Sulfonic acid heterogeneous catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide

doi:10.1016/S1872-2067(14)60020-6

Chinese Journal of Catalysis

Volume 35, Issue 5, May 2014, Pages 644-655

https://doi.org/10.1016/S1872-2067(14)60020-6 Get rights and content

Abstract

Sulfonic acid-functionalized heterogeneous catalysts have been evaluated in the catalytic dehydration of C₆ monosaccharides into 5-hydroxymethylfurfural (HMF) using dimethyl sulfoxide (DMSO) as solvent. Sulfonic commercial resin Amberlyst-70 was the most active catalyst, which was ascribed to its higher concentration of sulfonic acid sites as compared with the other catalysts, and it gave 93 mol% yield of HMF from fructose in 1 h. With glucose as the starting material, which is a much more difficult reaction, the reaction conditions (time, temperature, and catalyst loading) were optimized for Amberlyst-70 by a response surface methodology, which gave a maximum HMF yield of 33 mol% at 147 °C with 23 wt% catalyst loading based on glucose and 24 h reaction time. DMSO promotes the dehydration of glucose into anhydroglucose, which acts as a reservoir of the substrate to facilitate the production of HMF by reducing side reactions. Catalyst reuse without a regeneration treatment showed a gradual but not very significant decay in catalytic activity.

Graphical Abstract

Sulfonic acid-functionalized Amberlyst-70 was used in dimethyl sulfoxide (DMSO) as solvent for the catalytic dehydration of C₆ monosaccharides into 5-hydroxymethylfurfural (HMF), a biomass-derived platform molecule.

Introduction

As a consequence of the declining easily accessible fossil fuel reserves and the impact of CO₂ emission on climate change, interest in renewable resources such as chemical feedstocks has grown considerably. The production of fine chemicals, polymer precursors, and petroleum derived commodities from biomass can diminish our current dependence on non- renewable energy sources. Actually, biomass offers the only renewable source of organic molecules for the manufacture of bulk, fine and speciality chemicals, and it is necessary for the future needs of society. However, to be a truly sustainable strategy, biomass feedstocks must originate from the non-edible components of crops, cellulosic material from agricultural or forestry waste, or short rotation non-food crops requiring minimal cultivation. In this sense, lignocellulosic furanic derivatives should be the starting materials for products as well as for the replacement of oil-derived chemicals to establish a new set of chemical compounds with sustainable biomass origin [1]. In particular, 5-hydroxymethylfurfural (HMF) is considered an important platform chemical derived from cellulosic biomass that has a potential leading role in the development of biorefineries [2, 3, 4, 5]. The reason is that HMF is a versatile and multi-functional compound, which is an intermediate for polymers, pharmaceuticals, fine chemicals, liquid fuels and for the synthesis of dialdehydes, ethers, amino alcohols, and other organic derivatives [1, 3]. HMF can be obtained from acid-catalyzed dehydration of different C₆-based carbohydrates such as fructose, glucose, sucrose, cellulose, or inulin [6]. However, efficient HMF production requires the minimization of side reactions to soluble and insoluble polymers commonly known as humins, and HMF rehydration to levulinic and formic acids [5, 7, 8, 9]. The dehydration of C₆ sugars to HMF is frequently performed using liquid mineral acids including H₂SO₄, HCl, and H₃PO₄ as catalyst. However, the commercial implementation of HMF as a chemical intermediate is impeded by high production costs [10] because the large scale production of HMF from C₆ sugars is a low selectivity and complex process. Several aspects still remain a challenge, one of which is the utilization of glucose (inexpensive and highly available) as feedstock [8]. Hence, the control of undesired side reactions, which consume the starting monosaccharides, intermediates, and final product, is critical. One side reaction that is particularly important to prevent is the transformation of HMF in the aqueous phase to levulinic and formic acids. For this purpose, the use of organic solvents such as dimethylsulfoxide (DMSO) is a good alternative because it prevents the hydrolysis of HMF. Besides this, the use of solid acid catalysts has several advantages over the widely used mineral acids, especially in selectivity and the management of the transformation [1]. Most research has focused on the more facile conversion of fructose as a model saccharide to HMF, which avoids side products such as oligosaccharides and humins commonly reported in acid-catalyzed glucose conversion.

