Professional Documents
Culture Documents
net/publication/230777739
CITATIONS READS
200 783
4 authors, including:
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Md. Imteyaz Alam on 15 May 2014.
www.rsc.org/catalysis MINIREVIEW
Advances in conversion of hemicellulosic biomass to furfural and
upgrading to biofuels
Saikat Dutta, Sudipta De, Basudeb Saha* and Md. Imteyaz Alam
Received 14th April 2012, Accepted 28th May 2012
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
DOI: 10.1039/c2cy20235b
Recent approaches to furfural synthesis from hemicellulosic biomass and pentose sugars with
both homogeneous and solid acidic catalysts have been summarized by addressing the associated
sustainability issues. The features of deconstruction of hemicellulosic biomass by acid hydrolysis
to produce pentose sugar feedstock for furfural have been discussed in brief. Several strategies
including solvent extraction in a biphasic process, application of surface functionalized materials
such as acidic resins, mesoporous solids and mechanistic insight in limited cases are discussed.
The present status of the promising furfural platform in producing second generation biofuels
Downloaded on 03 September 2012
(furanics and hydrocarbon) is reviewed. The performances of each catalytic system are assessed
in terms of intrinsic reactivity and selectivity toward furfural production. Overall, this minireview
attempts to highlight the scope of further developments for a sustainable furfural process and
upgrading to fuels.
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
addressed the conversion of hemicellulose into chemicals and Scheme 1 Furfural platform for biofuels (modified from Fig. 1 in
fuels.7,8 Hemicellulosic fraction of biomass can be used as feed- ref. 13).
stock to produce many important chemicals, such as furfuryl
alcohol, furan, and THF.9 conversion of furfural to different components for example
This contribution is an account of most recent results in the 2-methylfuran, 2-methyltetrahydrofuran etc. Furfural hydrogena-
field of furfural synthesis from the biomass resources with a tion and acid–base-catalyzed reactions applied to upgrade furfural
variety of catalysts including metal salts and solid acidic to fuels have recently been initiated commercially.13
materials in aqueous, organic and biphasic media, highlighting Synthesis routes shown in Scheme 1 are ranked based on
their respective catalytic performances/efficiencies and overall their industrial potential by considering their manufacturing
Downloaded on 03 September 2012
advantages. Possible outlooks and scope of this work are also footprint, investment cost and CO2 emission of furfural upgrade.
included. For example, 2-methylfuran (2-MF) has been considered as a
promising liquid fuel candidate and an extensive road trial of
over 90 000 km with promising outcomes has been reported.13
2. Furfural platform
Furfural is the most common industrial chemical derived from
3. Hemicellulose structure
lignocellulosic biomass, with an annual production volume of
more than 200 000 tonnes.10,11 The commercial utility of furfural Hemicelluloses, a heterogeneous polymer constructed with C5
was first discovered at the Quaker Oats Company in 1921.12 and C6 sugars (such as xylose, arabinose, glucose, galactose,
Quaker Oats tested a variety of processes to valorize the hulls mannose, etc.), is typically the second-most-abundant component
and found that treating them with dilute sulfuric acid yields of biomass, after cellulose.14 In most grasses and hardwoods,
useful amounts of furfural. Furfural also deserves attention as a xylan, a polymer of xylose, is often found as the primary
potential platform for biofuels. Furfural is produced by the hemicellulose. As a result, xylan conversion is critical for
hydrolysis and dehydration of xylan contained in lignocellulose. utilization of important biomass feedstocks such as corn stover,
The value chains of furanic biofuels are realized in terms of Miscanthus, switchgrass, and poplar. Major hemicelluloses are
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012
View Online
In the hydrolysis of hemicelluloses, selective cleavage of the fibers, L-arabinose was selective when using dilute acids as
C–O bonds present between adjacent sugar units is very catalysts.28,29 From these results, it is revealed that furanosides
important to yield intact monomer sugar molecules. Mineral hydrolyze faster than pyranosides30 due to the fact that
acids and enzymes are generally used as catalyst to hydrolyze hydrolysis rate is faster for glycosidic linkages exhibiting
these polymeric carbohydrates.17 Selective acid hydrolysis of nonreducing ends.31 Sugars from hemicelluloses are easy to
hemicellulose substrates produces xylose in good yield which separate almost quantitatively32,33 due to their structures and
essentially depends on the hydrolysis kinetics. Furthermore, noncrystalline nature.
