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(Hmf) Via Fructose Dehydration: Effect of Solvent and Salting-Out Brazilian Journal of Chemical ISSN 0104-6632 Printed in Brazil Engineering www.abeq.org.br/bjche Vol. 32, No. 01, pp. 119 - 126, January - March, 2015 dx.doi.org/10.1590/0104-6632.20150321s00002914 PRODUCTION OF 5-HYDROXYMETHYLFURFURAL (HMF) VIA FRUCTOSE DEHYDRATION: EFFECT OF SOLVENT AND SALTING-OUT F. N. D. C. Gomes, L. R. Pereira, N. F. P. Ribeiro and M. M. V. M. Souza* Escola de Química, Universidade Federal do Rio de Janeiro (UFRJ), Centro de Tecnologia, Bloco E, Sala 206, CEP: 21941-909, Rio de Janeiro - RJ, Brazil. Phone: + (55) (21) 39387598, Fax: + (55) (21)39387596 E-mail: [email protected] (Submitted: August 13, 2013 ; Revised: October 19, 2013 ; Accepted: October 30, 2013) Abstract - 5-Hydroxymethylfurfural (HMF) is a key renewable platform compound for production of fuels and chemical intermediates. The production of 5-hydroxymethylfurfural (HMF) from fructose dehydration was studied using H3PO4 as catalyst, in organic/water system with different solvents (acetone, 2-butanol and ethyl ether). The effect of fructose concentration, temperature and acid concentration was investigated in acetone/water medium. The increase in fructose concentration favors the formation of condensation products and rehydration products are favored at high acid concentration. The solvents exhibited similar performance when the volume ratio of organic to aqueous phase was 1:1, but when this ratio increases to 2:1, the HMF yield obtained with ether was much lower. NaCl addition to the aqueous phase promoted the extraction of HMF to the organic phase, with an HMF yield of 80% in the case of 2:1 acetone/water medium. Keywords: 5-hydroxymethylfurfural; Dehydration; Fructose; Biphasic system; Salting-out. INTRODUCTION 2007). HMF is a versatile and multi-functional com- pound used as intermediate for polymers, pharma- The interest in renewable resources as chemical ceuticals, fine chemicals, liquid fuels and for the feedstocks has grown considerably in recent years. synthesis of dialdehydes, ethers, amino alcohols and The production of fine chemicals, polymer precur- other organic derivatives (Boisen et al., 2009; Tong sors and petrol-derived commodities from biomass et al., 2010). can contribute to diminish our current dependence on Despite the versatile application profile of HMF- non-renewable energy sources. Furanic derivatives derived intermediate chemicals, HMF is not yet pro- can be used as the starting materials for new duced on an industrial scale, mainly because of the products as well as for replacement of oil-derived high production costs (Zakrzewska et al., 2011). HMF chemicals, establishing a new set of chemical com- can be obtained by acid-catalyzed dehydration of pounds based on biomass (Tong et al., 2010). In different carbohydrates such as fructose, glucose, particular, 5-hydroxymethylfurfural (HMF) has been sucrose, cellulose or inulin (Rosatella et al., 2011). considered an important platform chemical in a bio- Glucose, which is the most abundant and the cheapest refinery because it is a precursor for the production monosaccharide, has been considered as the preferred of various high-volume plastics and biofuels (Boisen feedstock for the production of HMF. However, et al., 2009; Bozell and Petersen, 2010; Corma et al., HMF is typically produced from glucose with low *To whom correspondence should be addressed 120 F. N. D. C. Gomes, L. R. Pereira, N. F. P. Ribeiro and M. M. V. M. Souza yields, which is attributed to the stable pyranoside extracted into an organic phase of methylisobu- ring structure of glucose (Hu et al., 2012). Thus, tylketone (MIBK) modified with 2-butanol to en- current technologies in general include an additional hance the partitioning from reactive aqueous solu- isomerization step of glucose to fructose, since de- tion. It was reported that an 80% HMF selectivity at hydration of fructose to HMF takes place with better 90% conversion was achieved for 30 wt% fructose selectivity and higher rates (Chheda et al., 2007; solution at 180 °C. Grande et al., 2012). The isomerization step can be The salting-out technique can be used to change done either enzymatically or by using aqueous bases the partition coefficient of HMF in a biphasic system or solid catalysts, such as hydrotalcites, zeolites and and thus improve the HMF yield (Roman-Leshkov different oxides. and Dumesic, 2009; Hansen et al., 2011). The use of Efficient HMF production requires the minimi- salting-out for carbohydrate dehydration has been zation of side reactions that yield soluble and in- known since the 1930s (Fulmer et al., 1935). The ions soluble polymers and HMF rehydration to levulinic in solution alter the intermolecular forces between and formic acids (Corma et al., 2007; Roman-Leshkov the liquids in equilibrium, resulting in an increased et al., 2006; Chheda et al., 2007; Roman-Leshkov and immiscibility. The decreased mutual solubility of the Dumesic, 2009). Dehydration of fructose in pure aqueous and organic phases