Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose

Article abstract of DOI:10.1002/cssc.201200228

Hydroxyalkylation-alkylation (HAA) coupled with hydrodeoxygenation is a promising route for the synthesis of renewable high-quality diesel or jet fuel. In this work, a series of solid-acid catalysts were firstly used for HAA between lignocellulose-derived furan and carbonyl compounds. Among the investigated catalysts, Nafion-212 resin demonstrated the highest activity and stability. Owing to the high activity of the reactants and the advantage in industrial integration, the HAA of 2-methylfuran (2-MF) and furfural can be considered as a prospective route in future applications. Catalyst loading, reaction temperature, and time had evident effects on the HAA of 2-MF and furfural over Nafion-212 resin. Finally, the HAA product of 2-MF and furfural was hydrogenated over a Pd/C catalyst and hydrodeoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium phosphate (Pt/ZrP) was found to be the best catalyst for hydrodeoxygenation. Over the 4 % Pt/ZrP catalyst, a 94 % carbon yield of diesel and 75 % carbon yield of C15 hydrocarbons (with 6-butylundecane as the major component) was achieved. Furfural for all: High-quality diesel is obtained from hemicellulose-derived furfural and 2-methylfuran in a satisfactory yield by the combination of hydroxyalkylation-alkylation and hydrodeoxygenation technologies.

Full text of DOI:10.1002/cssc.201200228

DOI: 10.1002/cssc.201200228
Synthesis of High-Quality Diesel with Furfural and 2-
Methylfuran from Hemicellulose
[a, b]
[a]
[a, c]
[a]
[a]
[a]
Guangyi Li,
Ning Li, Zhiqiang Wang,
Changzhi Li, Aiqin Wang, Xiaodong Wang,
[a]
[a]
Yu Cong, and Tao Zhang*
Hydroxyalkylation–alkylation (HAA) coupled with hydrodeoxy-
genation is a promising route for the synthesis of renewable
high-quality diesel or jet fuel. In this work, a series of solid-acid
catalysts were firstly used for HAA between lignocellulose-de-
rived furan and carbonyl compounds. Among the investigated
catalysts, Nafion-212 resin demonstrated the highest activity
and stability. Owing to the high activity of the reactants and
the advantage in industrial integration, the HAA of 2-methyl-
furan (2-MF) and furfural can be considered as a prospective
route in future applications. Catalyst loading, reaction tempera-
ture, and time had evident effects on the HAA of 2-MF and fur-
fural over Nafion-212 resin. Finally, the HAA product of 2-MF
and furfural was hydrogenated over a Pd/C catalyst and hydro-
deoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium
phosphate (Pt/ZrP) was found to be the best catalyst for hy-
drodeoxygenation. Over the 4% Pt/ZrP catalyst, a 94% carbon
yield of diesel and 75% carbon yield of C15 hydrocarbons
(with 6-butylundecane as the major component) was achieved.
Introduction
[
6]
[3b,7]
Today, with the increasing oil price and social concern about
environmental problems (such as CO and SO emissions from
by the groups of Dumesic and Huber.
In their initial work,
C8–C15 oxygenates were produced by the aldol condensation
of furfural and acetone or the self-aldol condensation of tetra-
hydrofurfural (which can be produced by the selective hydro-
genation of furfural or the selective oxidation of tetrahydrofur-
furyl alcohol). Then the as-prepared C –C oxygenates were
2
2
[1]
the utilization of fossil energy), the production of fuels and
[
2]
chemicals from renewable lignocellulosic biomass has drawn
more and more attention. Furfural is a very important chemi-
cal, which has been produced for decades on an industrial
scale by the hydrolysis–dehydration of the hemicellulose part
of agricultural waste and forest residues (such as corncobs, oat
8
15
hydrogenated over a Pd/Al O catalyst at low temperatures to
2
3
remove the unsaturated C=C and C=O bonds. The hydrogenat-
ed aldol condensation products were hydrodeoxygenated to
C8–C15 alkanes over a Pt-loaded SiO -Al O bifunctional catalyst
[3]
hull, almond husks, bagasse, sunflower husks, and sawdust).
