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February 2011, Volume 2, No.

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: m_nouzari@yahoo.com

Abstract
Renewable biomass resources have the potential to serve as a sustainable supply of fuels and chemical intermediates. The spent-
biomass 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
1. Introduction use in food chemistry, find new applications as source of
We are entering an era of diminishing the availability green chemistry for the production of chemicals [20].
of petrochemical resources to produce energy and One of the interesting reactions of carbohydrates is
chemical materials which represent the basis for the acid catalyzed triple dehydration of C6-sugar monomers
synthesis of many useful products. Being concerned about to produce HMF [3-9].
the green house effect and future re-arrangement of the HMF (1) is a versatile intermediate between biomass-
economy from petroleum to biological raw materials have based carbohydrates chemistry and petroleum-based
resulted in using fuels from renewable resources. industrial organic chemistry, (2) and its derivatives could
Abundant biomass resources can provide alternative potentially replace voluminously consumed petroleum-
routes for a sustainable supply of both transportation fuels based building blocks, (3) is currently used to make
and valuable intermediates (such as alcohols, aldehydes, plastics and fine chemicals [21].
ketones and carboxylic acids) for production of drugs and
polymer materials [1, 19]. 2. The History of HMF
From the estimated annual production of biomass by In 1985, Dul and Kiermeyer while working
biosynthesis about 75% are carbohydrates (mainly in the independently, published a method for synthesis and
form of cellulose, starch and saccharose), 20% are lignin chemical reaction of the compounds which they called
and only 5% are compounds of completely different ''Oxymethyl Furfural" [22]. Several years later, other
structure, for example, fats, oils, protein and various other authors published their results. They worked out the
substances [2]. Therefore, attention should be focused on modern method of HMF synthesis and studied the
efficient access to carbohydrates and their conversion to mechanism of its formation. Till now, over 1000 papers
chemical materials. Carbohydrates are readily available, have been published, which is a proof for the great
relatively inexpensive and renewable, and they are importance of this kind of compounds [22].
precursor chemicals for the synthesis of a large number of
substances such as furfural and 5-hydroxymethyl-2- 3. Aspect of Synthesis of HMF
furaldehyde (HMF), levulinic acid, etc. via established The synthesis of HMF is based on the triple
chemical methods. dehydration of C6-sugar monomers in acidic moieties. By
The high content of oxygenated functional groups in looking at the scheme of producing HMF, one could have
carbohydrates is an advantage, in contrast to the drawback an impression that the synthesis of HMF is simple
of such functionality, for the conversion of carbohydrates (Scheme 1). But after dehydration, complications can
to fuels [3-19]. Indeed, carbohydrates in addition to their arise, such as the rehydrating of HMF, which often yield
the by-products levulinic acid and formic acid. Another and lignocellulosic material (such as cellulose, xylan,
competing side-reaction is the polymerization of HMF hemi-cellulose, etc.) [24]. Other mixed carbohydrate
and/or Fructose to form humin polymers [23]. sources include crude fructose, purified fructose, high
fructose corn syrup intermediates and by-products but are
not limited to them [24]. Sugarcane bagasse, as a by-
product of the sugar industry, is an abundant source of
hemicelluloses that can be hydrolyzed to yield
fermentation feed stock for the production of chemicals
[30]. The production of carbohydrates from
lignocellulosic biomass is technically performed using
diluted acids at high temperature [31, 32], concentrated
Scheme 1. Conversion of hexoses to HMF acids at low temperatures [33] or using biotechnological
methods such as enzyme or micro organism [34]. So the
As HMF has many functional groups (It is monosaccharides which are released during this process
simultaneously a primary aromatic alcohol, an aromatic can be used as carbohydrate sources. The other feed stock
aldehyde and has a furan ring system), it can be used as a which is from the converted industrial wastes is the
precursor to diesel fuel, fuel additives, fine chemicals and molasses of sugar cane or sugar beet which has
plant protect agents [4, 23, 24]. For example, HMF can be approximately 30%-50% sucrose. The usual sources for
converted to 2,5-furandicarboxylic acid (FDCA) by sucrose are the juice of sugar cane, sugar beet and other
selective oxidation. FDCA can be used as a replacement sucrose-containing materials. After the readily
of terephthalic acid in the production of polyesters such as recoverable sucrose has been extracted from these
polyethyleneterephthalate (PET) and polybutyleneterephthalate sources, the mother liquors which are generally termed
(PBT). HMF is also currently under investigation as a "molasses" will still contain a relatively large amount of
treatment for sickle cell anomia [25]. sucrose along with other sugars such as glucose, fructose,
HMF is itself a rather unstable molecule. It can be raffinose, etc. So it is highly desirable to use sucrose for
found in natural products such as honey and a variety of producing HMF [35].
