Reaction Kinetics, Mechanisms and Catalysis

, Volume 128, Issue 1, pp 523–538 | Cite as

Sulfonic acid-functionalized hierarchical SAPO-34 for fructose dehydration to 5-hydroxymethylfurfural

  • Zhonghai Liu
  • Zhenzhu Sun
  • Dongling Qin
  • Gang YangEmail author


Sulfonic acid-functionalized hierarchical SAPO-34 (S1-SAPO-34-SO3H) was prepared by post-grafting 3-mercaptopropyltriethoxysilane, and the sulfonic acid group was then oxidized by H2O2. The obtained catalysts were characterized by XRD, SEM, FTIR, TG, nitrogen adsorption, XRF, and acid–base titration. The acidity of the modified SAPO-34 increased, which confirmed the success of grafting. The catalytic properties during the dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) were investigated. The yield of 5-HMF was up to 72%, and a 34% increase was found compared with the case of SAPO-34. The findings were discussed and attributed to the synergistic effects caused by both the acid groups and the mesopores. More basic investigations with regard to the conditions, including the reaction time, temperature, solvent, load and regeneration, are needed.


S1-SAPO-34-SO3Fructose Dehydration 5-Hydroxymethylfurfural 



We make a great acknowledgment for the financial support of this work by National Science and Technology of China (No. 2013BAE11B03) and Prospective Joint Research Project of Industry, University and Research in Jiangsu Province (No. BY2016005-11).

Supplementary material

11144_2019_1603_MOESM1_ESM.docx (599 kb)
Supplementary material 1 (DOCX 599 kb)


