfural using molasses and bagasse-derived catalysts. ACS Sustain Chem Eng 6(64):4531–4538. https://doi.org/10.1021/acssuschemeng.7b02746
Jadhav AH, Kim H, Hwang IT (2013) An efficient and heterogeneous recyclable silicotungstic acid with modified acid sites as a catalyst for conversion of fructose and sucrose into 5-hydroxymethylfurfural in superheated water. Bioresour Technol 132:342–350. https://doi.org/10.1016/j.biortech.2013.01.030
Jiang L, Zhou L, Chao J, Zhao H, Lu T, Su Y, Yang X, Xu J (2018) Direct catalytic conversion of carbohydrates to methyl levulinate: synergy of solid Brønsted acid and Lewis acid. Appl Catal B-Environ 220:589–596. https://doi.org/10.1016/j.apcatb.2017.08.072
Kumar CR, Rao KTV, Prassad PSS, Lingaiah N (2011) Tin exchanged heteropoly tungstate: an efficient catalyst for benzylation of arenes with benzyl alcohol. J Mol Catal A: Chem 337(1–2):17–24. https://doi.org/10.1016/j.molcata.2011.01.008
Kumari PK, Rao BS, Padmakar D, Pasha N, Lingaiah N (2018) Lewis acidity induced heteropoly tungustate catalysts for the synthesis of 5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural. Mol Catal 448:108–115. https://doi.org/10.1016/j.mcat.2018.01.034
Kuo C-H, Poyraz AS, Jin L, Meng Y, Pahalagedara L, Chen S-Y, Kriz DA, Guild C, Gudz A, Suib SL (2014) Heterogeneous acidic TiO2 nanoparticles for efficient conversion of biomass derived carbohydrates. Green Chem 16(2):785–791. https://doi.org/10.1039/C3GC40909K
Lewkowski J (2001) Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its derivatives. Arkivoc i:17–54
Li H, Fang Z, Luo J, Yang S (2017) Direct conversion of biomass components to the biofuel methyl levulinate catalyzed by acid-base bifunctional zirconia-zeolites. Appl Catal B Environ 200:182–191. https://doi.org/10.1016/j.apcatb.2016.07.007
Liu Y, Liu C-L, Wu H-Z, Dong W-S (2013) An efficient catalyst for the conversion of fructose into methyl levulinate. Catal Lett 143(12):1346–1353. https://doi.org/10.1007/s10562-013-1094-3
Liu A, Liu B, Wang Y, Ren R, Zhang Z (2014) Efficient one-pot synthesis of 5-ethoxymethylfurfural from fructose catalyzed by heteropolyacid supported on K-10 clay. Fuel 117:68–73. https://doi.org/10.1016/j.fuel.2013.09.072
Méndez L, Torviso R, Pizzio L, Blanco M (2011) 2-Methoxynaphthalene acylation using aluminum or copper salts of tungstophosphoric and tungstosilicic acids as catalysts. Catal Today 173(1):32–37. https://doi.org/10.1016/j.cattod.2011.03.028
Mickek-Llnicka A (2009) The role of water in the catalysis on solid heteropolyacids. J Mol Catal A: Chem 308(1–2):1–4. https://doi.org/10.1016/j.molcata.2009.04.003
Mika LT, Cséfalvay E, Nemeth A (2018) Catalytic conversion of carbohydrates to initial platform chemicals: chemistry and sustainability. Chem Rev 118(2):505–613. https://doi.org/10.1021/acs.chemrev.7b00395
Okuhara T, Mizuno N, Misono M (1996) Catalytic chemistry of heteropoly compounds. Adv Catal 41:113–252. https://doi.org/10.1016/S0360-0564(08)60041-3
Parent MA, Moffat JB (1996) Metal-oxygen cluster compounds (heteropoly oxometalates) of 1B and 3B monovalent cations and their micropore structure. Langmuir 12(15):3733–3739. https://doi.org/10.1021/la9601667
Pileidis FD, Titirici MM (2016) Levulinic acid biorefineries: new challenges for efficient utilization of biomass. Chemsuschem 9(6):562–582. https://doi.org/10.1002/cssc.201501405
Pizzio LR, Blanco MN (2007) A contribution to the physicochemical characterization of nonstoichiometric salts of tungstosilicic acid. Microporous Mesoporous Mater 103(1–3):40–47. https://doi.org/10.1016/j.micromeso.2007.01.036
Pizzio LR, Caceres CV, Blanco MN (2002) Tungstophosphoric acid immobilized in polyvinyl alcohol hydrogel beads as heterogeneous catalyst. Stud Surf Sci Catal 143:731–738. https://doi.org/10.1016/s0167-2991(00)80716-8
Pulidindi IN, Kim TH (2018) Conversion of levulinic acid from various herbaceous biomass species using hydrochloric acid and effects of particle size and delignification. Energies 11(3):1. https://doi.org/10.3390/en11030621
Rao BS, Kumari PK, Lakshmi DD, Lingaiah N (2018) One pot selective transformation of biomass derived chemicals towards alkyl levulinates over titanium exchanged heteropoly tungstate catalysts. Catal Today 309:269–275. https://doi.org/10.1016/j.cattod.2017.05.040
