Elsevier

Carbohydrate Research

Volume 351, 1 April 2012, Pages 35-41
Carbohydrate Research

Selective dehydration of fructose to 5-hydroxymethylfurfural catalyzed by mesoporous SBA-15-SO3H in ionic liquid BmimCl

https://doi.org/10.1016/j.carres.2012.01.003Get rights and content

Abstract

Mesoporous SBA-15 materials functionalized with propylsulfonic acid groups (SBA-15-SO3H) were synthesized through a conventional one-pot route. It was used as a catalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from the dehydration of fructose using BmimCl as solvent. Reaction time, temperature and fructose concentration were investigated during the HMF synthesis procedure. The catalyst SBA-15-SO3H exhibits high fructose conversion (near 100%) and HMF selectivity (about 81%) with good stability in the HMF synthesis. It was a suitable catalyst to produce HMF from renewable carbohydrates in potential industrial process.

Graphical abstract

Propylsulfonic acid functionalized SBA-15 catalysts were used to prepare 5-hydroxymethylfurfural (HMF) using BmimCl as solvent. This made the simple SBA-15-SO3H-BmimCl system a promising choice for fructose dehydration.

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Highlights

► SBA-15-SO3H was an environmentally benign solid catalyst for the dehydration of fructose. ► The catalyst was tolerant to high concentration feedstock and can be reused. ► High HMF selectivity of 81.0% with above 97% fructose conversion was obtained. ► The separation of HMF was successfully achieved in a THF/BmimCl biphasic system.

Introduction

Biomass is a promising alternative for sustainable supply of precious intermediates and platform chemicals to the chemical industry.1, 2 Among many possible biomass derived chemicals, 5-hydroxymethylfurfural (5-HMF) can be used as a valuable intermediate for fine chemicals, pharmaceuticals, and furan-based polymers. It is considered to have the potential to be a sustainable substitute for petroleum-based building blocks.3, 4, 5

Acid catalyzed dehydration of d-fructose is the most convenient and efficient method for preparing HMF. Due to the increased interest and demand for industrial application, many efficient catalytic systems were recently developed.6 It is no doubt that developing a cheap, non-toxic or low-toxic, easily handled catalytic system is highly desirable but challenging. Many types of acid catalysts have been used in this process, such as mineral acids,7, 8 strong acid cation exchange resins,9, 10, 11 H-form zeolites12, 13 and supported heteropolyacids.14 Among these acid catalysts, heterogeneous acid catalysts offer the advantage of easy separation from the reaction products and can be recycled, thus appearing as the most suitable catalysts for a potential industrial process. However, up to now, the performances of different heterogeneous acid catalysts are still unsatisfactory. A progressive decrease of selectivity to HMF has been observed with time, due to the formation of formic and levulinic acids as well as of polymeric by-products, such as insoluble humins, as shown in Scheme 1.15 Furthermore, the above mentioned heterogeneous catalysts were not readily regenerated.16 Thus, more research is being conducted to find more efficient solid catalysts for fructose dehydration. Karam et al. reported17 that the mesoporous structure of SBA-SO3H was preserved after five catalytic runs for the reaction of indole with benzaldehyde in water. The drop in the yield can be attributed to a decrease of the acid strength of SBA-SO3H caused by a solvation of the catalytic sites by water. SBA-15 is a promising candidate for the catalyst supports due to its unique mesoporous structure and high thermal stability, which can be functionalized with different catalytic active groups. It has been reported that the mono-functionalized organo-sulfonic acid modified ordered mesoporous silica materials showed relative high performance for many heterogeneous acid-catalyzed reactions such as the dehydration of monoaccharides.18 Crisci synthesized a supported bifunctional acid catalyst and silica-supported alkylsulfonic acids for the selective conversion of carbohydrates which are efficient and selective fructose dehydration catalysts under batch conditions, the co-condensed material suffered loss of its mesopore ordering and most of its functional groups during the secondary derivatization step.19, 20

Both catalyst and solvent are crucial in the conversion of fructose into HMF. In an effort to achieve a high HMF yield, a great deal of work has been reported in the literature, using various media, such as water,21, 22 highly polar organic solvents,23, 24 and ionic liquids.25, 26, 27, 28, 29 Environmental concerns favor water as a solvent for the reaction, but water is not very selective for the production of HMF and many by-products comprising insoluble polymeric compounds (i.e. humins) and soluble polymers are often formed, leading to a comparably low HMF yield.30 Although high yields of HMF can be achieved in some high-boiling point organic solvents such as dimethyl sulfoxide (DMSO) and dimethylacetamide (DMA), the disadvantage of using those solvents is the high energy consumption during separation.

