Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Synthesis 5-hydroxymethylfurfural (5-HMF) from fructose over cetyl trimethylammonium bromide-directed mesoporous alumina catalyst: effect of cetyl trimethylammonium bromide amount and calcination temperature

  • 98 Accesses

Abstract

In this study, mesoporous alumina was synthesized using aluminium isopropoxide as Al precursor and cationic surfactant cetyl trimethylammonium bromide (CTAB) as structure directing agent and it was tested in the dehydration reaction of fructose into 5-HMF. The experiments were carried out in a microwave reactor at 200 °C for 5 min. The various ratio of CTAB/Al2O3 and calcination temperature between 400 and 700 °C were selected as synthesis parameters. The synthesized samples were analyzed by BET and XRD. The highest surface area was obtained as 602.22 m2/g with the weight ratio of CTAB to Al2O3 of 1.00 at the calcination temperature of 400 °C. When calcination temperature increased from 400 to 700 °C, surface area decreased into 286.14 m2/g. N2 adsorption/desorption isotherms of samples showed characteristic mesoporous type IV according to IUPAC classification. According to XRD patterns, all catalysts were in the amorphous structure. The maximum 5-HMF yield of 51% was achieved with the alumina catalyst calcined at 400 °C and CTAB/Al2O3 ratio of 1.0. Although the surface area decreased by rising the calcination temperature from 400 to 550 °C, the fructose conversion reached the highest value (97.54%).

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. 1.

    De Bhowmick G, Sarmah AK, Sen R (2018) Lignocellulosic biorefinery as a model for sustainable development of biofuels and value added products. Biores Technol 247:1144–1154

  2. 2.

    Cao Z, Fan Z, Chen Y, Li M, Shen T, Zhu C, Ying H (2019) Efficient preparation of 5-hydroxymethylfurfural from cellulose in a biphasic system over hafnyl phosphates. Appl Catal B 244:170–177

  3. 3.

    Svenningsen GS, Kumar R, Wyman CE, Christopher P (2018) Unifying mechanistic analysis of factors controlling selectivity in fructose dehydration to 5-hydroxymethylfurfural by homogeneous acid catalysts in aprotic solvents. ACS Catal 8:5591–5600

  4. 4.

    Yemiş O, Mazza G (2019) Catalytic performance of various solid catalysts and metal halides for microwave-assisted hydrothermal conversion of xylose, xylan, and straw to furfural. Waste Biomass Valor 10:1343–1345

  5. 5.

    Ahlkvist J, Wärnå J, Salmi T, Mikkola JP (2016) Heterogeneously catalyzed conversion of nordic pulp to levulinic and formic acids. Reac Kinet Mech Cat 119:415

  6. 6.

    Qi X, Watanabe M, Aida TM, Smith RL (2009) Sulfated zirconia as a solid acid catalyst for the dehydration of fructose to 5-hydroxymethylfurfural. Catal Commun 10:1771–1775

  7. 7.

    Kılıç E, Yılmaz S (2015) Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO2–SiO2, Ti-SBA-15, ZrO2, SiO2, and Activated Carbon Catalysts. Ind Eng Chem Res 54:5220–5225

  8. 8.

    de Carvalho EGL, Rodrigues FA, Monteiro RS, Ribas RM, da Silva MJ (2018) Experimental design and economic analysis of 5-hydroxymethylfurfural synthesis from fructose in acetone-water system using niobium phosphate as catalyst. Biomass Conv Bioref 8:635–646

  9. 9.

    Shahangi F, Chermahini AN, Saraji M (2018) Dehydration of fructose and glucose to 5-hydroxymethylfurfural over Al-KCC-1 silica. J Energy Chem 27:769–780

  10. 10.

    Wang H, Kong Q, Wang Y, Deng T, Chen C, Hou X, Zhu Y (2014) Graphene Oxide catalyzed dehydration of fructose into 5-hydroxymethylfurfural with isopropanol as cosolvent. ChemCatChem 6:728–732

  11. 11.

    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 296:209–216

  12. 12.

    Li Y, Liu H, Song C, Gu X, Li H, Zhu W, Yin S, Han C (2013) The dehydration of fructose to 5-hydroxymethylfurfural efficiently catalyzed by acidic ion-exchange resin in ionic liquid. Biores Technol 133:347–353

  13. 13.