heat processed food products formed in the thermal
decomposition of carbohydrates [26]. It is also important 5. Catalysts
that HMF show a weak cytotoxicity and mutagenicity in The first synthesis of HMF was catalyzed by oxalic
human [27]. The production of HMF has been studied for acid and till now 100 inorganic and organic compounds
years, but an efficient method which is cost-effective and were used for producing HMF [22]. Several mineral
can produce HMF in high yields has yet to be found. acids, such as HCl, H2SO4 and H3PO4 have been
Several extensive reviews are describing the chemistry of employed as homogeneous catalyzed dehydration of
HMF and its derivatives. Moreau et al. [4] described the fructose to HMF [7, 26, 36-38]. Organic acids such as
recent catalytic advances in substituted furans from oxalic acid, levulinic acid and maleic acid can be used,
biomass and focused especially on the ensuring polymers too. These acid catalysts are utilized in dissolved form, so
and their properties. A review by Lewkowski [22] on the it causes difficulties in their regeneration, reuse and their
chemistry of HMF and derivatives also appeared recently. disposal [29]. Acid catalysts may also promote a
The other relevant reviews are from Cottier and Descotes subsequent rehydration reaction of HMF, thus causing
[28], and Kuster [5]. The mechanism for the dehydration carbon-carbon bond cleavage on the aldehyde to yield
of fructose to HMF has been interpreted to proceed via levulinic acid and formic acid [5]. Moreover, in acidic
two different routes, either via acyclic compounds or media, oligomerization of fructose and/or HMF may
cyclic compounds [22]. Antal proved experimentally that occur, leading to both insoluble humins and soluble
the mechanism of the HMF formation went through polymeric by-products. Indeed, in homogeneous acid
cyclic intermediates [22]. catalyzed processes, too low selectivities (30%-50%)
towards HMF were observed at a quite high substrate
conversion (50%-70%) owing to the degradation to
4. Feed Stocks levulinic acid and formic acid [26].
The synthesis of HMF is based on the dehydration C6- In order to avoid these problems, reusable or
sugar monomers mainly glucose and fructose. This is recyclable catalysts are preferred for use in the reaction as
partly because fructose has been shown to be more they provide for increased efficiency, economic and
amenable to the dehydration reaction [29]. Early industrial feasibility. Examples of these kinds of catalysts
processes for the production of HMF used crystalline include solid acid catalysts, ion exchange resins, zeolites,
fructose, but its usage is prevented because of its high Lewis acids, clays and molecular sieves but are not
cost. Depending on the method which is used, the feed limited to them [29].
stocks can be hexoses other than glucose and fructose Solid acid catalysts often comprise a solid material
(such as mannose, galactose), as well as other mono- di-, which has been functionalized to influence acid groups
oligo- and poly-saccharides (such as sucrose, inulin, etc.) that are catalytically active. Sulfated zirconia used as an
63
effective solid catalyst for conversion of fructose to chloride, LaCl3 and MnCl2 did not work [21]. Zhang and
HMF in non-aqueous solutions such as acetone-DMSO co-workers have reported a metal chloride/ionic liquid
mixture. In this mixture, a high fructose conversion of system that gives good HMF yields for both fructose
93.6% with HMF yield of 72.8% could be obtained [39]. (83% with Pt or Rh chloride, 65% with CrCl2) and
The use of solid phase catalysts in a chromatography glucose (68% with CrCl2) [21].