Ionic liquids are a group of salts that exist as liquids at low temperatures (<100 °C). They have many attractive properties, including chemical and thermal stability, nonflammability, and immeasurably low vapor pressure, which is favorable for a catalytic reaction.31 Some authors studied the dehydration of fructose in ionic liquids. Zhao et al.32 reported that chromium(II) chloride was found to be uniquely effective, leading to the conversion of glucose to HMF with a yield near 70%, but the toxicity and recovery of the ionic liquids was not clear. Moreau et al., have demonstrated that neutral ionic liquids such as [Bmim]PF6 and [Bmim]BF4 can act as a suitable reaction medium for the dehydration of fructose to HMF in the presence of the acidic catalyst, Amberlyst-15.33 Recently, metal chlorides in neutral ionic liquid [Emim]Cl have been found to be effective catalysts for converting fructose and glucose to HMF. The water generated from the dehydration of fructose is diluted in the IL phase thus avoiding the important deactivation of catalytic sites. These results suggest that ionic liquids as solvents or catalysts can play a positive role in the development of effective processes for the dehydration of hexose to HMF.34, 35

In summary, many attempts have been made to develop new catalytic processes, mainly based on heterogeneous catalysis, for the transformation of fructose and fructose-precursors into HMF. Although multiple solvents have been reported for the production of HMF, we indicated that HMF can be produced in high yields by the acid-catalyzed dehydration of fructose in BmimCl.

In this work, functional propyl-sulfonic acid groups were grafted onto the pore surface of mesoporous SBA-15. The structure of the materials was investigated with electron microscopic and BET surface area techniques etc. Furthermore, the SBA-15-SO3H, was first used as a heterogeneous solid acid catalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from the dehydration of fructose in ionic liquids.

Section snippets

Materials

Fructose (99%), 5-hydroxymethylfurfural (99%) and HCl (37 wt %) were purchased from Sigma–Aldrich and were used without further purification. Triblock copolymer P123 (EO20PO70EO20, Aldrich), tetraethoxysilane (TEOS) and (3-mercaptopropyl) trimethoxysilane (MPTMS) were purchased from Aladdin Reagent Limited Company (China). Deionized water was used for the preparation of aqueous solutions. 1-Butyl-3-methylimidazolium chloride (BmimCl) (99%) was purchased from Shanghai Chengjie Chemical Co., Ltd.

Catalyst preparation

Characterization of the catalyst

The powder XRD patterns of SBA-15-SO3H samples are shown in Figure 1. All samples show one intense peak of (1 0 0) and two weak diffraction peaks of (1 1 0) and (2 0 0). The XRD patterns of SBA-15-SO3H indicate that the crystallographic order of mesopores is preserved after the incorporation of MPTMS into SBA-15. The well resolved (1 1 0) and (2 0 0) reflections for the samples reveal highly ordered mesopores in the SBA-15-SO3H materials. However, when x = 20, the reflections (1 1 0) and (2 0 0) are less

Conclusions

SBA-15-SO3H as a heterogeneous catalyst exhibits excellent performance in the selective synthesis of HMF from the dehydration of fructose. It is tolerant to high concentration of fructose and can be reused. High fructose conversion (near 100%) and HMF selectivity (about 81%) were obtained, which almost was the same with that of sulfuric acid. The activity of SBA-15-SO3H may be ascribed to the materials with suitable acidic sites as the active centers and the unique surface textural properties.

Acknowledgments

The authors are grateful for the financial support of the National High Technology Research and Development Program of China (No. 2009AA05Z410), the National Natural Science Foundation of China (No. 20803038), the Natural Science Foundation of Shandong Province, China (No. O92003110C), and the Knowledge Innovation Program of the Chinese Academy of Sciences (No. KSCX2-YW-G-075-13).

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