    Jin P, Zhang Y, Chen Y, Pan J, Dai X, Liu M, Yan Y, Li C (2017) Facile synthesis of hierarchical porous catalysts for enhanced conversion of fructose to 5-hydroxymethylfurfural. J Taiwan Inst Chem Eng 75:59–69

  14. 14.

    Raveendra G, Srinivas M, Pasha N, Rao AVP, Prasad PSS, Lingaiah N (2015) Heteropoly tungstate supported on tantalum oxide: a highly active acid catalyst for the selective conversion of fructose to 5-hydroxy methyl furfural. Reac Kinet Mech Cat 115:663–678

  15. 15.

    Liu Z, Sun Z, Qin D, Yang G (2019) Sulfonic acid-functionalized hierarchical SAPO-34 for fructose dehydration to 5-hydroxymethylfurfural. Reac Kinet Mech Cat. https://doi.org/10.1007/s11144-019-01603-y

  16. 16.

    Morales-Leal FJ, de la Rosa JR, Lucio-Ortiz CJ, De Haro-Del Rio DA, Maldonado CS, Wi S, Casabianca LB, Garcia CD (2019) Dehydration of fructose over thiol– and sulfonic– modified alumina in a continuous reactor for 5–HMF production: study of catalyst stability by NMR. Appl Catal B 244:250–261

  17. 17.

    Song C, Liu H, Li Y, Ge S, Wang H, Zhu W, Chang Y, Han C, Li H (2014) Production of 5-hydroxymethylfurfural from fructose in ionic liquid efficiently catalyzed by Cr(III)-Al2O3 Catalyst. Chin J Chem 32:434–442

  18. 18.

    Kurumada M, Koike C, Kaito C (2005) Laboratory production of δ and θ alumina grains and their characteristic infrared spectra. Mon Not R Astron Soc 359:643–647

  19. 19.

    Al’myasheva OV, Korytkova EN, Maslov AV, Gusarov VV (2005) Preparation of nanocrystalline alumina under hydrothermal conditions. Inorg Mater 41:460–467

  20. 20.

    Grant SM, Vinu A, Pikus S, Jaroniec M (2011) Adsorption and structural properties of ordered mesoporous alumina synthesized in the presence of F127 block copolymer. Colloids Surf A 385:121–125

  21. 21.

    Čejka J (2003) Organized mesoporous alumina: synthesis, structure and potential in catalysis. Appl Catal A 254:327–338

  22. 22.

    Yun YS, Park DS, Yi J (2014) Effect of nickel on catalytic behaviour of bimetallic Cu–Ni catalyst supported on mesoporous alumina for the hydrogenolysis of glycerol to 1,2-propanediol. Catal Sci Technol 4:3191–3202

  23. 23.

    Niesz K, Yang P, Somorjai AG (2005) Sol-gel synthesis of ordered mesoporous alumina. Chem Commun 15:1986–1987

  24. 24.

    Martín MI, Gómez LS, Milosevic O, Rabanal ME (2010) Nanostructured alumina particles synthesized by the Spray Pyrolysis method: microstructural and morphological analyses. Ceram Int 36:767–772

  25. 25.

    Lafficher R, Digne M, Salvatori F, Boualleg M, Colson D, Puel F (2017) Development of new alumina precipitation routes for catalysis applications. J Cryst Growth 468:526–530

  26. 26.

    Martins L, Alves Rosa MA, Pulcinelli SH, Santilli CV (2010) Preparation of hierarchically structured porous aluminas by a dual soft template method. Microporous Mesoporous Mater 132:268–275

  27. 27.

    Wu Z, Li Q, Feng D, Webley PA, Zhao D (2010) Ordered mesoporous crystalline γ-Al2O3 with variable architecture and porosity from a single hard template. J Am Chem Soc 132:12042–12050

  28. 28.

    Xu N, Liu Z, Bian S, Dong Y, Li W (2016) Template-free synthesis of mesoporous γ-alumina with tunable structural properties. Ceram Int 42:4072–4079

  29. 29.