Recently, an economic and highly efficient process for the si-
multaneous production of furfural and organic acids from the
hemicellulose solution from the pulp and paper industries was
2
2
3
in a four-phase reactor. In addition to the aqueous solution of
hydrogenated aldol condensation products and H , hexade-
2
[
3d]
developed by Huber’s group. In that work, furfural was pro-
duced by a two-step process. In the first step, xylose oligomers
were hydrolyzed to xylose monomers at 383 K. Then the
xylose was dehydrated to furfural at a higher temperature
cane was also pumped into the reactor to prevent the deacti-
vation of the Pt/SiO -Al O catalyst. The aldol condensation
2
2
3
[6]
[7b]
could be catalyzed by mineral-base, organic-base, or solid-
[6c,7a,8]
base catalysts.
Recently, it was found that the aldol con-
(
e.g., 473 K). Both reactions were catalyzed by HCl or H SO .
densation and hydrogenation could be integrated into an one-
2 4
The furfural produced was extracted from the NaCl-saturated
water solution with tetrahydrofuran. Under the optimized con-
ditions, a furfural yield of 90% was achieved with the hot
water extract containing 10.7 wt% xylose. It was estimated
that the cost of furfural could be greatly decreased to 366 US$
per metric ton with the application of this new process, which
makes it economically feasible to make diesel or jet fuel with
furfural as the feedstock.
[
a] G. Li, Dr. N. Li, Z. Wang, Dr. C. Li, Prof. A. Wang, Prof. X. Wang,
Prof. Y. Cong, Prof. T. Zhang
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics
Chinese Academy of Sciences
Dalian 116023 (PR China)
Fax: (+86)411-84691570
E-mail: taozhang@dicp.ac.cn
Furfural has only five carbon atoms. Therefore, CÀC coupling
reactions are required to make the oxygen-containing precur-
[
b] G. Li
Graduate University of Chinese Academy of Sciences
Beijing 10049 (PR China)
c] Z. Wang
[
4]
sors with carbon chain lengths in the diesel (C –C ) and jet
9
21
[
3b,5]
[
fuel (C –C ) range.
Subsequently, hydrodeoxygenation is
8
16
Department of Chemical Engineering
Sichuan University
Chengdu 610065 (PR China)
also necessary for the removal of oxygen atoms from these
precursors to make alkanes, which have higher thermal stabili-
ty and energy density. The idea of making diesel- and jet-fuel-
range alkanes with furfural as the feedstock was first proposed
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201200228.
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[
9]
pot reaction over a Pd-loaded Mg-ZrO2 or Pd/Co AlO cata-
2
4
lyst, which was synthesized by a facile coprecipitation pro-
[
10]
cess. Some improvements were also made to the bifunction-
al catalysts used in the hydrodeoxygenation step. With the ap-
plication of Nb-based supports, the presence of hexadecane
became unnecessary to prevent the deactivation of the cata-
[
1e,6a]
lyst.
In the first study on the acid-catalyzed CÀC coupling reac-
tion for the production of diesel and jet-fuel precursors with
[
7b]
furfural as the feedstock, Huber et al. found that trifurylme-
thane (a C13 oxygenate precursor for the production of renew-
able diesel or jet fuel) could be synthesized by the hydroxyal-
kylation–alkylation (HAA) of furan and furfural under the catal-
ysis of 72% H SO . After reaction under reflux for 1 h, a 76%
2
4
yield of trifurylmethane was achieved. A similar result was also
observed for the HAA of furan and 5-hydromethylfurfural
(HMF). However, further hydrodeoxygenation was not per-
formed to produce alkanes with the trifurylmethane. 2-Methyl-
furan (2-MF) is one of the important products in the selective
[
11]
[12]
hydrogenation of furfural.