enhances the extraction water using solid or mineral acids is generally non- of HMF from the aqueous phase (Roman-Leshkov selective due to degradation of HMF via rehydration and Dumesic, 2009). Roman-Leshkov and Dumesic reactions. Different strategies have been used in (2009) studied the effect of different inorganic salts HMF synthesis to decrease the formation of by- (LiCl, KCl, NaCl, CsCl, CaCl2, MgCl, KBr, NaBr and products. The use of aprotic solvents, such as di- Na2SO4) in biphasic systems using 1-butanol as the methylsulfoxide (DMSO), has been investigated by extracting solvent and HCl as catalyst. Na+ and K+ many authors to suppress unwanted side reactions showed the best combination of extracting power and generate high yields of HMF (Roman-Leshkov and HMF selectivity of the monovalent and divalent et al., 2006; Chheda et al., 2007; Musau and Munavu, chloride salts tested. Using NaCl an 82% HMF se- 1987). However, the separation of HMF from these lectivity at 87% fructose conversion was achieved at high-boiling point solvents is difficult, leading to 180 °C, with a partition coefficient of 3.1. Hansen et thermal degradation of the HMF product. Some in- al. (2011) also studied the effect of different salts in teresting results have been presented on the dehy- water:MIBK system, using boric acid as catalyst. dration of carbohydrates in ionic liquids, which have They reported 65% HMF selectivity at 70% fructose unique properties such as negligible vapor pressure conversion, using NaCl at 150 °C, with a partition and comparative thermal stability (Van Putten et al., coefficient of only 1.0. 2013; Zakrzewska et al., 2011). Nevertheless, the This paper studies the effect of different solvents high costs of ionic liquids, the limited data about and the use of the salting-out technique in HMF toxicity and complicated HMF separation and puri- production by dehydration of fructose. The solvents fication still limit their industrial application. chosen were acetone, 2-butanol and ethyl ether. Biphasic systems, in which a water-immiscible Acetone has the advantage of being a biomass-de- organic solvent is added to extract continuously rived solvent, 2-butanol showed the highest HMF HMF from the aqueous phase, offer an important selectivity of all solvents studied by Roman-Leshkov advantage in that the product is separated from the and Dumesic (2009), and ethyl ether is a very vola- reactant and reaction intermediates and is thereby tile solvent, favoring HMF separation by distillation protected against degradation reactions (Boisen et without degradation. The reaction conditions were al., 2009; Chheda et al., 2007; Roman-Leshkov et evaluated in the water/acetone system, and then these al., 2006; Van Putten et al., 2013). This extraction conditions were applied to the other solvents, with or shifts the equilibrium reaction to favor HMF pro- without NaCl addition to the aqueous phase. duction. However, this method requires a large amount of solvent due to the high HMF solubility in water and poor partitioning into the organic phase. Roman-Leshkov et al. (2006) reported a two-phase EXPERIMENTAL reaction system with HCl as the catalyst. In that work DMSO and poly(1-vinyl-2-pyrrolidine)(PVP) Fructose, phosphoric acid, organic solvents and were added to the aqueous phase to suppress the NaCl were obtained from Sigma-Aldrich in reagent undesired side reactions and HMF was continuously grade. Brazilian Journal of Chemical Engineering Production of 5-Hydroxymethylfurfural (HMF) Via Fructose Dehydration: Effect of Solvent And Salting-Out 121 All fructose dehydration reactions were carried levulinic and formic acids. Dehydration of fructose out in a 600 mL SS reactor (Parr) with 450 rpm of was carried out using H3PO4 as homogeneous catalyst. agitation and H3PO4 as catalyst, under autogeneous The choice of H3PO4 was based on its low corrosivity pressure. The reaction time was maintained constant towards stainless steel reactors, as compared to HCl, at 10 min. The first experiments were performed with and the good results presented by some authors in the 100 mL of water and 100 mL of acetone, varying literature using this catalyst. Takeuchi et al. (2008) -1 fructose concentration (25, 75 and 125 gL ), tem- compared HCl, H3PO4 and H2SO4 as catalysts for perature (120, 150, 180 and 200 °C), and H3PO4 con- glucose dehydration in water: the higher HMF yields centration (0.5, 1.0 and 1.5 wt%). were obtained using H3PO4. According to them, the Once the reaction conditions were defined, other use of a strong acid such as HCl accelerates the rehy- solvents were tested (2-butanol and ethyl ether), with dration of HMF to levulinic and formic acids. High the ratios of volumes of both phases (Vorg:Vaq) at HMF selectivities were also obtained when using 1:1 or 2:1 (100 mL of water and 100 or 200 mL of H3PO4 in glucose dehydration performed in biphasic organic solvent). In some experiments, NaCl was system (Chheda et al., 2007) and in fructose dehydra- added to saturate the water phase (300 g L-1).
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