    Aguado J, Escola JM, Castro MC, Paredes B (2005) Sol–gel synthesis of mesostructured γ-alumina templated by cationic surfactants. Microporous Mesoporous Mater 83:181–192

  30. 30.

    Yue MB, Jiao WQ, Wang YM, He MY (2010) CTAB-directed synthesis of mesoporous γ-alumina promoted by hydroxy polyacids. Microporous Mesoporous Mater 132:226–231

  31. 31.

    Sicard L, Llewellyn PL, Patarin J, Kolenda F (2001) Investigation of the mechanism of the surfactant removal from a mesoporous alumina prepared in the presence of sodium dodecylsulfate. Microporous Mesoporous Mater 44:195–201

  32. 32.

    Deng W, Bodart P, Pruski M, Shanks B (2002) Characterization of mesoporous alumina molecular sieves synthesized by nonionic templating. Microporous Mesoporous Mater 52:169–177

  33. 33.

    Wu Q, Zhang F, Yang J, Li Q, Tu B, Zhao D (2011) Synthesis of ordered mesoporous alumina with large pore sizes and hierarchical structure. Microporous Mesoporous Mater 143:406–412

  34. 34.

    Yuan Q, Yin AX, Luo C, Sun LD, Zhang YW, Duan WT, Liu HC, Yan CH (2008) Facile synthesis for ordered mesoporous γ-aluminas with high thermal stability. J Am Chem Soc 130:3465–3472

  35. 35.

    Ray JC, You KS, Ahn JW, Ahn WS (2007) Mesoporous alumina (I): comparison of synthesis schemes using anionic, cationic, and non-ionic surfactants. Microporous Mesoporous Mater 100:183–190

  36. 36.

    Berger D, Traistaru GA, Matei C (2012) Influence of different templates on the morphology of mesoporous aluminas. Cent Eur J Chem 10:1688–1695

  37. 37.

    Patel CK, Sarma PJ, De M (2015) Comparative parametric study on development of porous structure of aluminium oxide in presence of anionic and cationic surfactants. Ceram Int 41:3578–3588

  38. 38.

    Khalil KMS (2008) Formation of mesoporous alumina via hydrolysis of modified aluminum isopropoxide in presence of CTAB cationic surfactant. Appl Surf Sci 255:2874–2878

  39. 39.

    Liu Q, Wang A, Wang X, Zhang T (2007) Morphologically controlled synthesis of mesoporous alumina. Microporous Mesoporous Mater 100:35–44

  40. 40.

    Aguado J, Escola JM, Castro MC (2010) Influence of the thermal treatment upon the textural properties of sol–gel mesoporous γ-alumina synthesized with cationic surfactants. Microporous Mesoporous Mater 128:48–55

  41. 41.

    Zheng XL, Sun QP, Liu F, Zheng Y, Weng JB (2014) Effect of p-aminobenzoic acid on synthesizing ordered mesoporous alumina via the sol–gel method. J Porous Mater 21:819–825

  42. 42.

    Huang F, Zheng Y, Cai G, Zheng Y, Xiao Y, Wei K (2010) A new synthetic procedure for ordered mesoporous χ-alumina with a large surface area. Scripta Mater 63:339–342

  43. 43.

    Han D, Li X, Zhang L, Wang Y, Yan Z, Liu S (2012) Hierarchically ordered meso/macroporous γ-alumina for enhanced hydrodesulfurization performance. Microporous Mesoporous Mater 158:1–6

  44. 44.

    Wang J, Qu T, Liang M, Zhao Z (2015) Microwave assisted rapid conversion of fructose into 5-HMF over solid acid catalysts. RSC Adv. 5:106053–106060

Download references

Author information

Correspondence to Halit L. Hoşgün.

Additional information

Publisher's Note

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Hoşgün, H.L., Türe, A.G., Hoşgün, E.Z. et al. Synthesis 5-hydroxymethylfurfural (5-HMF) from fructose over cetyl trimethylammonium bromide-directed mesoporous alumina catalyst: effect of cetyl trimethylammonium bromide amount and calcination temperature. Reac Kinet Mech Cat 129, 337–347 (2020). https://doi.org/10.1007/s11144-019-01699-2

Download citation

Keywords

  • Alumina
  • Sol–gel synthesis
  • CTAB
  • Fructose
  • 5-HMF