column to synthesis and purity of HMF limited exposure NHC/metal (NHC=N-Heterocyclic Carbene)
time to heat and enabled synthesis at a lower temperature. complexes as catalyst for sugar dehydration reaction was
Lower temperature resulted in reducing energy cost and used [44]. Glucose might be converted into fructose first
time for heating and cooling the reaction. Another and subsequent into HMF over the NHC/Cr catalyst. In
advantage is the ability of the reaction to proceed and this case the fructose concentration would be relatively
separate the product from the unwanted side-products. low even when the glucose substrate loading was high
Studies concerning the application of ion-exchanging since fructose would merely be an intermediate in the
resin for the synthesis of HMF are numerous. Nakamura conversion of glucose into HMF [45]. The NHC/Cr
obtained HMF in 80% yield using strongly acidic ion- catalysts were also tested in dimethylsulfoxide (DMSO)
exchange resin [9]. Other researchers used different ion as the solvent and lower HMF yields were obtained both
exchange resin and Mercudier, Rigal, El-Hajj and Rapp from fructose (28%-52%) and glucose (25%-32%).
could produce HMF in high yield [22, 40]. Catalysts with bulky NHC ligands showed higher
Highly acidic cation-exchange resins such as those efficiency in the DMSO system.
derivatives with sulfonic acid groups are also effective NHC/Cr ionic liquid system has been used for the
catalysts, providing the acidity of mineral acids together selective conversion of sugar into HMF and HMF yields
with the advantages of the heterogeneous catalysts [41]. were as high as 96% and 81% for fructose and glucose
Ion exchange catalysts limit the reaction temperature to respectively [45]. The new system is tolerant towards
under 130 0C; however, this temperature range seems to high substrate loading and the catalyst and ionic liquid
be sufficient to overcome the activation energy barriers can be recycled and HMF is provided as the sole product
[29]. isolated after simple extraction [45].
The use of inorganic salts for the synthesis of HMF
was the subject of numerous studies. For example, 6. Types of Solvents for Converting
ammonium phosphates (the yield 32%), Carbohydrates to HMF
triethylaminephosphate (36%), pyridiniumphosphate The types of solvents and their influence on the
(44%), zirconiumphosphate and zirconyl chloride efficiency of the dehydration reaction are closely
improve the yield up to 90%. Ammonium sulphate, connected with temperature conditions. Cottier divided
chromium trichloride or zinc chloride were used, too [22]. methods into 5 groups depending on the types of solvents
Fayet and Gelas utilized various pyridinium salts such as and the temperature of the process [22]:
poly-4-vinylpyridinium hydrochloride, pyridinium - Aqueous processes carried out at temperature below
trifluoroacetate, hydrochloride, hydrobromide, 200 0C
perbromate and p-toluene sulfonate. Starting from - Aqueous processes carried out at temperature over
fructose, they obtained HMF in 70% average yield [22]. 200 0C
Metals such as Zn, Al, Cr, Ti, Th, Zr and V can be - Processes in non-aqueous medium
used as ions, salts or complexes as catalysts. Such use has - Processes in mixed solvents
not brought about improved results and yields of HMF - Processes without solvent and microwave processes
have continued to be low [29].
Szmant and Chundry used BF3 ET2O catalyst with The dehydration of fructose to form HMF has been
DMSO as a solvent in the conversion of high-fructose conducted in water [12, 14, 15], organic solvents [9],
corn syrup (HFCS), but it is not economically practical organic/water mixtures [19], ionic liquids [12, 21] and
since it cannot be recovered and reused [29]. more recently, biphasic water /organic systems [19, 46].