Recently, Corma et al.
found
that H SO and para-toluenesulfonic acid were active for the
2
4
HAA between 2-MF and some lignocellulose-derived aldehydes
butanal, HMF, and 5-methylfurfural). They suggested that 2-
(
MF had an advantage over furan because one of the two reac-
tive a-positions was protected by the unreactive methyl
group, which could reduce the chance of side reactions (i.e.,
overalkylation). At the same time, they noticed that 5,5-bisylv-
yl-2-pentanone could be synthesized by the trimerization of 2-
MF under the catalysis of 24% H SO . After reaction at 608C
for 16 h, a 94% yield of 5,5-bisylvyl-2-pentanone was obtained.
In the second step, the trimerization product was hydrodeoxy-
genated in a stainless-steel tubular flow reactor heated by
a gradient furnace. The temperature at the beginning of the
reactor was 1208C, a gradient to the middle of the reactor, and
Figure 1. Flow diagram for the production of diesel or jet fuel from lignocel-
lulosic biomass by HAA followed by hydrogenation and hydrodeoxygena-
tion.
treated and separated into cellulose, hemicelluloses, and
lignin. For example, the lignin can be extracted by depolymeri-
2
4
[1d]
zation–solubilization in alkaline/alcohol solution
and burnt
to supply the heat and energy for the whole process. The
hemicellulose can be extracted by steam explosion or hot
[1d]
water treatment. The polymeric xylanes obtained can be hy-
drolyzed to produce xylose monomers, which are then de-
hydrated to produce furfural. The furfural can be selectively hy-
drogenated to 2-MF, which has a reactive a site and can be
used as a feedstock for furan in the HAA reaction. Based on
the HAA reaction of 2-MF, three potential routes for renewable
diesel or jet fuel are proposed. As the first option, 2-MF can
react with furfural under solid-acid catalysis to generate 1c.
After the hydrogenation at low temperature over a Pd/C cata-
lyst followed by the hydrodeoxygenation over a Pt-loaded
solid-acid catalyst, 1c can be converted to 1d. Compared with
the 2-MF trimerization route, the synthesis of 1d by the HAA
of 2-MF and furfural followed by the hydrodeoxygenation is
more cost effective (particularly replacing 2-MF with furfural)
because furfural is the feedstock for the production of 2-MF.
However, to our knowledge, there is no report of this reaction.
As the second option, the HAA can also be carried out be-
tween 2-MF and levulinic esters produced by the hydrolysis–
3508C in the second half of the reactor. After hydrodeoxygena-
tion of this trimerization product, 6-butylundecane (1d in
Figure 1) with an excellent motor cetane number (70.9) and
pour point (183 K) could be obtained. The work of Huber and
Corma opened a new way for the synthesis of high-quality
diesel or jet fuel from lignocellulose-derived platform chemi-
cals. However, there are still many things to do before the real
application of this technology. As we know, H SO and para-
2
4
toluenesulfonic acid are corrosive, which will lead to higher
costs of facilities. The H SO or para-toluenesulfonic acid resi-
2
4
due in the HAA product may poison the catalysts used in the
downstream hydrogenation and hydrodeoxygenation. The re-
moval of H SO4 or para-toluenesulfonic acid residue in the
2
HAA products will produce a lot of wastewater. According to
the principles of green chemistry, the substitution of H SO4
2
and para-toluenesulfonic acid with a highly active, stable solid-
acid material will be preferable owing to the advantages of
less corrosion, less waste, and easier separation and recovery
of the catalyst.
[2h]
dehydration of cellulose. In the work of Mascal and Nikitin, it
was suggested that levulinic acid, ethyl levulinate, and butyl
levulinate could be produced by the solvolysis of 5-(chlorome-
thyl)furfural (CMF) derived from sugars, cellulose, or lignocellu-
Figure 1 shows a flow diagram for the production of diesel
or jet fuel from nonedible lignocellosic biomass, which is the
major component of agricultural waste and forest residues.
In a representative process, lignocellulosic biomass can be pre-
[13]
losic feedstocks. Recently, Dumesic et al. found that the hy-
drolysis–dehydration of cellulose to levulinic acid could be
coupled with the esterification of levulinic acid with alcohol.