softwoods contain arabinogalactan, xyloglucans, and other Acid hydrolysis of biomass starting from plant biomass
glucans. Pine (Pinus sylvestris) and spruce (Picea abies) contain substrates for production of xylose has been intensively
about 20 wt% O-acetyl-galactoglucomannan and 510 wt% studied (Table 2), for example, from sugar cane bagasse, wheat
arabino-4-O-methyl glucuronoxylan.18 The amounts of different straw, rice straw, cotton-seed, cotton stalk, sunflower stalk,
hemicelluloses in wood are listed in Table 1.19 corn stover, and many more.20 Different strategies of decon-
The selective acid hydrolysis of hemicelluloses to produce struction of hemicelluloses such as acid hydrolysis, enzymatic
pentose sugars is an interesting process, especially for the hydrolysis, hot water extraction, and microwave treatment, to
production of rare sugars (mannose, galactose, lactose), which prepare xylo-oligosaccharides have been reported.20 Unlike
are value-added compounds in biorefinery. Acid hydrolysis of pure xylan, hemicelluloses in biomass serve as linkers of
hemicelluloses from biomass can be compared with cellulose cellulose fibers to microfibrils, and cross-linkers of cellulose
hydrolysis. Selective dilute acid catalyzed hydrolysis of hemi- with lignin to create complex networks that provide structural
celluloses from both wood chips and agricultural wastes has stability.34 Such network in lignocellulosic biomass turns the
been investigated by many researchers in the past.20 The rate
of acid hydrolysis of hemicellulose is partially determined by
the anhydrosugar structure, for example, whether it is an a- or Table 2 The yield of xylose in acid hydrolysis of lignocellulosic
a b-anomer or it is furanose or pyranose form. It is known that biomass and hemicelluloses (Table 2 in ref. 20)
the b-anomers react faster than a-anomers.21 Furthermore, the
Biomass Acid Temp/1C Time/min Yield (%)
rate of acid hydrolysis is faster for furanose compared with
pyranose, thus indicating that arabinose undergoes easier Wheat straw TFA 99 420 80
hydrolysis than xylose.22 The reason for the faster furanose Wheat straw TFA 99 1380 70
Wheat straw HCl 99 120 73
Wheat straw H2SO4 90 720 97
Table 1 The percentage of hemicellulose in wood20 Rice straw H2SO4 145 20
Rice straw H2SO4 121 27 77
Hemicellulose Hardwood Softwood Corncob/corn stover H2SO4 140 50 81
Corn stover H2SO4 180 0.67 80
Methylglucuronoxylans 80–90 5–15 Sugarcane bagasse H2SO4 160 15 88
Arabinomethylglucuronoxylans 0.1–1 15–30 Sugarcane bagasse H2SO4 140 20 83.3
Glucomannans 1–5 1–5 Sugarcane bagasse H2SO4 120 60 80
Galactoglucomannans 0.1–1 60–70 Eucalyptus chips H2SO4 140 10 21.18
Arabinogalactans 0.1–1 1–15 Poplar H2SO4 180 1 80
Other galactans 0.1–1 0.1–1 Arpen wood H2SO4 140 16 76.4
Pectins 1–5 1–5 Oak hardwood H2SO4 150 83
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
hydrolysis of hemicellulose more difficult than that of pure It was found that a chromium-based process offers an
xylan. Although, cellulose hydrolysis with solid acid catalysts advantageous route from pentoses and pentosans to furfural.
has been reported,35,36 methods for one-pot conversion of solid Based on initial studies by Binder et al. xylose conversion into
hemicelluloses (without any pre-treatment) into xylose, arabinose furfural by using combination of chromium(II) or chromium(III)
and furfural using solid acid catalysts (HZSM-5 and HUSY zeolites salts and HCl cocatalyst results in moderate yields via isomeriza-
with 0.5 to 0.74 nm pore diameters, layered clays, aluminum tion and dehydration. This dual catalyst has been used for the
incorporated mesoporous silica Al-MCM-41, Al-SBA-15) in xylose and xylan conversion in N,N-dimethylacetamide containing
aqueous medium are also known.37 As per the results and claim, lithium chloride (DMALiCl) and related solvents.48 Halide
the method is also capable of selectively converting just the additives (LiCl, LiBr etc.) were found to be effective for the
hemicelluloses in lignocellulosic biomass using solid acid catalysts. xylose conversion, affording a maximum yield of furfural
A reaction using 1 wt% sulphuric acid catalyst at 170 1C produced (56%) with CrCl2 (6 mol%) in DMA containing 10 wt% LiBr
50% xylose + arabinose and 10% furfural in 1 h, however, a in 4 h at 100 1C. Analysis revealed a first-order dependence of
maximum of 41% xylose + arabinose was achieved at 170 1C in furfural formation on xylose concentration and half-order
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
3 h with HUSY (Si/Al = 15) catalyst. In this solid catalyzed dependence on CrII concentration, indicating direct involvement
process, maximum 12% furfural can be obtained when using of Cr in the process. Kinetic analyses and deuterium-labeling
HUSY (Si/Al = 15) and K10 montmorillonite clay catalyst. The experiments supported hydride-shift mechanism involving
higher yield of xylose + arabinose with sulfuric acid compared to chromium for xylose isomerization through a 1,2-hydride
HUSY (Si/Al = 15) can be explained by the fact that while sulfuric shift by forming xylulose, a reactive ketose intermediate that
acid releases 12 mmol H+ in the reaction mixture, HUSY releases dehydrates readily into furfural. More challenging xylan
0.165 mmol H+ under the reaction conditions. conversion into furfural, however, afforded 25% furfural,
and 22% from corn stover even at the higher temperature of
140 1C and with HCl as a cocatalyst.
Downloaded on 03 September 2012
4. Homogeneous catalytic strategy Zhao et al. obtained furfural from xylan in 63% yield with
Conversion of pentoses into furfural has been a well-explored CrCl3 catalyst in ionic liquids under microwave-assisted heating
process.38–40 The process invented by Quaker Oats employs a at B200 1C and later extended this method for real biomass corn
dilute sulfuric acid catalyst and stream pressure, achieving stalk, rice straw, and pinewood.49 Furfural yields from these
50% molar yields of furfural from xylan.41 Most industrial biomass variants were only 23–31%, including significant humin
processes reported similar yields, likely limited by side reactions formation. Solid residues (humins) have been a challenge for
such as homopolymerization and condensation with unreacted Jones et al. reported acid-catalyzed production of furfural from
xylose. Furfural can be produced from the dehydration of xylose in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) in
xylose by using Brønsted acids, such as HCl and H2SO4.42–44 the presence of Brønsted acid H2SO4.42
However, these mineral acids are limited by the fact that they In search of a new catalyst that would potentially replace
cause corrosion, safety problems, and require critical reaction the industrially used mineral acid catalysts, recent studies
conditions. Very recently, homogeneously catalyzed process of in aqueous–organic biphasic media showed new directions.
furfural synthesis from the pentose sugars and hemicellulosic Earlier, for sugar dehydration, metal chlorides (CrCl2, ZnCl2,
biomass has been investigated and will be the subject of the FeCl3) have been assessed in non-aqueous deep-eutectic
discussion herein. solvents such as chlorine chloride fructose mixtures50 as well
Dehydration reactions play vital roles in liquid-phase catalytic as in monophasic aqueous media.51,52 A biphasic medium
processing and aqueous phase reforming to produce jet and composed of aqueous solution of FeCl36H2O and NaCl
diesel fuel range alkanes from biomass-derived oxygenated combined with biomass derivable 2-methyltetrahydrofuran
hydrocarbons.45,46 Furfural is a feedstock to make gasoline, (2-MTHF) phase has been demonstrated as an effective
diesel, or jet fuel47 and a kinetic model for the dehydration of biorefinery strategy for xylose dehydration (Fig. 2) by Leitner
xylose in biphasic reaction using a homogeneous catalyst and Maria et al.53 This method exhibited a maximum of 71%
(Scheme 2) depicts the overall scheme. Furfural and xylose can furfural yield in the presence of 20 wt% of NaCl additive.
react together to form undesired solid humins, highly polymerized When 2-methyltetrahydrofuran (2-MTHF) was used as an
insoluble carbonaceous species. Self-reaction of furfural also can extractant, the authors reported an extraction of 98% furfural
result in solid humins. by enhancing the furfural production in aqueous phase.