Different strategies have been used in HMF synthesis from fructose to suppress the formation of byproducts, such as the use of a second reaction solvent. Biphasic systems, in which a water-immiscible organic solvent is added to continuously remove the HMF from the aqueous phase, offer an important advantage because the product is separated from the reaction media and it is thereby protected from degradation reactions [3, 7, 8]. However, this method requires a large amount of solvent due to high HMF water solubility and poor partitioning in the organic phase although the salting-out technique can partially overcome this drawback [9, 11]. Unlike the case of fructose, where the dehydration is quite easy, reactions to convert the cheaper and more abundant glucose to HMF have been much less reported and remain a challenge in several aspects. Operation in a biphasic system such as water/MIBK is still a promising approach to the continuous transformation of glucose into HMF [7, 12], both when using mineral [7, 8, 13] or solid acids [14, 15, 16]. A tandem homogeneous Lewis/Brönsted acid catalyzed process using AlCl₃ and HCl in the water/2-sec- butylphenol biphasic system allowed the isomerization of glucose into fructose followed by its dehydration to HMF, with 62% yield of the final product [13]. Other catalytic systems such as homogeneous metal halides [17, 18], including Cr(III), Zn(II), and Sn(IV) and more water tolerant lanthanide chloride [19], can also drive the conversion of glucose, but they give lower HMF selectivity. The application of the Lewis acidic Sn-β zeolite together with aqueous HCl can also convert glucose to HMF in a biphasic system at 180 °C with 60% HMF selectivity. However, the use of corrosive HCl is undesirable [20]. A tandem reaction using solid base hydrotalcites and solid acid resins in a single reactor conducted in N,N-dimethylformamide [21] is very promising.

As an alternative to a biphasic system, the use of aprotic solvents like DMSO to suppress undesired side reactions [22] to give high yields of HMF [7, 8, 23, 24] has been investigated by many authors. Amarasekara et al. [25] demonstrated the reaction mechanism of HMF production from fructose in DMSO by means of NMR spectroscopy. They explained the dehydration of the two furanose forms of D-fructose to HMF by the elimination of three water molecules and showed the participation of DMSO as a catalyst. DMSO at high temperature has the effect of modifying the tautomeric forms of fructose, increasing the presence of furanose over the pyranose forms, and making the dehydration into HMF easier. Furthermore, DMSO contributes to stabilize HMF, which significantly reduces undesired side reactions [23, 26]. Other authors have proposed the heterogenization of this system by the incorporation of the thioether groups onto mesoporous silica to generate a promoting effect similar to that introduced by DMSO [27]. Despite some improvement in the selectivity towards HMF, the catalytic activity of these materials is limited by the low extent of silica functionalization. In addition, the combination of a Brönsted acid catalyst, such as sulphated zirconia modified with aluminium, and DMSO as solvent has been shown to be an efficient catalytic system that gave high yields of HMF from glucose [28]. On the other hand, several authors have brought attention to the main drawback of using DMSO in HMF production, which is the difficulty of the separation of the chemicals by conventional processes such as distillation due to the high boiling point of HMF and its sensitivity to high temperatures. However, a recent work on the room temperature separation of HMF from DMSO by selective adsorption on porous activated carbons has provided a cost-effective recovery process [29] that avoided the disadvantages of high temperature separation.

In this contribution, we present a study of the dehydration of fructose and glucose to HMF over sulfonic-modified solid catalysts using DMSO as solvent. The catalytic performance of several sulfonic-containing heterogeneous acid catalysts was benchmarked. This was followed by a multivariate analysis to assess the optimal reaction conditions (catalyst loading, temperature, and reaction time) to maximize the production of HMF.

Section snippets

Materials

Glucose (99.5% purity), fructose (99% purity), levoglucosan, or anhydroglucose (1,6-anhydro-β-D-glucose, 99% purity), HMF (99% purity), and levulinic acid (98% purity) were purchased from Sigma-Aldrich. Formic acid (98% purity) and DMSO (99.8% purity) were obtained from Scharlab. All the chemicals were used as received without further purification.