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Synthesis of Diesel from Furfural and 2-Methylfuran
Due to its low solubility, the as-prepared levulinic ester was au-
tomatically separated with the aqueous solution. This process
can facilitate the separation and, therefore, greatly decrease
the cost of levulinic acid. Compound 2c, produced by the HAA
of 2-MF and levulinic ester, can be hydrogenated at low tem-
peratures and then hydrodeoxygenated to 2d. The alcohol
consumed during the esterification of levulinic acid can be re-
covered during the hydrogenation and reused for the produc-
[
13]
tion of levulinic ester. As the third option, the hemicellulose
[14]
and cellulose can be fermented to butanol and acetone. The
butanol can be used as midrange gasoline or converted to
[
15]
a variety of fuels and fuel products. The acetone can react
with 2-MF under solid-acid catalysis to produce 3c. The hydro-
genation and hydrodeoxygenation of 3c can produce 3d.
Compared with the other two options, the first has the advant-
age of easier industrial intergration.
Figure 2. Conversions of furfural (gray bars) and yields of 1c (black bars)
with different catalysts. Reaction conditions: 323 K, 2 h; 3.28 g 2-MF, 1.93 g
furfural (2-MF/furfural molar ratio 2:1), and 0.15 g catalyst were used for
each reaction.
In this work, to explore a more economic and environmental
friendly process for the production of renewable high-quality
diesel or jet fuel, we firstly investigated the HAA reaction of 2-
MF and furfural (first option) over a series of solid-acid cata-
lysts. Among the investigated catalysts, Nafion-212 resin,
a commercial solid-acid catalyst, exhibited the highest activity
and stability. The effects of different lignocellulose-derived
furan and carbonyl compounds were also studied. 2-MF and
furfural were found to be the most reactive furan and carbonyl
compounds, respectively, among the investigated candidates.
The effects of catalyst loading, reaction temperature, and time
on the HAA of 2-MF and furfural over Nafion-212 resin were
also explored. Finally, the HAA product of 2-MF and furfural
lite catalysts (such as H-ZSM-5 and H-Y) were inactive for this
reaction.
According to the catalytic performances at low catalyst load-
ing (Figure S1a) and the amounts of acid sites over different
catalysts (measured by NH3 chemisorption according to the
[16]
method described in our previous work ), we also calculated
the turnover numbers (TONs) and turnover frequencies (TOFs)
in the reaction of furfural to 1c over different catalysts.
As shown in Figure S1b, Nafion resins (especially Nafion-212)
exhibited significantly higher TONs and TOFs in the reaction of
furfural to 1c than the other catalysts investigated in this
work.
(i.e., 1c) was hydrogenated over a Pd/C catalyst, then hydro-
deoxygenated over a series of Pt-loaded solid-acid (TiO , SiO -
2
2
Al O , Nb O , ZrP) bifunctional catalysts.
2
3
2
5
Table S1 shows the structures of three families of the most
active catalysts (i.e., Nafion resins, Amberlyst resins, and sulfat-
ed carbon mesoporous materials). Nafion is a perfluorinated
sulfonic acid resin, which is often denoted as a superacid.
Amberlyst is a sulfonic-acid-functionalized cross-linked poly-
styrene resin. However, sulfated mesoporous carbon is amor-
Results and Discussion
Hydroxyalkylation–alkylation
Effect of different solid-acid catalysts
As the first step, we investigated the HAA of 2-MF and furfural
over a series of solid-acid catalysts. From the results shown in
Figures 2 and S1a in the Supporting Information, evident con-
version of 2-MF and furfural to 1c was observed under the cat-
alysis of acidic resins, sulfated carbon materials, sulfated zirco-
nia, and ZrP, which means that these acidic materials can be
used to replace H SO as the catalyst for the HAA of lignocellu-
phous carbon that bears SO H, COOH, and phenolic OH
3
groups, which function as acid sites. In Nafion resins, the acid
strength of the SO H group is enhanced by the presence of
3
fluorine, which makes its acid strength higher than that of Am-
berlyst resins and sulfated mesoporous carbons. In the previ-
[17]
ous work of Iovel and Lukevics, it was found that the HAA
reaction of 2-MF and formaldehyde was sensitive to the acid
strength of the catalyst, and strong acids were more active
than weak acids for this reaction. Analogously, in this work, the
activity sequence of Nafion resin, Amberlyst resin, and sulfated
carbon mesoporous materials can be rationalized by their acid
strength.
