Skip to main content
SpringerLink
Log in

Synthesis of 5-hydroxymethylfurfural from fructose catalyzed by sulfonated carbon-based solid acid

  • Original Article
  • Published:
Biomass Conversion and Biorefinery Aims and scope Submit manuscript

Abstract

Sulfonated carbon-based solid acid catalyst (AC-SO3H) was prepared by the sulfhydrylation and sulfonation of activated carbon (AC) with 3-thiol-propyl trimethoxy silane and sulfuric acid successively. The prepared solid acid catalyst was characterized by infrared spectroscopy (IR), thermogravimetric analysis (TGA), elemental analysis (EA), X-ray powder diffraction (XRD), and Brunauer-Emmet-Teller (BET) specific surface area analysis, and the acid density of AC-SO3H was determined by neutralization titration. AC-SO3H was then employed to catalyze the synthesis of 5-hydroxymethylfurfural (5-HMF) via the dehydration of fructose. The influence of the type of support, sulfonating agent and their concentration, catalyst amount, reaction temperature, and time was investigated. It was found that fructose was converted into 5-HMF with excellent selectivity and stability. The yield of 5-HMF reached up to 100% under the optimized conditions. The solid acid catalyst was reused without noticeable deactivation. The yield of 5-HMF was still up to 94.3% after 4 cycles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 2
Scheme 3
Fig. 5

Similar content being viewed by others

References

  1. Bhatia SK, Bhatia RK, Jeon JM, Pugazhendhi A, Awasthi MK, Kumar D, Kumar G, Yoon JJ, Yang YH (2021) An overview on advancements in biobased transesterification methods for biodiesel production: oil resources, extraction, biocatalysts, and process intensification technologies. Fuel 285:146–151

    Google Scholar 

  2. Agar DA, Svanberg M, Lindh I, Athanassiadis D (2020) Surplus forest biomass – The cost of utilisation through optimised logistics and fuel upgrading in northern Sweden. J Clean Prod 275:123151–123179

    Google Scholar 

  3. Chiappe C, Douton MJR, Mezzetta A, Guazzelli L, Pomelli CS, Assanelli G, Angelis AD (2018) Exploring and exploiting different catalytic systems for the direct conversion of cellulose into levulinic acid. New J Chem 42:1845–1852

    Google Scholar 

  4. Tiong YW, Yap CL, Gan S, Yap WSP (2020) Kinetic and thermodynamic studies of oil palm mesocarp fiber cellulose conversion to levulinic acid and upgrading to ethyl levulinate via indium trichloride-ionic liquids. Renew Energ 146:932–943

    Google Scholar 

  5. Fan GZ, Wang YX, Hu ZX, Yan JT, Li JF, Song GS (2018) Synthesis of 5-hydroxymethyl furfural from cellulose via a two-step process in polar aprotic solvent. Carbohyd Polym 200:529–535

    Google Scholar 

  6. Daorattanachai P, Khemthong P, Viriya-Empikul N, Laosiripojana N, Faungnawakij K (2012) Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot compressed water. Carbohyd Res 363:58–61

    Google Scholar 

  7. Peng WH, Lee YY, Wu C, Wu KCW (2012) Acid–base bi-functionalized, large-pored mesoporous silica nanoparticles for cooperative catalysis of one-pot cellulose-to-HMF conversion. J Mater Chem 22:23181–23185

    Google Scholar 

  8. Testa ML, Miroddi G, Russo M, Parola VL, Marci G (2020) Dehydration of fructose to 5-HMF over acidic TiO2 catalysts. Materials 13:1178–1190

    Google Scholar 

  9. Dou YW, Zhou S, Oldani C, Fang WH, Cao Q (2018) 5-Hydroxymethylfurfural production from dehydration of fructose catalyzed by Aquivion@silica solid acid. Fuel 214:45–54