Gratifyingly, in this case the direct use of seawater comprising
different salts with FeCl36H2O also resulted in an improved
furfural production rate. Conversion of nonpurified xylose
effluents e.g. beech wood (particle size 0.5 to 0.1 mm) in
biphasic water/2-MTHF using oxalic acid as catalyst to
furfural that has been performed also emphasizes the potential
of FeCl36H2O as catalyst.54
Similar to the iron system, AlCl36H2O was employed as catalyst
in biphasic water–THF medium at 140 1C giving 499% xylose
conversion with the formation of xylulose as intermediate with
maximum 30% furfural yield in 5 min.55 AlCl36H2O was
Scheme 2 Xylose dehydration in aqueous phase. also effective for the conversion of lignocellulosic biomass
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012
View Online
5. Solid catalysts
Unlike in the homogeneous regime, several factors such as
Fig. 2 Conversion of xylose to furfural in aqueous-2-MTHF biphasic preparation conditions of the catalyst, structural properties,
medium using iron catalyst starting from beech wood fractionation. and accessibility of acid sites are associated with the efficiency
(modified from Fig. 3 in ref. 53). of solid acid catalyzed conversion of xylose to furfural (Fig. 4).
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
for converting the hemicellulose fraction of lignocellulosic These include modified mesoporous silicas,61,62 exfoliated aggre-
biomass to FuAl by utilizing biphasic systems that consist of gated nanosheets of metal oxides,63 sulfonated metal oxides,64 and
an extractive organic layer (2-sec-butylphenol) and an aqueous microporous silicoaluminophosphates (SAPO).65 Their studies
layer that contains a mineral acid has been demonstrated by revealed that a delaminated zeolite (Si/Al = 29) prepared from
Dumesic and co-workers.56 This biphasic system achieved lamellar precursor (Nu-6(1)) can be an efficient catalyst in
high concentrations of FuAl with maximum 75% yield and water–toluene biphasic media at 170 1C affording 47% furfural
82% selectivity. The use of alkylphenol solvents (Fig. 3) was yield.66 It is revealed that del-Nu-6(1) material could be a
advantageous because of (i) high partition coefficients for promising alternative to conventional zeolites or mesoporous
extraction of FuAl; (ii) not extracting significant amounts of materials for the production of furfural probably due to
mineral acids from aqueous phase; (iii) higher boiling points the easier accessibility of its active sites. Possibly, catalyst
than the final product; and (iv) the fact that they can be performance can be further improved by optimizing the Si/Al
derived from biomass (i.e., lignin). We envisaged the potential ratio and the delamination procedure.
of similar solvents (e.g. eugenol) which can also be extracted Advantage was taken of the extraction solvent for the
from certain essential oil (mainly clove oil) and found them to conversion of xylose to furfural catalyzed by mesoporous
be an efficient extracting agent when used in a biphasic molecular sieve MCM-41 in biphasic water/1-butanol media
aqueous–organic system in the presence of cellulose-derived and the strategy was further enhanced by addition of NaCl as
solid acid for xylose conversion. an auxiliary catalyst.67 The ability to efficiently execute the
A recent study demonstrated an efficient xylose and xylan dehydration step with solid catalysts in a biphasic regime could
conversion process with 72% furfural yield using maleic acid be beneficial from both economical and ecological points of view.
as catalyst in an aqueous medium at 200 1C.54,57 A kinetic That being said, there are still many unanswered questions
study also revealed that xylose degradation rates are lower in pertaining to the behavior of solid catalysts in aqueous medium.
aqueous medium which may be due to the reason that furfural An area of particular focus is the interfacial interactions between
plays the role of a Brønsted base, which reacts with H3O+,
thus decreasing the total acid concentration of the aqueous
system and slowing the degradation of xylose as proposed by
Antel et al.58 It was demonstrated that xylose reaction
rate increases by the addition of potassium halides in the
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
Poisoning of the acid sites by water may also occur depending thermal stability under the xylose dehydration conditions.73
on the surface hydrophilicity/hydrophobicity of the catalyst.71 After 15 consecutive runs under the optimized reaction conditions,
With the objective of investigating the role of Lewis and the robust Nafion membrane remained intact with furfural yields
Brønsted sites in solid acid catalysts for the dehydration of ranging from 58 to 62% in 2 h at 150 1C in DMSO. Deprotona-
carbohydrates in aqueous media, it is desirable to maintain a tion of the sulfonic acid groups of Nafion 117 would deactivate the
high ratio of Brønsted to Lewis acid sites. This conclusion was catalyst by reducing the number of available acid sites for xylose
based on results of comparative catalytic activity for a series of dehydration. Nanoparticulate-sized organic residue deposits are
catalysts Zr–P, SiO2–Al2O3, WOx/ZrO2, g–Al2O3 and HY also responsible for covering up the smooth surface of the Naflon
zeolite for aqueous phase dehydration of xylose.72a Lewis acid as revealed from AFM study (Fig. 5(b)).73 Use of sulfonic acid
sites decrease furfural selectivity by catalyzing side reaction functionalized resin Amberlyst 70 as catalyst afforded 65% xylose
between xylose and furfural to form insoluble humins, e.g. HY conversion with B100% furfural selectivity, however, this process
zeolite due to strong irreversible adsorption of the furfural in challenges economics due to requirement of high xylose loadings.74
the pores, causing an increase in the rate of humin formation. In another approach, hydrothermally stable porous siliceous
Analysis also suggests that the catalyst with the highest materials containing solid silica core and porous silica shell were
number of Lewis acid sites was the most active. The catalyst investigated for the dehydration of xylose in aqueous media
pore confinement was found to have an adverse effect on furfural (Scheme 3). The modified mesoporous core–shell structured
selectivity. Adsorption–desorption studies in the aqueous phase silica (MSHS) spheres (260 nm diameter, solid core and shell)
and decomposition experiments with furfural in aqueous functionalized with sulfonic acid acted as an efficient catalyst
solutions have confirmed that HY zeolite causes furfural to for the dehydration of xylose to furfural with higher selectivity
irreversibly adsorb in the zeolite pores and polymerize to form than the aluminosilicate.75
humic substances. Therefore, it can be concluded that a Sulfated tin oxide (SO42/SnO2), with the SO42 group on
micropore containing catalyst may not be suitable for xylose SnO2 exhibited superior catalytic activity in producing furfural
dehydration due to strong adsorption of the product in from xylose.76 An aqueous phase cyclodehydration of xylose
the catalyst pore. Dehydration of xylose using ion-exchange was carried out using a composite material consisting of
polymer resins (Naflon SAC-13 and Amberlyst 70) with strong zeolite Beta (BEA) nanocrystals (Si/Al = 12) embedded in a
Brønsted acidic sites showed similar furfural selectivity to pure siliceous TUD-1 mesoporous matrix (BEATUD) at 170 1C.