2
4
lose-derived furan and carbonyl compounds. The activity of
the different solid-acid catalysts decreased in the order Nafion-
2
12>Nafion-1135>Nafion-115>Amberlyst-36, Amberlyst-15>
2À
CMK-3-SO H, MC-SO H, ZrP, SO /ZrO >AC-SO H. Over the
3
3
4
2
3
Nafion-212 resin, a high yield of 1c up to 67% could be ach-
ieved. This value is almost the same as that of 72% H SO4
From the analysis of the reaction mixtures by using HPLC
and NMR spectroscopy (Figure S2), 1c was identified as the
main product even at low furfural conversion. Besides 1c,
a small amount of 1b and oligomers were also detected in the
reaction mixtures. A two-step reaction pathway is proposed in
Scheme 1. In the first step, 1b was produced by the hydroxyal-
2
(70% yield) under the same reaction conditions. It is interest-
ing that the Nafion-212 resin was even more active than 72%
H SO at low catalyst loading (Figure S1a), which might be ex-
2
4
plained by the low solubility of H SO in the mixture of furfural
2
4
and 2-MF. In contrast, Nb O ·xH O, sulfated alumina, and zeo-
2
5
2
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T. Zhang et al.
cycle time. After the catalyst was
used four times, the yield of 1c
over Amberlyst-15 resin dropped
from 60 to 43%, whereas the
yield of 1c over Amberlyst-36
resin dropped from 59 to 31%.
Considering the excellent activity
and stability of Nafion-212 resin
for the HAA between 2-MF and
furfural, we think that it is
a promising catalyst for future
applications.
Scheme 1. The pathway for the reaction between 2-MF and furfural.
As described in the introduc-
tion, both the aldol condensa-
tion and HAA reactions have
kylation of one 2-MF molecule and one furfural molecule.
In the second step, 1b generated in the first step went on to
react with another 2-MF molecule to produce 1c by an alkyla-
tion reaction. Moreover, taking into account the much higher
yield of 1c compared to that of 1b even at low furfural or 2-
MF conversion, we think that the alkylation step is much faster
than the hydroxyalkylation step, which can be considered as
the rate-determining step in the whole reaction. To further
verify this hypothesis, we also investigated the effect of the 2-
MF/furfural molar ratio; it was found that 1c was always the
major product with the feedstock changed from an excess of
furfural to an excess of 2-MF. This result further confirmed that
hydroxyalkylation was the rate-determining step in the HAA re-
action.
been used to produce precursors for renewable diesel or jet
fuel with furfural as the feedstock. Both reactions can take
place over solid catalysts, which are environmentally friendly.
However, after comparing the two reactions, we think that the
HAA reaction has more advantages: 1) a solid-base catalyst is
used in the aldol condensation reaction, which is sensitive to
[18]
CO in air and the acidic impurities generated by the oxida-
2
tion of furfural. This problem can be avoided in HAA reactions
because a solid acid is used as the catalyst. Such an advantage
is more evident when stable acidic materials such as Nafion-
212 are used. 2) The HAA reaction over a solid-acid catalyst
can occur at a lower temperature (323 K) than that (>373 K) of
[
7a,8c]
the aldol condensation over a solid-base catalyst.
3) In the
straight-chain
alkanes were synthesized by the aldol condensation of furfural
[6]
[3b,7]
work of the groups of Dumesic and Huber,
[6a,c]
(
or HMF) and acetone followed by hydrodeoxygenation.