    Google Scholar 

  10. Cheng LZW, Everhart J, Tsilomelekis G, Nikolakis V, Saha B, Vlachos D (2018) Structural analysis of humins formed in the brnsted acid catalyzed dehydration of fructose. Green Chem 20:997–1006

    Google Scholar 

  11. Yan DX, Wang GY, Gao K, Lu XM, Xin JY, Zhang SJ (2018) One-pot synthesis of 2,5-furandicarboxylic acid from fructose in ionic liquids. Ind Eng Chem Res 57:1851–1858

    Google Scholar 

  12. Song YL, Wang XC, Qu YS, Huang CP, Li YX, Chen BH (2016) Efficient dehydration of fructose to 5-hydroxy-methylfurfural catalyzed by heteropolyacid salts. Catalysts 6:170–172

    Google Scholar 

  13. Ma YB, Qing SJ, Wang L, Islam N, Guan SZ, Gao Z, Mamat X, Li HY, Eli W, Wang TF (2015) Production of 5-hydroxymethylfurfural from fructose by a thermo-regulated and recyclable brønsted acidic ionic liquid catalyst. RSC Adv 5:47377–47383

    Google Scholar 

  14. Pedersen AT, Ringborg R, Grotkjær T, Pedersen S, Woodley JM (2015) Synthesis of 5-hydroxymethylfurfural (HMF) by acid catalyzed dehydration of glucose-fructose mixtures. Chem Eng J 273:455–464

    Google Scholar 

  15. Songo MM, Moutloali R, Ray SS (2019) Development of TiO2-carbon composite acid catalyst for dehydration of fructose to 5-hydroxymethylfurfural. Catalysts 9:126–141

    Google Scholar 

  16. Issaabadi Z, Nasrollahzadeh M, Sajadi SM (2017) Efficient catalytic hydration of cyanamides in aqueous medium and in the presence of Naringin sulfuric acid or green synthesized silver nanoparticles by using Gongronema latifolium leaf extract. J Colloid Interf Sci 503:57–67

    Google Scholar 

  17. Modarresi-Alam AR, Khamooshi F, Nasrollahzadeh M, Amirazizi HA (2007) Silica supported perchloric acid (HClO4–SiO2): an efficient reagent for the preparation of primary carbamates under solvent-free conditions. Tetrahedron 63:8723–8726

    Google Scholar 

  18. Modarresi-Alam AR, Nasrollahzadeh M, Khamooshi F (2007) Solvent-free preparation of primary carbamates using silica sulfuric acid as an efficient reagent. ARKIVOC 16:238–245

    Google Scholar 

  19. Li M, Jiang HN, Zhang L, Yu XJ, Liu H, Yagoub AEA, Zhou CS (2020) Synthesis of 5-HMF from an ultrasound-ionic liquid pretreated sugarcane bagasse by using a microwave-solid acid/ionic liquid system. Ind Crop Prod 149:112361–211270

    Google Scholar 

  20. Li MF, Zhang QT, Luo B, Chen CZ, Wang SF, Min DY (2020) Lignin-based carbon solid acid catalyst prepared for selectively converting fructose to 5-hydroxymethylfurfural. Ind Crop Prod 145:111920–111928

    Google Scholar 

  21. Nasrollahzadeh M, Bidgoli NSS, Shafiei N, Momenbeik F (2021) Biomass valorization: Sulfated lignin-catalyzed production of 5-hydroxymethylfurfural from fructose. Intl J Biol Macromol 182:59–64

    Google Scholar 

  22. Savaliya ML, Dholakiya BZ (2015) A simpler and highly efficient protocol for the preparation of biodiesel from soap stock oil using a BBSA catalyst. RSC adv 5:74416–74424

    Google Scholar 

  23. Nahavandi M, Kasanneni T, Yuan ZS, Xu CB, Rohani S (2019) Efficient conversion of glucose into 5-hydroxymethylfurfural using a sulfonated carbon-based solid acid catalyst: an experimental and numerical study. ACS Sustain Chem Eng 7:11970–11984