The procedure for obtaining HMF from carbohydrate The use of water as a solvent does increase the solubility
resources in the presence of niobium-based catalysts and of fructose in the solvent phase, but it also promotes side-
niobic acid (Nb2O5 .nH2O) has been reported to have an reactions such as humin formation and HMF
intermediate selectivity of about 30% for 80% conversion decomposition to acids (HMF yields <20%) [29, 46, 47].
of fructose. Niobium pentoxide and niobium phosphate In pure water, glucose dehydration to HMF is non-
are known to display quite high Brønsted acid strength, selective (about 6%) leading to formation of insoluble
while no levulinic and formic acids were obtained as well humins, too [47].
[42, 43]. Furthermore, solvation of protons in water highly
The dehydration of fructose can be achieved using reduces the catalytic activity of the dehydration reaction,
metal halides such as FeCl2, CrCl2, CrCl3, FeCl3, CuCl2, and simultaneously leads to increased polymerization
CuCl2, VCl3, MoCl3, PdCl2, PtCl2, PtCl4, RuCl3 or RhCl3 reactions and humin formation which also interfere with
and HMF yields ranging from 63% to 83%. Not all of the the synthesis of HMF [29]. Fructose and by-products
metal halides were effective, for example the alkali seem to be more pronounced in an aqueous reaction
64
medium than an organic one [26]. the reaction in DMF, Brown in acetonitrile, Morikawa
In an attempt to solve such a problem associated with proposed the application of quinoline, and Smith and
aqueous systems, one proposed solution involves an Moye performed the reaction in polyglycol ethers [22].
improvement by simultaneously extracting HMF after the Problems concerning the solubility of hexoses in
dehydration reaction. A similar attempt to improve yields organic solvents were resolved by the application of
involves the adsorption of HMF on activated carbon. The mixed-solvent (water-organic) systems [22]. Atlas
key factor in these processes is a rapid removal of HMF Powder Co. laboratories and Kuster tested polyethylene
from the acidic medium in which it is formed. However, glycols [22]. High selectivity has also been obtained when
these systems generally suffer from high dilution or using PEG-600 as a solvent together with the catalytic
partially irreversible adsorption of HMF [45]. HCl [26]. This method allowed a decrease in the degree
Another attempt to solve the problems of aqueous of HMF degradation to levulinic acid [22].
systems is adding an organic solvent to the aqueous Solvents including aprotic polar solvents are preferred
solution. because they are miscible with water which helps with the
solubility of fructose. In a further attempt to provide an
7. Modified Aqueous Media and Non-aqueous adequate solvent system, aqueous solvent mixtures and
Organic Solvents anhydrous organic solvents have also been employed to
Polar organic solvents that are miscible with water are ensure favorable reaction conditions [46].
added in order to increase the rate of reaction. Commonly Examples of anhydrous organic solvents used include
employed aqueous phase modifiers are acetone, dimethylformamide (DMF), acetonitrile,
dimethylsulfoxide (DMSO) and polyethylene glycol dimethylsulfoxide (DMSO) and polyethylene glycol
(PEG) [24-26, 48]. (PEG) [46].
Fructose has a good solubility in DMSO and HMF The addition of the aprotic solvent N-methyl
yields of 90% can be obtained in pure DMSO solvent. pyrolidinone (NMP) to the aqueous-phase in the biphasic
DMSO can prevent the formation of by-products, but the system increases the selectivity to HMF similar to the
corresponding question of product separation from effect of DMSO. Importantly, replacing NMP with poly
DMSO must be raised because of the high boiling point (1-vinyl-2-pyrrolidinone) (PVP), a hydrophilic polymer
of DMSO [46, 47]. that has NMP moieties along the polyethylene chain,
The reactive nature of pure HMF at high temperature retains the advantage of increased selectivity, but
leads to substantial carbonization of the isolated product significantly reduces carryover into the organic phase
upon distilling HMF from DMSO [46], so vacuum [19].