Catalyst stabilities
In contrast, branched alkanes can be obtained by the HAA
route. As we know, branched alkanes usually have a lower
pour point than straight-chain alkanes. Consequently,
branched alkanes can be used at lower temperatures. Taking
into account the above advantages of HAA, we think it is
a promising route for the synthesis of precursors for high-qual-
ity diesel or jet fuel with lignocellulose-derived platform chemi-
cals.
As another important criterion for the HAA catalysts, the stabil-
ities of the three most active solid-acid catalysts were investi-
gated. Among them, Nafion-212 resin is the most active solid-
acid catalyst, which is less expensive than Nafion-1135 and
-115 resins. Amberlyst-36 and -15 resins have activities compa-
rable to Nafion resins under certain reaction conditions and
their prices are lower. In the stability test, the catalysts were
used four times under the same reaction conditions (323 K,
2
h). To exclude the disturbance of the residues on the used
catalysts (including the hydroxyalkylation and HAA products,
unreacted furfural, and 2-MF), the catalysts were washed thor-
oughly with methanol after each use and dried at 353 K for
1
h. The yield of 1c over Nafion-212 resin slightly increased
then stabilized with increasing recycle time (Figure 3). Con-
versely, evident deactivation was observed over Amberlyst-15
and -36 resins. This result can be explained by the overalkyla-
tion or generation of polymer on the Amberlyst-15 and -36
resins (confirmed by the increased catalyst mass after use).
From the high-resolution SEM images (Figure S3), the number
of pores on the Amberlyst-15 and -36 significantly decreased
after being used under the investigated conditions four times,
which means that the pores in these resin beads have been
plugged with large polymeric molecules generated during the
reaction. Compared with that of Amberlyst-15 resin, the activi-
ty of Amberlyst-36 resin was reduced more with increasing re-
Figure 3. Yields of 1c over Nafion-212 (black bars), Amberlyst-15 (gray bars),
and Amberlyst-36 (white bars) resins. Reaction conditions: 323 K, 2 h; 3.28 g
2-MF, 1.93 g furfural (2-MF/furfural molar ratio 2:1), and 0.15 g catalyst were
used for each reaction.
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Synthesis of Diesel from Furfural and 2-Methylfuran
Effect of different reactants
We compared the HAA reaction of furfural and two
furfural-derived furan compounds. Among them,
[
19]
furan is the decarbonylation product of furfural,
and 2-MF can be produced by the selective hydroge-
nation of furfural. From the analysis of the liquid-
phase products after reaction at room temperature
for 2 h (the chromatograms of the liquid products
are shown in Figure S4), when 2-MF was used as the
furan compound, the furfural conversion (30%) was
higher than that (6%) with furan as the feedstock.
This result can be explained by the greater nucleo-
philicity of 2-MF than furan (owing to the electron
Scheme 3. The pathway for the reaction between 2-MF and acetone.
[
17]
donating effect of the methyl group).
From the
higher reactivity of 2-MF, we think that it is the best candidate
for the furan compound.
To investigate the effect of different carbonyl compounds,
we investigated the HAA of 2-MF with furfural, ethyl levulinate,
and acetone over Nafion-212 resin. From the analysis of the
products of the reaction of 2-MF with ethyl levulinate by using
HPLC and NMR spectroscopy (Figure S5), 2c was identified as
the major product, and 2b was hardly detected in the reaction
mixture. Likewise, when acetone was used as the carbonyl
compound, the only major product identified by using HPLC
and NMR spectroscopy (Figure S6) was 3c instead of 3b. These
results were consistent with that found with furfural as the
feedstock and can be explained by the much higher rate of
the alkylation reaction than the hydroxyalkylation reaction.
From these results, two-step reaction pathways are proposed
in Schemes 2 and 3. A comparison of these pathways with that
shown in Scheme 1 shows that tertiary instead of secondary al-
cohols are generated by the hydroxyalkylation reaction be-
tween 2-MF and ethyl levulinate or acetone. As we know, a ter-
tiary carbocation is more stable than a secondary carbocation,
which leads to the higher rates of alkylation between these hy-
droxyalkylation products and 2-MF. This may be the reason for
the predominance of HAA products when acetone and ethyl
levulinate were used as the carbonyl compounds.