    Google Scholar 

  24. Zhang MH, Sun A, Meng YL, Wang LT, Jiang HX, Li GM (2015) High activity ordered mesoporous carbon-based solid acid catalyst for the esterification of free fatty acids. Micropor Mesopor Mat 204:210–217

    Google Scholar 

  25. Tian X, Su F, Zhao XS (2008) Sulfonated polypyrrole nanospheres as a solid acid catalyst. Green Chem 10:951–956

    Google Scholar 

  26. Li XY, Zhou HH, Wu WQ, Wei SD, Xu Y, Kuang YF (2015) Studies of heavy metal ion adsorption on chitosan/sulfydryl-functionalized graphene oxide composites. J Colloid Interf Sci 448:389–397

    Google Scholar 

  27. Khder AS, Ahmed AI (2009) Selective nitration of phenol over nanosized tungsten oxide supported on sulfated SnO2 as a solid acid catalyst. Appl Catal A-Gen 354:153–160

    Google Scholar 

  28. Wang YT, Yang XX, Xu J, Wang HL, Wang ZB, Zhang L, Wang SL, Liang JL (2019) Biodiesel production from esterification of oleic acid by a sulfonated magnetic solid acid catalyst. Renew Energ 139:688–695

    Google Scholar 

  29. Yuan D, Zhao N, Wang Y, Xuan K, Pu Y, Wang F, Li L, Xiao F (2019) Dehydration of sorbitol to isosorbide over hydrophobic polymer-based solid acid. Appl Catal B-Environ 240:182–192

    Google Scholar 

  30. Wu JB, Ling LX, Xie JB, Ma GZ, Wang BJ (2014) Surface modification of nanosilica with 3-mercaptopropyl trimethoxysilane: experimental and theoretical study on the surface interaction. Chem Phys Lett 591:227–232

    Google Scholar 

  31. Umar UIN, RamLi I, Muhamad EN, Yap YHT, Azri N (2020) Synthesis and characterization of sulfonated carbon catalysts derived from biomass waste and its evaluation in glycerol acetylation. Biomass Convers Bior 6:1–16

    Google Scholar 

  32. Ghosh A, Singha A, Auroux A, Das A, Sen D, Chowdhury B (2020) A green approach for the preparation of a surfactant embedded sulfonated carbon catalyst towards glycerol acetalization reactions. Catal Sci Technol 10:4827–4844

    Google Scholar 

  33. Sun S, Zhao LJ, Yang JR, Wang XQ, Qin XY, Qi XH, Shen F (2020) Eco-friendly synthesis of SO3H-containing solid acid via mechanochemistry for the conversion of carbohydrates to 5-hydroxymethylfurfural. ACS Sustain Chem Eng 8:7059–7067

    Google Scholar 

  34. Kastner JR, Miller J, Geller DP, Locklin J, Keith LH, Johnson T (2012) Catalytic esterification of fatty acids using solid acid catalysts generated from biochar and activated carbon. Catal Today 190:122–132

    Google Scholar 

  35. Valiollah M, Majid M, Shahram T, Iraj MB, Mohammad M (2009) Preparation of an improved sulfonated carbon-based solid acid as a novel, efficient, and reusable catalyst for chemoselective synthesis of 2-oxazolines and bis-oxazolines. Monatsh Chem 140:1489–1494

    Google Scholar 

  36. Mao DL, Zhang XG, Zhang XF, Jia MM, Yao JF (2019) Glucose-derived solid acids and their stability enhancement for upgrading biodiesel via esterification. Chinese J Chem Eng 27:1067–1072

    Google Scholar 

  37. Shukla PR, Wang SB, Sun HQ, Ang HM, Tade M (2010) Activated carbon supported cobalt catalysts for advanced oxidation of organic contaminants in aqueous solution. Appl Catal B-Environ 100:529–534

    Google Scholar 

  38. Onda A, Ochi T, Yanagisawa K (2019) Hydrolysis of cellulose selectively into glucose over sulfonated activated-carbon catalyst under hydrothermal conditions. Top Catal 52:801–807