Zr–P and HCl. This confirms that furfural selectivity is a direct A significantly higher xylose conversion to furfural was noted
function of the Brønsted acid sites concentration. Ebitani et al. with the BEATUD catalyst than that with the BEA catalyst as
have reported high yield of furfural and 5-hydroxymethylfurfural the former contained a lower amount of carbonaceous matter
(HMF) from xylose and polysaccharides, respectively, in their and hence favourable for an efficient adsorption caused by the
one-pot synthetic approach using Amberlyst-15 and hydrotalcite surrounding silica matrix.77 Fine tuning of the Si/Al ratio
catalysts.72b–c These furfurals are also efficiently synthesized might change the total amount of acid sites and surface
using tin–tungsten mixed oxide catalyst.72d polarity which may affect the dispersion and the total number
Ion-exchange membrane Nafion 117 (Fig. 5), a sulfonated of accessible acid sites of the zeolite.
tetrafluroethylene based fluropolymer-copolymer, as robust Carbonaceous materials are promising catalysts due to their
and reusable catalyst is promising in terms of economical high surface area and hence provide adequate catalytic active
furfural production as this possesses excellent chemical and sites. Sulfonated graphene oxide (SGO) has been demonstrated
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012
View Online
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
behavior, although the latter was more active and stable. Sen and Yang have demonstrated that pentose sugars and
However, the catalysts deactivated rapidly and regeneration lignocellulosic biomass (e.g. corn stover) can be converted into
process at 400 1C was energy expensive. Carbon-supported 2-methyltetrahydrofuran (2-MTHF) by employing a soluble
Cu-chromite was found to be selective for 2-MF, however, robust rhodium catalyst and HI/HCl + NaI additive in the
deactivated within a few days.91 In a recent study, furfural was presence of H2.87,104 Using corn stover (glucan 40.1% and xylan
hydrogenated over a Cu/Fe catalyst in gas phase with 99% 24.1%) as feed, maximum 63% 2-MTHF yield was achieved. Even
conversion and 98% selectivity in 2-MTHF.92 2-MTHF was though the process is uneconomical due to the use of expensive
also obtained via hydrogenation of furfural over the Cu-based rhodium salt, corrosive acids, and dihydrogen, lignocellulosic
catalyst in the vapor phase.93 In the case of 2-MF synthesis, a pretreatment, enzymatic hydrolysis of cellulose/hemicelluloses,
Downloaded on 03 September 2012
rapid deactivation of the catalyst was observed in gas-phase to obtain sugars is simplified to obtain 2-MTHF as the final
hydrogenation which triggered the necessity of a process at product. Previously, 2-MTHF was synthesized by the coupling
milder temperature and in liquid phase. Nudelman et al.94 of the dehydrogenation of cyclohexanol and the hydrogenation
described the hydrogenolysis of furfural to 2-MF and of of furfural over the Cu–Zn–Al catalyst with optimal hydrogen
5-methylfurfural to DMF, using Pd supported on carbon utilization.105 In vapor phase hydrogenation of furfural to
(Pd/C) at room temperature and 0.2 MPa H2. Sun et al.95 2-methylfuran (2-MF), unselective formation of several furan
reported a polymer-supported PdII complex that catalyzed the products including 2-MTHF was recorded.106 Similarly, 2-MF
hydrogenolysis of furfural to MF. and 2-MTHF were obtained as a mixture of products from
Ethyl levulinate (EL), being known as a potential fuel super critical carbon dioxide (scCO2) mediated continuous-flow
additive with a boiling point of 206 1C, is a novel diesel hydrogenation using a commercial catalyst containing copper
miscible biofuel usually produced by esterification of levulinic chromite and Pd/activated C.107 Liquid phase hydrogenation of
acid (LA) in ethanol.96,97 Traditionally, the formation of EL furfural was also attempted with the NiMoB/g–Al2O3 catalyst
depends on the yield of levulinic acid obtained from biomass affording furfuryl alcohol as a major product.108
by the treatment with aqueous mineral acid (H2SO4 and HCl) In a recent study, the vapor phase conversion of furfural
at 100 1C which provided maximum 40% yield of LA.98 The with SiO2-supported Ni and Ni–Fe bimetallic catalysts in the
same was improved to 60–70% by continuous flow conditions presence of H2 (1 bar) demonstrated a significant deviation in
at higher temperatures and pressure using H2SO4 as catalyst activity. When monometallic Ni catalyst favors formation of
associated with complicated work-up during the separation.99 furfuryl alcohol and furan as primary products via hydrogena-
However, furfural to ethyl levulinate conversion via hydro- tion and decarbonylation, the Ni–Fe bimetallic catalyst
genation to furfuryl alcohol over copper-based catalysts and formed 2-MF as a major product via C–O hydrogenolysis of
subsequent ethanolysis in the presence of strong acids has been furfuryl alcohol.109 In this case, addition of Fe suppresses the
reported (Scheme 5).100 decarbonylation activity of Ni while promoting the CQO