Figure 4. Conversions of carbonyl compounds (gray bars) and yields of HAA
products (black bars) over Nafion-212 resin. Reaction conditions: 323 K, 2 h;
3.28 g 2-MF, 1.93 g furfural or 20 mmol acetone, ethyl levulinate (2-MF/car-
bonyl compound molar ratio 2:1), and 0.15 g catalyst were used for each re-
action.
of an aldehyde compared to a ketone for the HAA of 2-MF.
[12]
In the work of Corma et al. on the trimerization of 2-MF,
water was added to 2-MF under acidic conditions, which led to
the opening of the furan ring to produce 4-oxopentanal. In
such a compound, aldehyde and ketone functional groups
exist simultaneously. However, because the HAA of 2-MF with
the aldehyde part of 4-oxopen-
From the results listed in Figure 4, the highest yield of the
HAA product was observed when furfural was used as the
feedstock. This result may be explained by the higher reactivity
tanal was much faster than that
of the ketone part, the major
product in the trimerization of 2-
MF was 5,5-bisylvyl-2-pentanone.
Effects of reaction conditions on
HAA over Nafion-212
As described above, Nafion-212
resin is the most active and
stable catalyst for the HAA reac-
tion, and 2-MF and furfural are
the most reactive furan and car-
bonyl compounds, respectively,
Scheme 2. The pathway for the reaction between 2-MF and ethyl levulinate.
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T. Zhang et al.
among the investigated candidates. In the following work, we
concentrated on the HAA of these two reactants and investi-
gated the effects of the reaction conditions (catalyst loading,
reaction temperature, and time) on the yield of 1c over
Nafion-212 resin.
The influence of catalyst loading on the yield of 1c over
Nafion-212 resin is shown in Figure 5. The yield of 1c over the
Figure 7. Conversion of furfural (
&
) and yield of 1c (
&
) over Nafion-212 resin
as a function of reaction time. Reaction conditions: 338 K; 3.28 g 2-MF,
.93 g furfural (2-MF/furfural molar ratio 2:1), and 0.15 g catalyst were used
1
for each reaction.
with reaction time in the first 1 h. With the further increase of
reaction time to 6 h, the yield of 1c remained constant.
Figure 5. Conversions of furfural (
&
) and yields of 1c (
&
) over Nafion-212
Hydrodeoxygenation
resin at different catalyst loadings. Reaction conditions: 323 K, 2 h; 3.28 g 2-
MF, and 1.93 g furfural (2-MF/furfural molar ratio 2:1).
As the final aim of this work, the hydrodeoxygenation of hy-
drogenated 1c was also investigated over the Pt catalysts
loaded onto four kinds of acidic supports. From the analysis of
the gas- and liquid-phase products, hydrogenated 1c was
completely converted to hydrocarbons (including linear paraf-
Nafion-212 resin increased with the catalyst mass at low cata-
lyst loading, which can be explained by an increase in the
number of active sites. When more than 0.15 g of catalyst was
used, the yield of 1c did not increase.
A similar relationship between the yield of 1c and reaction
temperature was observed over Nafion-212 resin. As shown in
Figure 6, the yield of 1c over Nafion-212 resin continuously in-
creased as the reaction temperature increased from 273 to
fins, branched paraffins, and cycloparaffins) at 623 K. No CO or
2
CO was detected in the gas-phase products. From the carbon
yields of the different hydrocarbons shown in Figure 8, the Pt/
338 K, and then stabilized with the further increase of reaction
temperature to 353 K.
Figure 7 shows the yield of 1c over Nafion-212 resin as
a function of reaction time at 338 K. The yield of 1c increased
Figure 8. Carbon yields of different alkanes from the hydrodeoxygenation of
hydrogenated 1c over Pt-loaded solid-acid catalysts (
: Pt/SiO –Al O , : Pt/ZrP). Reaction conditions: 623 K, 2.0 g catalyst; liquid
&
2 2 5
: Pt/SiO , : Pt/Nb O ,
&
&
&
3
2
2
À1
À1
2
feedstock flow rate 0.02 mLmin ; H flow rate: 60 mLmin .