distillation is necessary to separate HMF from DMSO 8. Sub- and Supercritical Solvents
[46], on the other hand, DMSO is environmentally
questionable [29]. Since the best results for the dehydration of hexoses
Acetone has quite low boiling point, so solvent have been in high-boiling organic solvents, the use of low
recovery via distillation is easily achieved, and no solid boiling solvents in their sub- or supercritical state would
by-products are formed in the organic solvent [49], but be an interesting alternative [26].
unfortunately, the solubility of fructose in pure acetone is When glucose is dehydrated in pure subcritical water,
negligible (0.5 g/L at 25 0C) and thus, either water or HMF has greater selectivity than when using sulfuric acid
another solvent is needed to allow conversion at a or sodium hydroxide as a catalyst under the same pressure
practical scale [47]. A 70:30 (w/w) acetone/water reaction and temperatures [26].
medium resulted in yield of HMF as high as 73.4% for Yields of up to 50% were obtained when using
94% conversion in the presence of a strong cation- fructose as the starting sugar and different zirconium
exchange resin as the catalyst under microwave heating phosphates as catalysts in subcritical water. No
[47]. rehydration products were observed, yet the highest
Acetone/DMSO mixtures can be effectively suppress selectivity was not more than 61% and by-products were
the formation of levulinic acid, so that the HMF yield humins and furaldehyde [18].
increases, and compared with acetone/water, it has lower The overall results from sub- and supercritical water
activation (HMF yield of 89.8% and selectivity of 91.7% have so far been unsatisfactory in terms of yield.
for fructose) [47]. Bicker et al. examined the dehydration of fructose to
A study of Antal and co-workers suggested that HMF HMF in sub- and supercritical acetone/water mixtures and
is formed by dehydration of D-fructose from its furanose obtained the results that both HMF selectivity and the
form [50]; therefore, higher furanoid form concentration fructose conversion increased with decreasing water
of D-fructose in acetone/DMSO mixtures might be the content and the optimal selectivity was 77% with 99%
reason for the lower activation compared with fructose conversion [47].
acetone/water mixtures [47].
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
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9. Ionic Liquids contain at least one modifier to improve selectivity of the
process to yield furan derivative compounds in general
Another attractive alternative to high-boiling organic and HMF in particular [46, 56].
solvents is the use of ionic liquids [26]. Their unique In these systems, the fructose dehydrated in aqueous
physical properties such as negligible vapor pressure and medium and the water immiscible organic solvent is
non-flammability make them particularly suitable as added to extract continuously the HMF from the aqueous
solvents for large-scale production [26]. phase, so the reaction is separated from the reactant and
Biomass can be depolymerized in ionic liquids at reaction intermediates and is thereby protected against
considerably lower temperature than in comparable degradation reaction; however, most extracting solvents
processes that use water as the medium [51, 52]. The first used show poor partitioning of HMF into the organic
dehydration of fructose and glucose with the help of ionic phase, necessitating large amount of solvent and hence
liquids was done in the presence of pyridinium chloride to large energy expenditures to purify the diluted HMF
HMF in high purity with 70% yield for glucose [26]. product [46, 56].
Zhao et al. studied the catalytic conversion of fructose Roman-Leskov et al. studied acid catalyzed fructose
to HMF in 1-alkyl-3-methylimidazolium chloride dehydration in a two-phase reactor system, where fructose
([AMIM] Cl), with metal halides such as chromium (II) was dehydrated in the aqueous phase with DMSO and
chloride as catalyst, achieving 73% yield of HMF [21, poly (1-vinyl-2-pyrrolidinone) (PVP). The HMF was
47]. continuously extracted into an organic phase
The yields of HMF were found to be closely (methylisobutylketone) modified with 2-butanol to
dependent on the acidity type of the ionic liquids, the enhance partitioning from the reactive aqueous solution.