Furfuryl alcohol derived from furfural was then converted hydrogenation (at low temperatures) and the C–O hydro-
to EL by the use of several strong acidic resins on a sulphonated genolysis (at high temperatures). DFT analysis of the possible
polystyrene framework (Amberlyst) and zeolites as solid acid surface species on the mono- and bimetallic surfaces suggests
catalysts since these are known to sustain cock burnt-off during that the differences in selectivity displayed by these catalysts
regeneration.101 The optimum result was achieved by balancing can be attributed to the stability of the Z2-(C,O) surface
the number of acid sites with their accessibility in the resin. The species, which is higher on the NiFe than on pure Ni. As
data presented by authors showed that the efficiency of the acid a result, Z2-(C,O) species can be readily hydrogenated to
catalysts decreases in the following order: H2SO4 4 macro- furfuryl alcohol and subsequently hydrogenolyzed to 2-MF
reticular resins 4 gel resins 4 zeolites. This ranking, however, on the bimetallic alloy due to a strong interaction between the
appears to result from two critical catalysts parameters, carbonyl O and the oxyphilic Fe atoms. On the pure Ni
namely, the acidity of the catalyst and the accessibility of its surface, Z2-(C,O) species can be converted into a surface acyl
acid sites. Good accessibility of the acid sites, for example, species, which can be decomposed to produce furan and CO.
through surface sulfonation as in the case of Amberlyst 46, DFT calculations for geometries and relative stabilities of the
seems therefore favorable. Furfural platform has been further possible furfural species on the catalyst surface showed the
upgraded to alkyl levulinate by the use of a novel hybrid difference in heats of adsorption and bond lengths of furfuryl
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012
View Online
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
1. The mineral acid catalyzed industrial process of furfural is carried out over homogeneous and solid catalysts and coupled
must be replaced with an environmentally sustainable process to other reactions for a better utilization of the feedstock.
towards which limited developments have been made. Ionic Hemicellulosic fraction of lignocellulosic biomass is the best
liquid catalyzed xylose dehydration to furfural and subsequent source for pentose sugars and it does not compete with food
molecular level monitoring of the process using 1H NMR supply. However, these materials are resistant to chemicals
spectroscopy is something yet to be investigated. In spite of transformation. Current practice has demonstrated that there is
tremendous interest in this topic, mechanistic studies on ionic indeed promise. Transformation of sugars into transportation
liquids are rather complicated due to the lack of a powerful fuels and chemical commodities has received much more
analytic tool. Though many investigations have claimed to attention. In the long term, however, the success of the
reveal the mechanistic nature of hexose to 5-hydroxymethyl- biorefinery concept also depends on the development of
fural conversion via cyclic and acyclic routes in aqueous and energetically efficient processes to convert lignocellulosic
organic solvents,118,119 such studies are missing for the pentose biomass directly into biofuels.
sugars to xylose conversion except in limited cases where
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
would provide better insight into the reaction and would trace Production, ed. G. Centi and R. A. van Santen, Wiley-VCH,
the conformational changes that the sugar units have under- Weinheim, 2007, pp. 21–51.
2 J.-P. Lange, Biofuels, Bioprod. Biorefin., 2007, 1, 39–48.
gone during the process. It is revealed that the xylose to 3 J.-P. Lange, R. Price, P. M. Ayoub, J. Louis, L. Petrus, L. Clarke and
furfural conversion goes through the formation of xylulose H. Gosselink, Angew. Chem., 2010, 122, 4581–4585 (Angew. Chem.,
and the steps need Lewis and Brønsted acid catalyst. We hope Int. Ed., 2010, 49, 4479–4483).
to develop and apply dual acidic ionic liquid which can 4 J. Q. Bond, D. M. Alonso, D. Wang, R. M. West and
J. A. Dumesic, Science, 2010, 327, 1110–1114.
operate the process under much lower temperature than the 5 M. Mascal and E. B. Nikitin, Angew. Chem., 2008, 120,
temperature required for an aqueous phase version. 8042–8044 (Angew. Chem., Int. Ed., 2008, 47, 7924–7926).
2. An efficient solid catalyst with dual acidic functionality 6 Y. Roman-Leshkov, J. N. Chheda and J. A. Dumesic, Science,
2006, 312, 1933–1937.
(Lewis and Brønsted) which can initiate the dehydration in
7 J. N. Chheda, Y. Roman-Leshkov and J. A. Dumesic, Green
aqueous medium without much loss of activity must be Chem., 2007, 9, 342–350.
designed. Toward this direction we envisaged the application 8 R. Xing, A. V. Subrahmanyam, H. Olcay, W. Qi, W. G. P. van,
of immobilized sulfonic acid functionalized ionic liquids, H. Pendse and G. W. Huber, Green Chem., 2010, 12, 1933–1946.