Catalyst preparation

Several sulfonic acid-containing heterogeneous catalysts were evaluated in the dehydration of C₆-monosaccharides. Propylsulfonic-acid and

Dehydration of fructose

The sulfonic acid-based heterogeneous catalysts selected for this work were first assayed in the dehydration of fructose to HMF using DMSO as solvent. The catalysts included propyl- and arene-sulfonic acid-modified SBA-15, which have been shown to be very active catalysts in other acid-catalyzed reactions [32]. They have been benchmarked with sulfonic macroporous resins, which are commercially available and conventionally used in acid-catalyzed processes, such as Amberlyst 70 and the composite

Conclusions

The use of Brönsted solid acids and DMSO as solvent catalyzed the catalytic dehydration of C₆ monosaccharides into HMF. With fructose, the reaction proceeded fast with high yields. The sulfonic acid resin Amberlyst-70 gave 93 mol% yield to HMF with 100% fructose conversion after 1 h. However, with glucose, the reaction was more difficult and required longer reaction times, which promoted the undesired side reactions of glucose degradation. Amberlyst-70 gave the best results because of its high

Acknowledgements

Financial support from the Spanish Ministry of Economy and Competitiveness through the project CTQ2011-28216- C02–01 is kindly acknowledged. Blanca Hernández thanks Spanish Ministry of Economy and Competitiveness for an FPI grant.