Shimizu K-I, Niimi K, Satsuma A (2008) Polyvalent-metal salts of heteropolyacid as efficient heterogeneous catalysts for Friedel–Crafts acylation of arenes with carboxylic acids. Catal Commun 9(6):980–983. https://doi.org/10.1016/j.catcom.2007.09.030
Shimizu K-I, Furukawa H, Kobayashi N, Itay Y, Satsuma A (2009) Effects of Brønsted and Lewis acidities on activity and selectivity of heteropolyacid-based catalysts for hydrolysis of cellobiose and cellulose. Green Chem 11(10):1627–1632. https://doi.org/10.1039/B913737H
Trombettoni V, Lanari D, Prinsen P, Luque R, Marrocchi A, Vaccaro L (2018) Recent advances in sulfonated resin catalysts for efficient biodiesel and bio-derived additives production. Prog Energ Combust 65:136–162. https://doi.org/10.1016/j.pecs.2017.11.001
Vakulenko A, Dobrovolsky Y, Leonova L, Karelin A, Kolesnikova A, Bukun N (2000) Protonic conductivity of neutral and acidic silicotungstates. Solid State Ion 136:285–290. https://doi.org/10.1016/S0167-2738(00)00404-5
Welfle A (2017) Balancing growing global bioenergy resource demands-Brazil’s biomass potential and the availability of resource for trade. Biomass Bioener 105:83–95. https://doi.org/10.1016/j.biombioe.2017.06.011
Yang Y, Qi Y, Yuan X, Shen J, Kim J (2005) Direct synthesis, characterization and catalytic application of SBA-15 containing heteropolyacid H3PW12O40. J Mol Catal A: Chem 229(1–2):199–205. https://doi.org/10.1016/j.molcata.2004.11.024
Yang Y, Abu-Omar MM, Hu C (2012) Heteropolyacid catalyzed conversion of fructose, sucrose, and inulin to 5-ethoxymethylfurfural, a liquid biofuel candidate. Appl Energy 99:80–84. https://doi.org/10.1016/j.apenergy.2012.04.049
Yoshimune M, Yoshinaga Y, Okuhara T (2002) Effect of alkaline metal on microporosity of acidic alkaline salts of 12-tungstophosphoric acid. Microporous Mesoporous Mater 51(2):165–174. https://doi.org/10.1016/S1387-1811(01)00480-2
Yu F, Zhong R, Chong H, Smet M, Dehaen W, Sels BF (2017) Fast catalytic conversion of recalcitrant cellulose into alkyl levulinates and levulinic acid in the presence of soluble and recoverable sulfonated hyperbranched poly (arylene oxindole) s. Green Chem 19(1):153–163. https://doi.org/10.1039/C6GC02130A
Zhang L, Xi G, Yu K, Yu H, Wang X (2017) Furfural production from biomass-derived carbohydrates and lignocellulosic residues via heterogeneous acid catalysts. Ind Crops Prod 98:68–75. https://doi.org/10.1016/j.indcrop.2017.01.014
Zhang X, Li Y, Xue L, Wang S, Wang X, Jiang Z (2018) Catalyzing cascade production of methyl levulinate from polysaccharides using heteropolyacids HnPW11MO39 with Brønsted/Lewis acidic sites. ACS Sustain Chem Eng 6(1):165–176. https://doi.org/10.1021/acssuschemeng.7b02042
Zhao S, Xu G, Chang J, Chang C, Bai J, Fang S, Liu Z (2015a) Direct production of ethyl levulinate from carbohydrates catalyzed by H-ZSM-5 supported phosphotungstic acid. BioResources 10(2):2223–2234. https://doi.org/10.15376/biores.10.2.2223-2234
Zhao S, Xu G, Chang C, Fang S, Liu Z, Du F (2015b) Direct conversion of carbohydrates into ethyl levulinate with potassium phosphotungstate as an efficient catalyst. Catalysts 5(4):1897–1910. https://doi.org/10.3390/catal5041897
Zhou L, Zou H, Nan J, Wu L, Yang X, Su Y, Lu T, Xu J (2014) Conversion of carbohydrate biomass to methyl levulinate with Al2(SO4)3 as a simple, cheap and efficient catalyst. J Catal Commun 50:13–16. https://doi.org/10.1016/j.catcom.2014.02.021
Zhu S, Gao X, Dong F, Zhu Y, Zheng H, Li Y (2013) Design of a highly active silver-exchanged phosphotungstic acid catalyst for glycerol esterification with acetic acid. J Catal 306:155–163. https://doi.org/10.1016/j.jcat.2013.06.026
Acknowledgments
The authors are grateful for the financial support from CAPES, CNPq, and FAPEMIG (Brazil). This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES)—Finance Code 001.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Pinheiro, P.F., Chaves, D.M. & da Silva, M.J. One-pot synthesis of alkyl levulinates from biomass derivative carbohydrates in tin(II) exchanged silicotungstates-catalyzed reactions. Cellulose 26, 7953–7969 (2019). https://doi.org/10.1007/s10570-019-02665-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-019-02665-w