9 A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
mesoporous materials with sulfonated surface etc. Using such 2411–2502.
dual functional material as catalyst, we hope to extract direct 10 R. H. Kottke, in Kirk-Othmer Encyclopedia of Chemical Technol-
evidence in favor of the isomerization process, including the ogy, Wiley Interscience, New York, 2004.
characterization of the xylulose intermediate. Catalytic strategies 11 Biorefineries—Industrial Processes and Products, ed. B. Kamm,
P. R. Gruber and M. Kamm, Wiley-VCH, Weinheim, 2006.
may also involve the application of mesoporous carbonaceous 12 H. J. Brownlee and C. S. Miner, Ind. Eng. Chem., 1948, 40,
materials (e.g. Starbon) with surfaces ranging from hydrophilic 201–204.
to hydrophobic based on the degree of carbonization. Such 13 J.-P. Lange, E. van der Heide, J. V. Buijtenen and R. Price,
ChemSusChem, 2012, 5, 150–166.
material with ordered porous structure can then be modified 14 Polysaccharides: Structural Diversity and Functional Versatility,
post-synthetically by incorporating Lewis and Brønsted acidic ed. S. Dumitriu, Marcel Dekker, New York, 2nd edn, 2005.
sites (SnCl4 and SO3H) to develop a one-pot process. Recently 15 K. Sjöström and E. Puukemia, Forest chemistry, Otakustantamo,
Sn-beta zeolite has been successful in catalyzing xylose to Espoo, Finland, 1978.
16 C. Laine, Structures of hemicelluloses and pectins in wood and pulp,
xylulose isomerization process.80 This advocates the requirement Doctoral Dissertations, Helsinki University of Technology, 2005.
of a Lewis acidic site in the catalyst which promotes the 17 Y. Lu and N. Moiser, Biotechnol. Bioeng., 2008, 101, 1170–1181.
isomerization of xylose and subsequent dehydration catalyzed 18 J. Lundqvist, A. Jacobs, M. Palm, G. Zacchi, O. Dahlman and
H. Stalbrand, Carbohydr. Polym., 2003, 51, 203–211.
by a Brønsted acidic site in the catalyst may lead to an efficient
19 I. Spiridon and V. I. Popa, in Monomers, polymers and composites
conversion. from renewable resources, ed. M. N. Belgacem and A. Gandhini,
3. A liquid phase process of furfural hydrogenation–hydro- Elsevier, Amsterdam, 2008, pp. 289–304.
genolysis with high selectivity for 2-MF is something yet to be 20 P. Maki-Arvela, T. Salmi, B. Holmbom, S. Willfor and
D. Y. Murzin, Chem. Rev., 2011, 111, 5638–5666.
developed. Using a supported monometallic or bimetallic 21 Y.-Z. Lai, in Wood and cellulosic chemistry, ed. D. N.-S. Hon and
catalyst (Pd/C or Pd–Ru/C) in the presence of formic acid as N. Shiraishi, Dekker, Basel, Switzerland, 2001, 2nd edn, p. 443.
a hydrogen source, we hope to develop a simple synthesis 22 A. Sharples, Trans. Faraday Soc., 1957, 53, 1003–1013.
protocol for potential fuels and solvents starting from furfural. 23 T. Marzialetti, M. B. V. Olarte, C. Sievers, T. Hoskins,
P. K. Agrawal and C. W. Jones, Ind. Eng. Chem. Res., 2008,
Deconstruction of biomass (celluloses and hemicelluloses) 47, 7131–7140.
has experienced a new development cycle, in which this process 24 J. T. Edward, Chem. Ind., 1955, 1102–1104.
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012
View Online
25 T. P. Nevell and W. R. Upton, Carbohydr. Res., 1976, 49, 65 S. Lima, A. Fernandes, M. Antunes, M. Pillinger, F. Ribeiro and
163–174. A. A. Valente, Catal. Lett., 2010, 135, 41–47.
26 H.-J. Sun, S. Yoshida, N.-H. Park and I. Kusakabe, Carbohydr. 66 S. Lima, M. Pillinger and A. A. Valente, Catal. Commun., 2008, 9,
Res., 2002, 337, 657–661. 2144–2148.
27 B. Kusema, C. Xu, P. Meaki-Arvela, S. Willfor, B. Holmbom, 67 J. Zhang, J. Zhuang, L. Lin, S. Liu and Z. Zhang, Biomass
T. Salmi and D. U. Murzin, Int. J. Chem. React. Eng., 2010, 8, Bioenergy, 2012, 39, 73–77.
1–20. 68 G. E. Brown, V. E. Henrich, W. H. Casey, D. L. Clark,
28 S. J. Hizukuri, Journal of Applied Glycoscience, 1999, 46, 159–165. C. Eggleston, A. Felmy, D. W. Goodman, M. Gratzel,
29 M. Hatanaka, E. Yokoyama, M. Sano, S. Kumazawa and G. Maciel, M. I. McCarthy, K. H. Nealson, D. A. Sverjensky,
T. Takagi, UK Patent GB 2168980 A, 1985. M. F. Toney and J. M. Zachara, Chem. Rev., 1998, 99, 77–174.
30 J. N. BeMiller, Adv. Carbohydr. Chem., 1967, 22, 25–108. 69 R. Rinaldi and F. Schuth, Energy Environ. Sci., 2009, 2, 610–626.
31 J. Hollo, E. Laszlo, K. Szejtli and G. Zala, Starch/Staerke, 1964, 70 B. Kasprzyk-Hordern, Adv. Colloid Interface Sci., 2004, 110, 19–48.
16, 211–220. 71 T. Okuhara, Chem. Rev., 2002, 102, 3641–3666.
32 W. A. Farone and J. E. Cuzens, US Patent, 5,782,982, 1998. 72 (a) R. Weingarten, G. A. Tompsett, W. C. Conner Jr. and
33 K. H. Kim, M. P. Tucker and Q. A. Nguyen, Appl. Biochem. G. W. Huber, J. Catal., 2011, 279, 174–182; (b) A. Takagaki,
Biotechnol., 2002, 98, 100–147. M. Ohara, S. Nishimura and K. Ebitani, Chem. Lett., 2010, 39,
34 E. M. Rubin, Nature, 2008, 454, 841–845. 838–840; (c) J. Tuteja, S. Nishimura and K. Ebitani, Bull. Chem.
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
35 A. Fukuoka and P. L. Dhepe, Angew. Chem., Int. Ed., 2006, 45, Soc. Jpn., 2012, 85, 275–281; (d) K. Yamaguchi, T. Sakurada,
5161–5163. Y. Ogasawara and N. Mizuno, Chem. Lett., 2011, 40, 542–543.