  1. 1.
    Mesa L, Lopez N, Cara C, Castro E (2016) Techno-economic evaluation of strategies based on two steps organosolv pretreatment and enzymatic hydrolysis of sugarcane bagasse for ethanol production. Renew Energy 86:270–279CrossRefGoogle Scholar
  2. 2.
    Peng X, Nges I, Liu J (2016) Improving methane production from wheat straw by digestate liquor recirculation in continuous stirred tank processes. Renew Energy 85:12–18CrossRefGoogle Scholar
  3. 3.
    Zhang Y, Wang J, Li X, Liu X, Xia Y, Hu B (2015) Direct conversion of biomass-derived carbohydrates to 5-hydroxymethylfurural over water-tolerant niobium-based catalysts. Fuel 139:301–307CrossRefGoogle Scholar
  4. 4.
    Rao K, Souzanchi S, Yuan Z, Ray M, Xu C (2017) Simple and green route for preparation of tin phosphate catalysts by solid-state grinding for dehydration of glucose to 5-hydroxymethylfurfural (HMF). RSV Adv 7:48501–48511CrossRefGoogle Scholar
  5. 5.
    Gomes F, Mendes F, Souza M (2017) Synthesis of 5-hydroxymethylfurfural from fructose catalyzed by phosphotungstic acid. Catal Today 279:296–304CrossRefGoogle Scholar
  6. 6.
    Irantzu S, Yury Y, Gorbanev S, Siva S, Rolf W, Anders R (2013) Catalytic performance of zeolite-supported Vanadia in the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran. ChemcatChem 5:284–293CrossRefGoogle Scholar
  7. 7.
    Deng J, Liu X, Li C, Jiang Y, Zhu J (2015) Synthesis and properties of a bio-based epoxy resin from 2,5-furandicarboxylic acid (FDCA). RSC Adv 5:15930–15939CrossRefGoogle Scholar
  8. 8.
    Qin Y, Zong M, Lou W, Li N (2016) Biocatalytic upgrading of 5-hydroxymethylfurfural (HMF) with levulinic acid to HMF levulinate in biomass-derived solvents. ACS Sustain Chem Eng 4:4050–4054CrossRefGoogle Scholar
  9. 9.
    Li H, Saravanamurugan S, Yang S, Riisager A (2016) Direct transformation of carbohydrates to the biofuel 5-ethoxymethylfurfural by solid acid catalysts. Green Chem 18:726–734CrossRefGoogle Scholar
  10. 10.
    Stephanie G, David M, Elif I, James A (2012) A roadmap for conversion of lignocellulosic biomass to chemicals and fuels. Curr Opin Chem Eng 1:218–224CrossRefGoogle Scholar
  11. 11.
    Sun X, Wang J, Chen J, Zheng J, Shao H, Huang C (2018) Dehydration of fructose to 5-hydroxymethylfurfural over MeSAPOs synthesized from bauxite. Microporous Mesoporous Mater 259:238–243CrossRefGoogle Scholar
  12. 12.
    Morales I, Gonzale J, Lopez A, Torres P (2014) Glucose dehydration to 5-hydroxymethylfurfural on zirconium containing mesoporous MCM-41 silica catalysts. Fuel 265:265–271CrossRefGoogle Scholar
  13. 13.
    Yang F, Li Y, Zhang Q, Sun X, Fan H, Xu N, Li G (2015) Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO42−/MxOy solid superacid catalyst. Carbohyd Polym 131:9–14CrossRefGoogle Scholar
  14. 14.
    Leshkov Y, Dumesic J (2009) Solvent effects on fructose dehydration to 5-hydroxymethylfurfural in biphasic systems saturated with inorganic salts. Top Catal 52:297–303CrossRefGoogle Scholar
  15. 15.
    Enomoto K, Hosoya T, Miyafuji H (2018) High-yield production of 5-hydroxymethylfurfural from d-fructose, d-glucose, and cellulose by its in situ removal from the reaction system. Cellulose 4:2249–2257CrossRefGoogle Scholar
  16. 16.
    Gallo J, Alonso M, Mellmer M, Dumestic J (2012) Production and upgrading of 5-hydroxymethylfurfural using heterogeneous catalysts and biomass-derived solvents. Green Chem 15:85–91CrossRefGoogle Scholar
  17. 17.
    Jin H, Ansari B, Park S (2015) Sulfonic acid functionalized mesoporous ZSM-5: synthesis, characterization and catalytic activity in acidic catalysis. Catal Today 245:116–121CrossRefGoogle Scholar
  18. 18.
    Yang F, Liu Q, Bai X, Du Y (2011) Conversion of biomass into 5-hydroxymethylfurfural using solid acid catalyst. Bioresour Technol 102:3424–3429CrossRefGoogle Scholar
  19. 19.
    Qi X, Watanable M, Aida T, Smith R (2008) Catalytic dehydration of fructose into 5-hydroxymethylfurfural by ion-exchange resin in mixed-aqueous system by microwave heating. Green Chem 10:799–805CrossRefGoogle Scholar
  20. 20.
    Li X, Xia Q, Nguyen V, Peng KH, Liu X, Essayem N, Wang Y (2016) High yield production of HMF from carbohydrates over silica–alumina composite catalysts. Catal Sci Technol 6:7586–7597CrossRefGoogle Scholar
  21. 21.
    Bhaumik P, Dhepe P (2013) Influence of properties of SAPO’s on the one-pot conversion of mono-, di- and poly-saccharides into 5-hydroxymethylfurfural. RSC Adv 3:17156–17165CrossRefGoogle Scholar
  22. 22.
    Pande A, Niphadkar P, Pandare K, Bokade V (2018) Acid modified H-USY zeolite for efficient catalytic transformation of fructose to 5-HydroxymethylFurfural (Biofuel Precursor) in methyl isobutyl ketone-water biphasic system. Energy Fuels 32:3783–3794CrossRefGoogle Scholar
  23. 23.
    Rac V, Rakic V, Stosic D, Otman O, Aline A (2014) Hierarchical ZSM-5, Beta and USY zeolites: Acidity assessment by gas and aqueous phase calorimetry and catalytic activity in fructose dehydration reaction. Microporous Mesoporous Mater 194:126–134CrossRefGoogle Scholar
  24. 24.
    Bhanja P, Modak A, Sauvik C, Asim B (2017) Bifunctionalized mesoporous SBA-15: a new heterogeneous catalyst for the facile synthesis of 5-hydroxymethylfurfural. ACS Sustain Chem Eng 5:2763–2781CrossRefGoogle Scholar
  25. 25.