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Optimization of reaction parameters by using response surface methodology (RSM) for the selective dehydration of glucose to 5-hydroxymethylfurfural (5-HMF), a valuable platform chemical over a mesoporous TiO<inf>2</inf> catalyst in dimethylsulfoxide (DMSO) medium
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Citation Excerpt :
LA was not detected at higher glucose concentration (> 30 wt%) and lower temperature region (~100–140 °C). However, the formation of LA was found to be favorable at high temperatures (~140–180 °C) in the entire glucose amount domain, as shown in Fig. 4(b) [11]. The formation of LA via 5-HMF rehydration was favorable at high reaction temperatures.
A highly active and selective mesoporous TiO₂ was developed by the sol-gel hydrolysis technique for the selective transformation of glucose to 5-hydroxymethylfurfural (5-HMF). The catalytic performance was tested in a glass tube reactor, and the reaction parameters were optimized using response surface methodology (RSM). The best-optimized reaction conditions were obtained using four-factors, four-responses, and the 5-level central composite design (CCD) integrated with the desirability approach. At the optimum reaction condition, RSM predicted complete conversion of glucose and a very high 5-HMF yield of ~56% in the dimethylsulfoxide (DMSO) solvent. The predicted yield of other major products, including formic acid (FA) and levulinic acid (LA), was ~18% and ~2%, respectively. The empirical process model developed by RSM was validated by the experimental data generated. Experimental results demonstrated that the TiO₂ catalyst developed can easily be recycled with a constant glucose conversion and 5-HMF yield. Further, a new liquid-liquid extraction method (LLE) is proposed to extract 5-HMF from the product. The results depicted that 5-HMF can easily be extracted from the product mixture with very high purity (~96%). Additionally, the Power-Law kinetic study suggested that the conversion of glucose over TiO₂ followed the first-order kinetics, and the calculated activation energy was 67.5 kJ mol⁻¹.
Dehydration of glucose over sulfate impregnated ZnO (hexagonal-monoclinic) catalyst in dimethyl sulfoxide (DMSO) medium: Production, separation, and purification of 5-hydroxymethylfurfural (5-HMF) with high purity
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Dehydration of glucose for the production and separation of 5-hydroxymethylfurfural (5-HMF) with high purity has been performed. For selective production of 5-HMF from glucose, a new sulfated-ZnO catalyst with a combined hexagonal-monoclinic phase was developed and characterized by several techniques. The catalyst characterization results demonstrated a significant variation of physicochemical properties of hexagonal ZnO after sulfate impregnation. The glucose dehydration was performed in a glass reactor in a dimethyl sulfoxide (DMSO) medium. The effect of several important reaction parameters including temperature (120–160 °C), time (1–8 h), catalyst loading (25–100 wt%), and sulfate loading on ZnO with respect to glucose (1.5–4.5M) was evaluated. Results demonstrated that the sulfated-ZnO catalyst containing both the Brønsted (B) and Lewis (L) acid sites was very active and selective to 5-HMF compared to pure hexagonal ZnO containing only Lewis acidic sites (LAS). It was also observed that the higher (B + L) acidity of catalysts propagated the rehydration process, which led to the formation of various unwanted side products. The maximum glucose conversion of 96.2% with ~35% yield of 5-HMF was obtained at 160 °C after 6 h of reaction, with 2.5M-SO₄²⁻/ZnO catalyst. Among all others, the 2.5M-SO₄²⁻/ZnO catalyst was the best due to the presence of an optimum acidity with an appropriate B/L ratio. Further, the catalyst separation and recycling studies were performed. The results revealed that the 2.5M-SO₄²⁻/ZnO catalyst could be recycled multiple times without substantial loss of catalytic activity and 5-HMF yield. Furthermore, a liquid-liquid extraction process was developed, demonstrating that almost 100% of 5-HMF could be extracted from the product solution with ~97% purity.
Reaction kinetics study and the estimation of thermodynamic parameters for the conversion of glucose to 5-hydroxymethylfurfural (5-HMF) in a dimethyl sulfoxide (DMSO) medium in the presence of a mesoporous TiO<inf>2</inf> catalyst
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Glucose is a potential feedstock for the production of 5-HMF, a top ten platform chemical. The kinetics of glucose conversion to 5-HMF in organic dimethylsulfoxide (DMSO) medium is not known. In this study, glucose dehydration kinetics is performed over TiO₂ catalyst in the DMSO medium.
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Hydrothermal liquefaction (HTL) as a waste management technology has been investigated to produce renewable bio-crude and other valuable products from wet biomass and bio-waste. However, carbohydrates as a vital component in biomass have shown to increase the complexity of the process. Undesirable solid yields produced by the carbonisation/re-condensation of reactive carbohydrate intermediates could limit the renewable crude yield and recovery. In the present study, the reaction mechanism and kinetic models for the HTL of monosaccharides and polysaccharides are investigated using gas chromatography–mass spectrometry (GC–MS) and high-performance liquid chromatography (HPLC) to characterise, validate and quantify the most abundant organic species in the aqueous phase. The experimental data and models presented provide an unbiased understanding of the carbohydrate decomposition during HTL conversion, while the analysis of solid products clarifies solid transformations and integrates both phases into a more comprehensive reaction mechanism approach, including a shrinking core model for cellulose. Finally, ethanol and acetic acid were added as co-solvents to elucidate the effects of a fully renewable hydrogen donor solvent system to generate 5-ethoxymethyl furfural and ethyl levulinate (validated with GC–MS), two renewable fuel additives and promising tunable monomers candidates. Experiments were conducted with glucose, fructose, and cellulose in a batch reactor with 20% by mass premixed feedstock at 250 °C and 300 °C.

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: Published 20 May 2014

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Article (Special Issue on the 2nd International Congress on Catalysis for Biorefineries (CatBior 2013))Sulfonic acid heterogeneous catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide

Abstract

Graphical Abstract

Introduction

Section snippets

Materials

Catalyst preparation

Dehydration of fructose

Conclusions

Acknowledgements

Appl Catal A

Chem Eng Res Design

Appl Catal A

J Catal

Appl Catal A

Catal Today

Biomass

Carbohydr Res

Catal Commun

Microporous Mesoporous Mater

Appl Catal A

J Catal

Chem Rev

Green Chem

Chem Rev

Green Chem

Science

Article (Special Issue on the 2nd International Congress on Catalysis for Biorefineries (CatBior 2013))
Sulfonic acid heterogeneous catalysts for dehydration of C₆-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide