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1 International Journal of Chemical and Environmental Engineering
The Study of Hydroxymethylfurfural as a Basic Reagent for Liquid Alkanes Fuel Manufacture from Agricultural Wastes
Kambiz Tahvildari, a Saeed Taghvaei ,a Maryam Nozari *a a Department of Chemistry, Islamic Azad University, North Tehran branch, Tehran, Iran *Corresponding author: email@example.com Abstract
Renewable biomass resources have the potential to serve as a sustainable supply of fuels and chemical intermediates. The spentbiomass residues will contain fragments from lignin, residual carbohydrates and other organic matter. Two of these biomass residues are the molasses and bagasse of sugar cane which have several carbohydrates compounds in them. This paper discusses the relative advantages of different process options to convert carbohydrates to 5-hydroxymethyl-2-furaldehyde (HMF), a valuable intermediate for fine chemicals, pharmaceuticals and furan-based polymers. A great variety of acid catalysts has been used in this process, such as mineral acids, Lewis acids, strong acid cation-exchange resins, H-form zeolites and supported heteropolyacids. Several reaction media have been adopted, such as the more convenient water, but also anhydrous organic solvents, ionic liquids and recently biphasic water/organic co-solvent systems. Keywords: 5-hydroxymethyl-2-furaldehyde, Carbohydrates, Acid catalysis, Fuels
We are entering an era of diminishing the availability of petrochemical resources to produce energy and chemical materials which represent the basis for the synthesis of many useful products. Being concerned about the green house effect and future re-arrangement of the economy from petroleum to biological raw materials have resulted in using fuels from renewable resources. Abundant biomass resources can provide alternative routes for a sustainable supply of both transportation fuels and valuable intermediates (such as alcohols, aldehydes, ketones and carboxylic acids) for production of drugs and polymer materials [1, 19]. From the estimated annual production of biomass by biosynthesis about 75% are carbohydrates (mainly in the form of cellulose, starch and saccharose), 20% are lignin and only 5% are compounds of completely different structure, for example, fats, oils, protein and various other substances . Therefore, attention should be focused on efficient access to carbohydrates and their conversion to chemical materials. Carbohydrates are readily available, relatively inexpensive and renewable, and they are precursor chemicals for the synthesis of a large number of substances such as furfural and 5-hydroxymethyl-2furaldehyde (HMF), levulinic acid, etc. via established chemical methods. The high content of oxygenated functional groups in carbohydrates is an advantage, in contrast to the drawback of such functionality, for the conversion of carbohydrates to fuels [3-19]. Indeed, carbohydrates in addition to their
use in food chemistry, find new applications as source of green chemistry for the production of chemicals . One of the interesting reactions of carbohydrates is acid catalyzed triple dehydration of C6-sugar monomers to produce HMF [3-9]. HMF (1) is a versatile intermediate between biomassbased carbohydrates chemistry and petroleum-based industrial organic chemistry, (2) and its derivatives could potentially replace voluminously consumed petroleumbased building blocks, (3) is currently used to make plastics and fine chemicals .
2. The History of HMF
In 1985, Dul and Kiermeyer while working independently, published a method for synthesis and chemical reaction of the compounds which they called ''Oxymethyl Furfural" . Several years later, other authors published their results. They worked out the modern method of HMF synthesis and studied the mechanism of its formation. Till now, over 1000 papers have been published, which is a proof for the great importance of this kind of compounds .
3. Aspect of Synthesis of HMF
The synthesis of HMF is based on the triple dehydration of C6-sugar monomers in acidic moieties. By looking at the scheme of producing HMF, one could have an impression that the synthesis of HMF is simple (Scheme 1). But after dehydration, complications can arise, such as the rehydrating of HMF, which often yield
the by-products levulinic acid and formic acid. Another competing side-reaction is the polymerization of HMF and/or Fructose to form humin polymers .
Scheme 1. Conversion of hexoses to HMF
As HMF has many functional groups (It is simultaneously a primary aromatic alcohol, an aromatic aldehyde and has a furan ring system), it can be used as a precursor to diesel fuel, fuel additives, fine chemicals and plant protect agents [4, 23, 24]. For example, HMF can be converted to 2,5-furandicarboxylic acid (FDCA) by selective oxidation. FDCA can be used as a replacement of terephthalic acid in the production of polyesters such as
polyethyleneterephthalate (PET) and polybutyleneterephthalate
(PBT). HMF is also currently under investigation as a treatment for sickle cell anomia . HMF is itself a rather unstable molecule. It can be found in natural products such as honey and a variety of heat processed food products formed in the thermal decomposition of carbohydrates . It is also important that HMF show a weak cytotoxicity and mutagenicity in human . The production of HMF has been studied for years, but an efficient method which is cost-effective and can produce HMF in high yields has yet to be found. Several extensive reviews are describing the chemistry of HMF and its derivatives. Moreau et al.  described the recent catalytic advances in substituted furans from biomass and focused especially on the ensuring polymers and their properties. A review by Lewkowski  on the chemistry of HMF and derivatives also appeared recently. The other relevant reviews are from Cottier and Descotes , and Kuster . The mechanism for the dehydration of fructose to HMF has been interpreted to proceed via two different routes, either via acyclic compounds or cyclic compounds . Antal proved experimentally that the mechanism of the HMF formation went through cyclic intermediates .
and lignocellulosic material (such as cellulose, xylan, hemi-cellulose, etc.) . Other mixed carbohydrate sources include crude fructose, purified fructose, high fructose corn syrup intermediates and by-products but are not limited to them . Sugarcane bagasse, as a byproduct of the sugar industry, is an abundant source of hemicelluloses that can be hydrolyzed to yield fermentation feed stock for the production of chemicals . The production of carbohydrates from lignocellulosic biomass is technically performed using diluted acids at high temperature [31, 32], concentrated acids at low temperatures  or using biotechnological methods such as enzyme or micro organism . So the monosaccharides which are released during this process can be used as carbohydrate sources. The other feed stock which is from the converted industrial wastes is the molasses of sugar cane or sugar beet which has approximately 30%-50% sucrose. The usual sources for sucrose are the juice of sugar cane, sugar beet and other sucrose-containing materials. After the readily recoverable sucrose has been extracted from these sources, the mother liquors which are generally termed "molasses" will still contain a relatively large amount of sucrose along with other sugars such as glucose, fructose, raffinose, etc. So it is highly desirable to use sucrose for producing HMF .
The first synthesis of HMF was catalyzed by oxalic acid and till now 100 inorganic and organic compounds were used for producing HMF . Several mineral acids, such as HCl, H2SO4 and H3PO4 have been employed as homogeneous catalyzed dehydration of fructose to HMF [7, 26, 36-38]. Organic acids such as oxalic acid, levulinic acid and maleic acid can be used, too. These acid catalysts are utilized in dissolved form, so it causes difficulties in their regeneration, reuse and their disposal . Acid catalysts may also promote a subsequent rehydration reaction of HMF, thus causing carbon-carbon bond cleavage on the aldehyde to yield levulinic acid and formic acid . Moreover, in acidic media, oligomerization of fructose and/or HMF may occur, leading to both insoluble humins and soluble polymeric by-products. Indeed, in homogeneous acid catalyzed processes, too low selectivities (30%-50%) towards HMF were observed at a quite high substrate conversion (50%-70%) owing to the degradation to levulinic acid and formic acid . In order to avoid these problems, reusable or recyclable catalysts are preferred for use in the reaction as they provide for increased efficiency, economic and industrial feasibility. Examples of these kinds of catalysts include solid acid catalysts, ion exchange resins, zeolites, Lewis acids, clays and molecular sieves but are not limited to them . Solid acid catalysts often comprise a solid material which has been functionalized to influence acid groups that are catalytically active. Sulfated zirconia used as an
4. Feed Stocks
The synthesis of HMF is based on the dehydration C6sugar monomers mainly glucose and fructose. This is partly because fructose has been shown to be more amenable to the dehydration reaction . Early processes for the production of HMF used crystalline fructose, but its usage is prevented because of its high cost. Depending on the method which is used, the feed stocks can be hexoses other than glucose and fructose (such as mannose, galactose), as well as other mono- di-, oligo- and poly-saccharides (such as sucrose, inulin, etc.)
effective solid catalyst for conversion of fructose to HMF in non-aqueous solutions such as acetone-DMSO mixture. In this mixture, a high fructose conversion of 93.6% with HMF yield of 72.8% could be obtained . The use of solid phase catalysts in a chromatography column to synthesis and purity of HMF limited exposure time to heat and enabled synthesis at a lower temperature. Lower temperature resulted in reducing energy cost and time for heating and cooling the reaction. Another advantage is the ability of the reaction to proceed and separate the product from the unwanted side-products. Studies concerning the application of ion-exchanging resin for the synthesis of HMF are numerous. Nakamura obtained HMF in 80% yield using strongly acidic ionexchange resin . Other researchers used different ion exchange resin and Mercudier, Rigal, El-Hajj and Rapp could produce HMF in high yield [22, 40]. Highly acidic cation-exchange resins such as those derivatives with sulfonic acid groups are also effective catalysts, providing the acidity of mineral acids together with the advantages of the heterogeneous catalysts . Ion exchange catalysts limit the reaction temperature to under 130 0C; however, this temperature range seems to be sufficient to overcome the activation energy barriers . The use of inorganic salts for the synthesis of HMF was the subject of numerous studies. For example, ammonium phosphates (the yield 32%), triethylaminephosphate (36%), pyridiniumphosphate (44%), zirconiumphosphate and zirconyl chloride improve the yield up to 90%. Ammonium sulphate, chromium trichloride or zinc chloride were used, too . Fayet and Gelas utilized various pyridinium salts such as poly-4-vinylpyridinium hydrochloride, pyridinium trifluoroacetate, hydrochloride, hydrobromide, perbromate and p-toluene sulfonate. Starting from fructose, they obtained HMF in 70% average yield . Metals such as Zn, Al, Cr, Ti, Th, Zr and V can be used as ions, salts or complexes as catalysts. Such use has not brought about improved results and yields of HMF have continued to be low . Szmant and Chundry used BF3 ET2O catalyst with DMSO as a solvent in the conversion of high-fructose corn syrup (HFCS), but it is not economically practical since it cannot be recovered and reused . The procedure for obtaining HMF from carbohydrate resources in the presence of niobium-based catalysts and niobic acid (Nb2O5 .nH2O) has been reported to have an intermediate selectivity of about 30% for 80% conversion of fructose. Niobium pentoxide and niobium phosphate are known to display quite high Brønsted acid strength, while no levulinic and formic acids were obtained as well [42, 43]. The dehydration of fructose can be achieved using metal halides such as FeCl2, CrCl2, CrCl3, FeCl3, CuCl2, CuCl2, VCl3, MoCl3, PdCl2, PtCl2, PtCl4, RuCl3 or RhCl3 and HMF yields ranging from 63% to 83%. Not all of the metal halides were effective, for example the alkali
chloride, LaCl3 and MnCl2 did not work . Zhang and co-workers have reported a metal chloride/ionic liquid system that gives good HMF yields for both fructose (83% with Pt or Rh chloride, 65% with CrCl2) and glucose (68% with CrCl2) . NHC/metal (NHC=N-Heterocyclic Carbene) complexes as catalyst for sugar dehydration reaction was used . Glucose might be converted into fructose first and subsequent into HMF over the NHC/Cr catalyst. In this case the fructose concentration would be relatively low even when the glucose substrate loading was high since fructose would merely be an intermediate in the conversion of glucose into HMF . The NHC/Cr catalysts were also tested in dimethylsulfoxide (DMSO) as the solvent and lower HMF yields were obtained both from fructose (28%-52%) and glucose (25%-32%). Catalysts with bulky NHC ligands showed higher efficiency in the DMSO system. NHC/Cr ionic liquid system has been used for the selective conversion of sugar into HMF and HMF yields were as high as 96% and 81% for fructose and glucose respectively . The new system is tolerant towards high substrate loading and the catalyst and ionic liquid can be recycled and HMF is provided as the sole product isolated after simple extraction .
6. Types of Solvents for Converting Carbohydrates to HMF
The types of solvents and their influence on the efficiency of the dehydration reaction are closely connected with temperature conditions. Cottier divided methods into 5 groups depending on the types of solvents and the temperature of the process : - Aqueous processes carried out at temperature below 200 0C - Aqueous processes carried out at temperature over 200 0C - Processes in non-aqueous medium - Processes in mixed solvents - Processes without solvent and microwave processes The dehydration of fructose to form HMF has been conducted in water [12, 14, 15], organic solvents , organic/water mixtures , ionic liquids [12, 21] and more recently, biphasic water /organic systems [19, 46]. The use of water as a solvent does increase the solubility of fructose in the solvent phase, but it also promotes sidereactions such as humin formation and HMF decomposition to acids (HMF yields <20%) [29, 46, 47]. In pure water, glucose dehydration to HMF is nonselective (about 6%) leading to formation of insoluble humins, too . Furthermore, solvation of protons in water highly reduces the catalytic activity of the dehydration reaction, and simultaneously leads to increased polymerization reactions and humin formation which also interfere with the synthesis of HMF . Fructose and by-products seem to be more pronounced in an aqueous reaction
medium than an organic one . In an attempt to solve such a problem associated with aqueous systems, one proposed solution involves an improvement by simultaneously extracting HMF after the dehydration reaction. A similar attempt to improve yields involves the adsorption of HMF on activated carbon. The key factor in these processes is a rapid removal of HMF from the acidic medium in which it is formed. However, these systems generally suffer from high dilution or partially irreversible adsorption of HMF . Another attempt to solve the problems of aqueous systems is adding an organic solvent to the aqueous solution.
7. Modified Aqueous Media and Non-aqueous Organic Solvents
Polar organic solvents that are miscible with water are added in order to increase the rate of reaction. Commonly employed aqueous phase modifiers are acetone, dimethylsulfoxide (DMSO) and polyethylene glycol (PEG) [24-26, 48]. Fructose has a good solubility in DMSO and HMF yields of 90% can be obtained in pure DMSO solvent. DMSO can prevent the formation of by-products, but the corresponding question of product separation from DMSO must be raised because of the high boiling point of DMSO [46, 47]. The reactive nature of pure HMF at high temperature leads to substantial carbonization of the isolated product upon distilling HMF from DMSO , so vacuum distillation is necessary to separate HMF from DMSO , on the other hand, DMSO is environmentally questionable . Acetone has quite low boiling point, so solvent recovery via distillation is easily achieved, and no solid by-products are formed in the organic solvent , but unfortunately, the solubility of fructose in pure acetone is negligible (0.5 g/L at 25 0C) and thus, either water or another solvent is needed to allow conversion at a practical scale . A 70:30 (w/w) acetone/water reaction medium resulted in yield of HMF as high as 73.4% for 94% conversion in the presence of a strong cationexchange resin as the catalyst under microwave heating . Acetone/DMSO mixtures can be effectively suppress the formation of levulinic acid, so that the HMF yield increases, and compared with acetone/water, it has lower activation (HMF yield of 89.8% and selectivity of 91.7% for fructose) . A study of Antal and co-workers suggested that HMF is formed by dehydration of D-fructose from its furanose form ; therefore, higher furanoid form concentration of D-fructose in acetone/DMSO mixtures might be the reason for the lower activation compared with acetone/water mixtures . Non-aqueous solvents require high dilution system; owing to the hydrophilic character of reagents. Various solvents were tested; Bonner and Shur et al. carried out
the reaction in DMF, Brown in acetonitrile, Morikawa proposed the application of quinoline, and Smith and Moye performed the reaction in polyglycol ethers . Problems concerning the solubility of hexoses in organic solvents were resolved by the application of mixed-solvent (water-organic) systems . Atlas Powder Co. laboratories and Kuster tested polyethylene glycols . High selectivity has also been obtained when using PEG-600 as a solvent together with the catalytic HCl . This method allowed a decrease in the degree of HMF degradation to levulinic acid . Solvents including aprotic polar solvents are preferred because they are miscible with water which helps with the solubility of fructose. In a further attempt to provide an adequate solvent system, aqueous solvent mixtures and anhydrous organic solvents have also been employed to ensure favorable reaction conditions . Examples of anhydrous organic solvents used include dimethylformamide (DMF), acetonitrile, dimethylsulfoxide (DMSO) and polyethylene glycol (PEG) . The addition of the aprotic solvent N-methyl pyrolidinone (NMP) to the aqueous-phase in the biphasic system increases the selectivity to HMF similar to the effect of DMSO. Importantly, replacing NMP with poly (1-vinyl-2-pyrrolidinone) (PVP), a hydrophilic polymer that has NMP moieties along the polyethylene chain, retains the advantage of increased selectivity, but significantly reduces carryover into the organic phase .
8. Sub- and Supercritical Solvents
Since the best results for the dehydration of hexoses have been in high-boiling organic solvents, the use of low boiling solvents in their sub- or supercritical state would be an interesting alternative . When glucose is dehydrated in pure subcritical water, HMF has greater selectivity than when using sulfuric acid or sodium hydroxide as a catalyst under the same pressure and temperatures . Yields of up to 50% were obtained when using fructose as the starting sugar and different zirconium phosphates as catalysts in subcritical water. No rehydration products were observed, yet the highest selectivity was not more than 61% and by-products were humins and furaldehyde . The overall results from sub- and supercritical water have so far been unsatisfactory in terms of yield. Bicker et al. examined the dehydration of fructose to HMF in sub- and supercritical acetone/water mixtures and obtained the results that both HMF selectivity and the fructose conversion increased with decreasing water content and the optimal selectivity was 77% with 99% fructose conversion .
9. Ionic Liquids
Another attractive alternative to high-boiling organic solvents is the use of ionic liquids . Their unique physical properties such as negligible vapor pressure and non-flammability make them particularly suitable as solvents for large-scale production . Biomass can be depolymerized in ionic liquids at considerably lower temperature than in comparable processes that use water as the medium [51, 52]. The first dehydration of fructose and glucose with the help of ionic liquids was done in the presence of pyridinium chloride to HMF in high purity with 70% yield for glucose . Zhao et al. studied the catalytic conversion of fructose to HMF in 1-alkyl-3-methylimidazolium chloride ([AMIM] Cl), with metal halides such as chromium (II) chloride as catalyst, achieving 73% yield of HMF [21, 47]. The yields of HMF were found to be closely dependent on the acidity type of the ionic liquids, the concentration of the ionic liquids and the reaction temperature and time . Acid catalyzed dehydration of fructose was performed using two commercially available ionic liquids, a hydrophilic one; 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM+ BF4-) as a solvent and Amberlyte-15 as catalyst which HMF yields up to 50% and a hydrophobic one; 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM+ PF6-) with Amberlyst-15 as catalyst and DMSO to solubilize fructose in the hydrophobic ionic liquid which HMF yields close to 80% [4, 53]. In another attempt the dehydration of fructose and sucrose in the presence of Brønsted acidic ionic liquid 1H-3-methylimidazolium chloride (HMIM+ Cl -) achieved in high yields HMF (92% for fructose) at relatively low temperature and short reaction time [45, 54, 55]. Preparation of HMF in the presence of the Brønsted acidic ionic liquid, 3-allyl-1-(4-sulfobutyl) imidazolium trifluoromethanesulfonate as well as its Lewis acid derivative, 3-allyl -1-(4-sulforylchloride butyl) imidazolium trifluoromethanesulfonate, concluded that the type of acidic ionic liquid used played a significant role in the reaction and the Lewis acidic ionic liquids act more effectively. So it shows that the Lewis acidic ionic liquid was a better reaction medium than the Brønsted acidic ionic liquid . It was demonstrated that when these acidic ionic liquids were immobilized on silica gel, they can be used as effective and reusable solid catalysts for the dehydration reaction to convert fructose to HMF .