concentration of the ionic liquids and the reaction A maximum selectivity of 85% with 89% fructose
temperature and time [53]. conversion was obtained. In these systems, feed solutions
Acid catalyzed dehydration of fructose was performed consisting of mixed fractions such as hemicelluloses and
using two commercially available ionic liquids, a cellulose can be effectively handled without component
hydrophilic one; 1-butyl-3-methylimidazolium separation [29].
tetrafluoroborate (BMIM+ BF4-) as a solvent and Recently, Dumesic and co-workers invented a
Amberlyte-15 as catalyst which HMF yields up to 50% biphasic system in which the aqueous phase layer
and a hydrophobic one; 1-butyl-3-methylimidazolium comprises of water and one or more aqueous phase
hexafluorophosphate (BMIM+ PF6-) with Amberlyst-15 as modifiers which are selected from water-miscible
catalyst and DMSO to solubilize fructose in the inorganic salts selected from the groups consisting of
hydrophobic ionic liquid which HMF yields close to 80% halides, sulfates, sulfides, phosphates, nitrates, acetates,
[4, 53]. carbonates and ionic liquids; and/or dipolar, aprotic
In another attempt the dehydration of fructose and compounds such as sulfoxides (e.g., DMSO), amides
sucrose in the presence of Brønsted acidic ionic liquid 1- (e.g., dimethylformamide), pyrrolidinones (e.g., NMP),
H-3-methylimidazolium chloride (HMIM+ Cl -) achieved nitriles, pyrones, lactones, water-miscible alcohols or
in high yields HMF (92% for fructose) at relatively low ketones and dioxane, and water-soluble polymers such as
temperature and short reaction time [45, 54, 55]. PVP and PEG [24, 25].
Preparation of HMF in the presence of the Brønsted In this system, the preferred extractive organic
acidic ionic liquid, 3-allyl-1-(4-sulfobutyl) imidazolium solvents are 1-butanol, MIBK, and dichloromethane
trifluoromethanesulfonate as well as its Lewis acid (DCM). Other organic phases, especially other alcohols,
derivative, 3-allyl -1-(4-sulforylchloride butyl) ketones and halogenated alkanes may also be utilized.
imidazolium trifluoromethanesulfonate, concluded that Nitriles, aliphatic and cycloaliphatic ethers,
the type of acidic ionic liquid used played a significant cycloalkanones, saturated and unsaturated aliphatic or
role in the reaction and the Lewis acidic ionic liquids act aromatic hydrocarbons (decane, toluene, benzene),
more effectively. So it shows that the Lewis acidic ionic oxygenated hydrocarbons and nitroalkanes may be used
liquid was a better reaction medium than the Brønsted as well. The organic phase modifiers are selected from the
acidic ionic liquid [53]. group consisting of C1 to C8 aliphatic alcohols, and the
It was demonstrated that when these acidic ionic most preferred is 2-butanol [24, 25]. In the preferred
liquids were immobilized on silica gel, they can be used embodiment using 1-butanole or MIBK as the extracting
as effective and reusable solid catalysts for the solvent, an acid catalyst should be used, such as HCl,
dehydration reaction to convert fructose to HMF [53]. H2SO4, HNO3, etc.
10. Biphasic System With an Organic Extraction By using this modified biphasic reaction in the reactor
Solvent system, high conversion of fructose with high yields of
HMF can be obtained (in one preferred experiment 83%
A biphasic reaction medium comprises of an aqueous HMF selectivity with 83% conversion).
reaction solution and the substantially immiscible organic
extraction solution in which the aqueous reaction
solution, the organic extraction solution or both of them

66
11. Conclusion [8] F.S. Asghari, H. Yoshida,"Acid-catalyzed production of 5-
hydroxymethylfurfural from D-fructose in subcritical water," Ind.
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2-furaldehyde by heterogeneous niobium catalysts,"J. Appl. Catal.
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appreciated. Sbrana," Acid sites characterization of niobium phosphate catalysts
and their activity in fructose dehydration to 5-hydroxymethyl-2-
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