    Zhou L, Liu Z, Shi M, Du S, Su Y, Yang X, Xu J (2013) Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose. Carbohyd Polym 98:146–151CrossRefGoogle Scholar
  26. 26.
    Karimi B, Mirzaei H, Behzadnia H, Vali H (2015) Novel ordered mesoporous carbon based sulfonic acid as an efficient catalyst in the selective dehydration of fructose into 5-HMF: the role of solvent and surface chemistry. ACS App Mater Interfaces 7:19050–19059CrossRefGoogle Scholar
  27. 27.
    Zhang L, Huang Y (2016) New insights into formation of molecular sieve SAPO-34 for MTO reactions. J Phys Chem 120:25945–25957Google Scholar
  28. 28.
    Zhang L, Xi G, Chen Z, Qi Z, Wang X (2017) Enhanced formation of 5-HMF from glucose using a highly selective and stable SAPO-34 catalyst. Chem Eng J 307:877–883CrossRefGoogle Scholar
  29. 29.
    Wang C, Wang J, Shen M, Wang W, Li W (2017) The effect of sulfate species on the activity of NH3-SCR over Cu/SAPO-34. Appl Catal B-Environ 204:239–249CrossRefGoogle Scholar
  30. 30.
    Li S, Zong Z, Huang Y, Yu M, Carreon M (2015) SAPO-34 membranes for N2/CH4 separation: preparation, characterization, separation performance and economic evaluation. J Membr Sci 487:141–151CrossRefGoogle Scholar
  31. 31.
    Yang H, Liu X, Lu G, Wang Y (2016) Synthesis of SAPO-34 nanoplates via hydrothermal method. Microporous Mesoporous Mater 225:144–153CrossRefGoogle Scholar
  32. 32.
    Liu B, Zhang Z (2015) Catalytic conversion of biomass into chemicals and fuels over magnetic catalysts. ACS Catal 6:326–339CrossRefGoogle Scholar
  33. 33.
    Wang J, Zhu L, Cui H, Zhang Y (2016) Fructose dehydration to 5-HMF over three sulfonated carbons: effect of different pore structures. J Chem Technol Biotechnol 92:1454–1463CrossRefGoogle Scholar
  34. 34.
    Mbaraka I, Radu D, Lin V, Shanks B (2003) Organosulfonic acid-functionalized mesoporous silicas for the esterification of fatty acid. J Catal 219:329–336CrossRefGoogle Scholar
  35. 35.
    Di C, Li X, Wang P, Li Z, Fan B (2017) Green and efficient dry gel conversion synthesis of SAPO-34 catalyst with plate-like morphology. Pet Sci 14:203–213CrossRefGoogle Scholar
  36. 36.
    Ren S, Liu G, Wu X, Chen X, Liu Z, Wu M, Sun Y (2017) Enhanced MTO performance over acid treated hierarchical SAPO-34. Chin J Catal 38:123–130CrossRefGoogle Scholar
  37. 37.
    Saravanamurugan S, Prasetyanto Sujandi, Park S (2008) Liquid-phase reaction of 20-hydroxyacetophenone and benzaldehyde over SO3H-SBA-15 catalysts: influence of microwave and thermal effects. Microporous Mesoporous Mater 112:97–107CrossRefGoogle Scholar
  38. 38.
    Shalmani F, Halladj R, Askari S (2017) Physicochemical characterization to assess Ni and Zn incorporation into zeotype SAPO-34 nanoparticles synthesized with different mixing methods through ultrasound-promoted crystallization. RSC Adv 7:26756–26769CrossRefGoogle Scholar
  39. 39.
    Yang X, Wei Y, Su Y, Zhou L (2010) Characterization of fused Fe–Cu based catalyst for higher alcohols synthesis and DRIFTS investigation of TPSR. Fuel Process Technol 91:1168–1173CrossRefGoogle Scholar
  40. 40.
    Yang Z, Qi W, Huang R, Fang J, Su R, He Z (2016) Functionalized silica nanoparticles for conversion of fructose to 5-hydroxymethylfurfural. Chem Eng J 296:209–216CrossRefGoogle Scholar
  41. 41.
    Wang L, Zhang L, Li H (2019) High selective production of 5-hydroxymethylfurfural from fructose by sulfonic acid functionalized SBA-15 catalyst. Compos B 156:88–94CrossRefGoogle Scholar
  42. 42.
    Wang C, Yang M, Zhang W, Liu Z (2016) Organophosphorous surfactant-assistant synthesis of SAPO-34 molecular sieve with special morphology and improved MTO performance. RSC Adv 6:47864–47872CrossRefGoogle Scholar
  43. 43.
    Solis Maldonado C, Javier RDLR, Lucio-Ortiz CJ (2016) Synthesis and characterization of functionalized alumina catalysts with thiol and sulfonic groups and their performance in producing 5-hydroxymethylfurfural from fructose. Fuel 198:134–144CrossRefGoogle Scholar
  44. 44.
    Wang K, Zhang YL, Li CX, Yan YS (2018) Facile synthesis of hierarchical porous solid catalysts with acid–base bifunctional active sites for the conversion of cellulose to 5-hydroxymethylfurfural. New J Chem 42:18084–18095CrossRefGoogle Scholar
  45. 45.
    Gan LH, Shen TR, Wang S (2019) Sulfonated lignin-derived ordered mesoporous carbon with highly selective and recyclable catalysis for the conversion of fructose into 5-hydroxymethylfurfural. Appl Catal A 25:132–143CrossRefGoogle Scholar
  46. 46.
    Girisuta B, Dussan K, Haverty K, Leahy J, Hayes M (2013) A kinetic study of acid catalysed hydrolysis of sugar cane bagasse to levulinic acid. Chem Eng J 217:61–70CrossRefGoogle Scholar
  47. 47.
    Shao H, Chen J, Zhao J, Wang J (2015) Development of MeSAPO-5 molecular sieves from attapulgite for dehydration of carbohydrates. Ind Eng Chem Res 54:1470–1477CrossRefGoogle Scholar
  48. 48.
    Hafizi H, Chermahini A, Saraji M (2016) The catalytic conversion of fructose into HMF over acid-functionalized KIT-6, an ordered mesoporous silica. Che Eng J 294:380–388CrossRefGoogle Scholar
  49. 49.
    Cao Z, Li M, Chen Y (2018) Dehydration of fructose into 5-hydroxymethylfurfural in a biphasic system using edta as a temperature-responsive catalyst. Appl Catal A 569:93–100CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical EngineeringNanjing Tech UniversityNanjingChina

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