10. Biphasic System With an Organic Extraction Solvent
A biphasic reaction medium comprises of an aqueous reaction solution and the substantially immiscible organic extraction solution in which the aqueous reaction solution, the organic extraction solution or both of them
contain at least one modifier to improve selectivity of the process to yield furan derivative compounds in general and HMF in particular [46, 56]. In these systems, the fructose dehydrated in aqueous medium and the water immiscible organic solvent is added to extract continuously the HMF from the aqueous phase, so the reaction is separated from the reactant and reaction intermediates and is thereby protected against degradation reaction; however, most extracting solvents used show poor partitioning of HMF into the organic phase, necessitating large amount of solvent and hence large energy expenditures to purify the diluted HMF product [46, 56]. Roman-Leskov et al. studied acid catalyzed fructose dehydration in a two-phase reactor system, where fructose was dehydrated in the aqueous phase with DMSO and poly (1-vinyl-2-pyrrolidinone) (PVP). The HMF was continuously extracted into an organic phase (methylisobutylketone) modified with 2-butanol to enhance partitioning from the reactive aqueous solution. A maximum selectivity of 85% with 89% fructose conversion was obtained. In these systems, feed solutions consisting of mixed fractions such as hemicelluloses and cellulose can be effectively handled without component separation . Recently, Dumesic and co-workers invented a biphasic system in which the aqueous phase layer comprises of water and one or more aqueous phase modifiers which are selected from water-miscible inorganic salts selected from the groups consisting of halides, sulfates, sulfides, phosphates, nitrates, acetates, carbonates and ionic liquids; and/or dipolar, aprotic compounds such as sulfoxides (e.g., DMSO), amides (e.g., dimethylformamide), pyrrolidinones (e.g., NMP), nitriles, pyrones, lactones, water-miscible alcohols or ketones and dioxane, and water-soluble polymers such as PVP and PEG [24, 25]. In this system, the preferred extractive organic solvents are 1-butanol, MIBK, and dichloromethane (DCM). Other organic phases, especially other alcohols, ketones and halogenated alkanes may also be utilized. Nitriles, aliphatic and cycloaliphatic ethers, cycloalkanones, saturated and unsaturated aliphatic or aromatic hydrocarbons (decane, toluene, benzene), oxygenated hydrocarbons and nitroalkanes may be used as well. The organic phase modifiers are selected from the group consisting of C1 to C8 aliphatic alcohols, and the most preferred is 2-butanol [24, 25]. In the preferred embodiment using 1-butanole or MIBK as the extracting solvent, an acid catalyst should be used, such as HCl, H2SO4, HNO3, etc. By using this modified biphasic reaction in the reactor system, high conversion of fructose with high yields of HMF can be obtained (in one preferred experiment 83% HMF selectivity with 83% conversion).
Renewable biomass resources have the potential to serve as a sustainable supply of fuels and chemical intermediates. One of these important intermediate is 5hydroxymethyl-2-furaldehyde (HMF), which obtained by triple dehydration of C6-sugar solution, especially fructose in acidic medium. Compared to fructose, glucose is preferred feed source because it is more abundant and has low cost, but the stable ring structure of glucose leading to a lower fraction, so it has lower reaction rate. A large variety of acid catalysts has been used in this process, such as mineral acids, Lewis acids, strong acid cation-exchange resins, H-form zeolites and supported heteropolyacids. As in green chemistry, recycling of the catalyst is very important, so heterogeneous catalysts offered the advantage of a very easy separation from the reaction products, thus appearing the most suitable catalysts for potential industrial applications. Several reaction media have been adopted as well, and many methods have been used for production of HMF in satisfactory yield with minimizing the by-products formation. As an efficient method which is cost-effective and can produce HMF in high yields has yet to be found, so chemists keep on working to find easy and inexpensive mode for producing HMF. ACKNOWLEDGMENT We would like to thank Dr. Jahanbakhsh Nikoopour for his comments on the final draft of the article. His editing comments both grammar and punctuated are wellappreciated. REFERENCES
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