    Google Scholar 

  39. Sompech S, Dasri T, Thaomola S (2016) Preparation and characterization of amorphous silica and calcium oxide from agricultural wastes. Orient J Chem 32:1923–1928

    Google Scholar 

  40. Zhou LP, Liu Z, Shi MT, Du SS, Su YL, Yang XM, Xu J (2013) Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose. Carbohyd Polym 98:146–151

    Google Scholar 

  41. Kang SM, Fu JX, Zhang G (2018) From lignocellulosic biomass to levulinic acid: a review on acid-catalyzed hydrolysis. Renew Sust Energ Rev 94:340–362

    Google Scholar 

  42. Flores KP, Omega JLO, Cabatingan LK, Go AW, Agapay RC, Ju YH (2018) Simultaneously carbonized and sulfonated sugarcane bagasse as solid acid catalyst for the esterification of oleic acid with methanol. Renew Energ 130:510–523

    Google Scholar 

  43. Shang FP, Sun JR, Wu SJ, Yang Y, Kan QB, Guan JQ (2010) Direct synthesis of acid–base bifunctional mesoporous MCM-41 silica and its catalytic reactivity in deacetalization–Knoevenagel reactions. Micropor Mesopor Mat 134:44–50

    Google Scholar 

  44. Sreekanth P, Kim SW, Hyeon T, Kim BM (2003) A Novel Mesoporous Silica-Supported Lewis Acid Catalyst for C-C Bond Formation Reactions in Water. Adv Synth Catal 345:936–938

    Google Scholar 

  45. Li SH, Gu ZR, Bjornson BE, Muthukumarappan A (2013) Biochar based solid acid catalyst hydrolyze biomass. J Environ Chem Eng 1:1174–1181

    Google Scholar 

  46. Zali A, Shokrolahi A, Keshavarz M, Zarei MA (2008) Carbon-based solid acid catalyzed highly efficient selective oxidations of sulfides to sulfoxides or sulfones with hydrogen peroxide. Acta Chim Slov 55:257–260

    Google Scholar 

  47. Huang CC, Li HS, Chen CH (2008) Effect of surface acidic oxides of activated carbon on adsorption of ammonia. J Hazard Mater 159:523–527

    Google Scholar 

  48. Thapa I, Mullen B, Saleem A, Cora LR, Tom B, Javier B (2017) Efficient green catalysis for the conversion of fructose to levulinic acid. Appl Catal A: Gen 539:70–79

    Google Scholar 

  49. Kröger M, Prüße U, Vorlop KD (2000) A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose. Top Catal 13:237–242

    Google Scholar 

Download references

Funding

This work was supported by Wuhan Science and Technology Bureau through Applied Basic Research Programs (2020020601012263).

Author information

Authors and Affiliations

  1. College of Chemical and Environmental Engineering, Wuhan Polytechnic University, Wuhan, 430023, People’s Republic of China

    Qiao He, Yuchan Lu, Qiao Peng, Wenhai Chen, Guozhi Fan, Bo Chai & Guangsen Song

Authors
  1. Qiao He
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuchan Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qiao Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wenhai Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Guozhi Fan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bo Chai
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Guangsen Song
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Guozhi Fan.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Highlights

• Carbon-based solid acid catalyzed the conversion of fructose into 5-hydroxymethylfurfural (5-HMF) with excellent selectivity and stability.

• A maximum 5-HMF yield of 100% was obtained.

• The yield of 5-HMF was still up to 94.3% after 4 cycles.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

He, Q., Lu, Y., Peng, Q. et al. Synthesis of 5-hydroxymethylfurfural from fructose catalyzed by sulfonated carbon-based solid acid. Biomass Conv. Bioref. 13, 9195–9203 (2023). https://doi.org/10.1007/s13399-021-01847-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13399-021-01847-6

Keyword

Search

Navigation