36 C. Luo, S. Wang and H. Liu, Angew. Chem., Int. Ed., 2007, 46, 73 E. Lam, E. Majid, A. C. W. Leung, J. H. Cong, K. A. Mahmoud
7636–7639. and J. H. T. Luong, ChemSusChem, 2011, 4, 535–541.
37 P. L. Dhepe and R. Sahu, Green Chem., 2010, 12, 2153–2156. 74 I. Agirrezabal-Telleria, A. Larreategui, J. Requires, M. B. Güemez
38 R. D. Sproull, P. R. Bienkowski and G. T. Tsao, Biotechnol. and P. L. Arias, Bioresour. Technol., 2011, 102, 7478–7485.
Bioeng. Symp., 1985, 15, 561–577. 75 G. H. Jeong, E. G. Kim, S. B. Kim, E. D. Park and S. W. Kim,
39 C. Moreau, R. Durand, D. Peyron, J. Duhamet and P. Rivalier, Microporous Mesoporous Mater., 2011, 144, 134–139.
Ind. Crops Prod., 1998, 7, 95–99. 76 T. Suzuki, T. Yokoi, R. Otomo, J. N. Kondo and T. Tatsumi,
40 H. D. Mansilla, J. Baeza, S. Urzua, G. Maturana, J. Villasenor Appl. Catal., A, 2011, 408, 117–124.
and N. Duran, Bioresour. Technol., 1998, 66, 189–193. 77 S. Lima, M. M. Antunes, A. Fernandes, M. Pillinger, M. F. Ribeiro
Downloaded on 03 September 2012
41 K. J. Zeitsch, The Chemistry and Technology of Furfural and Its and A. A. Valente, Appl. Catal., A, 2010, 388, 141–148.
Many By-Products, Elsevier, Amsterdam, 2000. 78 E. Lam, J. H. Chong, E. Majid, Y. Liu, S. Hrapovic, A. C. W.
42 C. Sievers, I. Musin, T. Marzialetti, M. B. Valenzuela Olarte, Leung and J. H. T. Luong, Carbon, 2012, 50, 1033–1043.
P. K. Agrawal and C. W. Jones, ChemSusChem, 2009, 2, 665–671. 79 (a) A. Takagasi, M. Ohara, S. Nishimura and K. Ebitani, Chem.
43 R. Weingarten, J. Cho, W. C. Conner Jr. and G. W. Huber, Green Commun., 2009, 6276–6278; (b) M. Moliner, Y. Roman-Leshkov
Chem., 2010, 12, 1423–1429. and M. E. Davis, Proc. Natl. Acad. Sci. U. S. A., 2010, 107,
44 O. Yemis and G. Mazza, Bioresour. Technol., 2011, 102, 6164–6168.
7371–7378. 80 E. Nikolla, Y. Roman-Leshkov, M. Moliner and M. E. Davis,
45 G. W. Huber, R. D. Cortright and J. A. Dumesic, Angew. Chem., ACS Catal., 2011, 1, 408–410.
Int. Ed., 2004, 43, 1549–1551. 81 V. Choudhary, A. B. Pinar, S. I. sandler, D. G. Vlachos and
46 R. R. Davda, J. W. Shabaker, G. W. Huber, R. D. Cortright and R. F. Lobo, ACS Catal., 2011, 1, 1724–1728.
J. A. Dumesic, Appl. Catal., B, 2005, 56, 171–186. 82 S. R. Bare, S. D. Kelly, W. Sinkler, J. J. Low, F. S. Modica,
47 G. W. Huber, J. N. Chheda, C. J. Barrett and J. A. Dumesic, S. Valencia, A. Corma and L. T. Nemeth, J. Am. Chem. Soc.,
Science, 2005, 308, 1446–1450. 2005, 127, 12924–12932.
48 J. B. Binder, J. J. Blank, A. V. Cefali and R. T. Raines, ChemSusChem, 83 C. A. Collyer and D. M. Blow, Proc. Natl. Acad. Sci. U. S. A.,
2010, 3, 1268–1272. 1990, 87, 1362–1366.
49 Z. Zhang and Z. K. Zhao, Bioresour. Technol., 2010, 101, 84 A. Corma, L. T. Nemeth, M. Renz and S. Valencia, Nature, 2001,
1111–1114. 412, 423–425.
50 F. Ilgen, D. Ott, D. Kralisch, C. Reil, A. Palmberger and B. Kçnig, 85 R. Sahu and P. L. Dhepe, ChemSusChem, 2012, 5, 751–761.
Green Chem., 2009, 11, 1948–1954. 86 R. M. West, Z. Y. Liu, M. Peter and J. A. Dumesic, ChemSusChem,
51 G. Marcotullio and W. De Jong, Green Chem., 2010, 12, 2008, 1, 417–424.
1739–1746. 87 W. Yang and A. Sen, ChemSusChem, 2010, 3, 597–603.
52 C. Liu and C. E. Wyman, Carbohydr. Res., 2006, 341, 2550–2556. 88 Y. Román-Leshkov, C. J. Barrett, Z. Y. Liu and J. A. Dumesic,
53 T. vom Stein, P. M. Grande, W. Leitner and P. D. De Maria, Nature, 2007, 447, 982–986.
ChemSusChem, 2011, 4, 1592–1594. 89 D. J. Hayes, S. Fitzpatrick, M. H. B. Hayes and J. R. H. Ross, in
54 T. vom Stein, P. Grande, H. Kayser, F. Sibilla, W. Leitner and Biorefineries—Industrial Processes and Products, ed. B. Kamm,
P. De Maria, Green Chem., 2011, 13, 1772–1777. P. R. Gruber and M. Kamm, Wiley-VCH, Weinheim, 2006, vol. I,
55 Y. Yang, C.-W. Hu and M.-M. Abu-Omar, ChemSusChem, 2012, pp. 139–164.
5, 405–410. 90 (a) J. N. Chheda, G. W. Huber and J. A. Dumesic, Angew. Chem.,
56 E. I. Gürbüz, S. G. Wettstein and J. A. Dumesic, ChemSusChem, Int. Ed., 2007, 46, 7164–7183; (b) M. Chidambaram and A. T. Bell,
2012, 5, 383–387. Green Chem., 2010, 12, 1253–1262; (c) J. G. M. Bremner and R. K. F.
57 E. S. Kim, S. Liu, M. M. Abu-Omar and N. S. Mosier, Energy Keeys, J. Chem. Soc., 1947, 1068–1080.
Fuels, 2012, 26, 1298–1304. 91 L. W. Burnette, I. B. Johns, R. F. Holdren and R. M. Hixon, Ind.
58 M. J. Antel, T. Leesomboon, W. S. Mok and G. N. Richards, Eng. Chem., 1948, 40, 502–505.
Carbohydr. Res., 1991, 217, 71–85. 92 J. Lessard, J.-F. Morin, J.-F. Wehrung, D. Magnin and
59 G. Marcotullio and W. De Jong, Carbohydr. Res., 2011, 346, E. Chornet, Top. Catal., 2010, 53, 1231–1234.
1291–1293. 93 Y.-L. Zhu, H.-W. Xiang and Y.-W. Li, New J. Chem., 2003, 27,
60 X. Shi, Y. Wu, H. Yi, G. Rui, P. Li, M. Yang and G. Wang, 208–210.
Energies (Basel, Switz.), 2011, 4, 669–684. 94 G. Garcia Liñares and N. S. Nudelman, J. Phys. Org. Chem.,
61 A. S. Dias, M. Pillinger and A. A. Valente, J. Catal., 2005, 229, 2003, 16, 569–576.
414–423. 95 Q. Sun, S. Liu, X. Yao, Y. Su and Z. Zhang, Hecheng Huaxue,
62 A. S. Dias, M. Pillinger and A. A. Valente, Microporous Mesoporous 1996, 4, 146–150.
Mater., 2006, 94, 214–225. 96 B. C. Windom, T. M. Lovestead, M. Mascal, E. B. Nikitin and
63 A. S. Dias, S. Lima, D. Carriazo, V. Rives, M. Pillinger and T. J. Bruno, Energy Fuels, 2011, 25, 1878–1890.
A. A. Valente, J. Catal., 2006, 244, 230–237. 97 E. S. Olson, M. R. Kjelden, A. J. Schlag and R. K. Sharma, in
64 A. Dias, S. Lima, M. Pillinger and A. Valente, Catal. Lett., 2007, Chemicals and Materials from Renewable Resources, ed. J. J. Bozell,
114, 151–160. Oxford University Press, 2001, p. 51.
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol.
View Online
98 V. Sunjik, J. Horvat and B. Klaic, Kem. Ind., 1984, 33, 599–606. 110 I. Alam, S. De, S. Dutta and B. Saha, RSC Adv., 2012, DOI:
99 S. W. Fitzpatrick, WO Pat., 8910362, 1989. 10.1039/c2ra20574b.
100 B. Capai and G. Lartigau, US Patent, 5,175,358, 1992. 111 S. De, S. Dutta and B. Saha, ChemSusChem, 2012, DOI: 10.1002/
101 J.-P. Lange, W. D. Van De Graaf and R. J. Haan, ChemSusChem, cssc.201200031.
2009, 2, 437–441. 112 A. Corma, O. De La Torre, M. Renz and N. Villandier, Angew
102 Z. Zhang, K. Dong and Z. K. Zhao, ChemSusChem, 2011, 4, Chem., Int. Ed., 2011, 50, 2375–2378.
112–118. 113 A. Corma, O. De La Torre and M. Renz, ChemSusChem, 2011, 4,
103 R. I. Khusnutdinov, A. R. Baiguzina, A. A. Smirnov, 1574–1577.
R. R. Mukminov and U. M. Whemilev, Russ. J. Appl. Chem., 114 I. Agirrezabal-Telleria, A. Larreategui, J. Requies, M. B. Guemez
2007, 80, 1687–1690. and P. L. Arias, Bioresour. Technol., 2011, 102, 7478–7485.
104 A. Sen and W. Yang, US Patent, 0307050, 2010. 115 R. Weingarten, J. Cho, W. C. Conner and G. W. Huber, Green
105 H.-Y. Zheng, Y.-L. Zhu, Z.-Q. Bai, L. Huang, H.-W. Xiang and Chem., 2010, 12, 1423–1429.
Y.-W. Li, Green Chem., 2006, 8, 107–109. 116 M. J. Climent, A. Corma and S. Iborra, Green Chem., 2011, 13,
106 H.-Y. Zheng, Y.-L. Zhu, B.-T. Teng, Z.-Q. Bai, C.-H. Zhang, 520–540.
H.-W. Xiang and Y.-W. Li, J. Mol. Catal. A: Chem., 2006, 246, 117 G. Marcotullio and W. D. Jong, Green Chem., 2010, 12, 1739–1746.
18–23. 118 M. E. Zakrzewska, E. Bogel-Łukasik and R. Bogel-Łukasik,
107 J. G. Stevens, R. A. Boume, M. V. Twigg and M. Poliakoff, Angew. Chem. Rev., 2011, 111, 397–417.
Published on 01 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CY20235B
Chem., Int. Ed., 2010, 49, 8856–8859. 119 T. Ståhlberg, W. Fu, J. M. Woodley and A. Riisager, ChemSusChem,
108 S. Wei, H. Cui, J. Wang, S. Zhuo, W. Yi, L. Wang and Z. Li, 2011, 4, 451–458.
Particuology, 2011, 9, 69–74. 120 S. J. Dee and A. T. Bell, ChemSusChem, 2011, 4, 1166–1173.
109 S. Sitthisa, W. An and D. E. Resasco, J. Catal., 2011, 284, 121 S. K. R. Patil and C. R. F. Lund, Energy Fuels, 2011, 25,
90–101. 4745–4755.
Downloaded on 03 September 2012
Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2012