ZrP catalyst exhibited the highest carbon selectivities towards
diesel and C15 hydrocarbons among the investigated catalysts.
Over the 4% Pt/ZrP catalyst, a 94% carbon yield of diesel and
Figure 6. Conversions of furfural (
&
) and yields of 1c ( ) over Nafion-212
&
resin at different reaction temperatures. Reaction conditions: 2 h; 3.28 g 2-
MF, 1.93 g furfural (2-MF/furfural molar ratio 2:1), and 0.15 g catalyst were
used for each reaction. The reaction at 353 K was carried out in an auto-
clave.
75% carbon yield of C15 hydrocarbons (with 1d as the major
component; carbon yield=47%) was achieved. These values
are comparable with the best results observed by Corma
&6
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ChemSusChem 0000, 00, 1 – 10
ÝÝ
These are not the final page numbers!

Synthesis of Diesel from Furfural and 2-Methylfuran
[
12]
et al. over a complex catalyst system that contained 3.4% Pt,
.3% Na, 78% C, and 19% Al O using 1,1-bissylvylbutane as
solid-acid catalysts, Nafion-212 resin exhibited the highest ac-
tivity and stability for the HAA of 2-methylfuran (2-MF) and fur-
fural to 1c (a precursor for high-quality diesel or jet fuel). The
influences of different biomass-derived furan and carbonyl
compounds on the yield of the HAA products over Nafion-212
were investigated. Among the investigated candidates, 2-MF
and furfural were found to be the best options for the furan
and carbonyl compounds, respectively. The yield of 1c over
Nafion-212 resin increased with increasing catalyst loading, re-
action temperature, and time, then stabilized. Under the opti-
mized conditions, a 1c yield of up to 75% was obtained. Final-
ly, we also studied the hydrodeoxygenation of hydrogenated
1c over a series of Pt-loaded solid-acid catalysts. Pt/ZrP was
found to be the best catalyst for the hydrodeoxygenation.
Over a 4% Pt/ZrP catalyst, a 94% carbon yield of diesel and
75% carbon yield of C15 hydrocarbons (with 6-butylundecane
as the main component) was achieved.
0
2
3
the feedstock. In the recent work of Huber et al. on the aque-
ous-phase hydrodeoxygenation of sorbitol and xylitol to make
[
20]
gasoline with a high octane number, ZrP was found to be
the best support for the hydrodeoxygenation of carbohydrates
owing to its good catalytic performance and stability. Huber
et al. also studied the dehydration of xylose to furfural over
[
3c]
a series of solid-acid catalyst. Among the investigated cata-
lysts, ZrP was found to be very stable and the most selective
owing to the higher Brønsted and Lewis acid ratio of this ma-
terial. In this work, we also characterized the four different sup-
ports by FTIR spectroscopy with pyridine as a probe. To be
consistent with our activity test, the supports were pre-re-
duced in a H2 flow at 723 K for 2 h. From Figure S7 and
Table S2, we can see that ZrP has the highest Brønsted and
Lewis acid ratio among the four supports, which may be
a reason for the high activity and selectivity of the Pt/ZrP cata-
lyst. To understand the better catalytic performance of Pt/ZrP
from the aspect of the Pt species, we also characterized the Pt-
loaded solid-acid catalysts by XRD and transmission electron
microscopy (TEM). From the results shown in Figures S8 and S9
and Table S3, it was found that the average Pt particle size in
Pt/ZrP was higher than those in the other catalysts. In the pre-
Experimental Section
Preparation of catalysts
Nafion-115, -212, and -1135 resins were supplied by Dupont.
Amberlyst-15 and -36 resins were purchased from Sigma Aldrich.
H-Y (SiO /Al O =4) and H-ZSM-5 (SiO /Al O =140) were provided
[
21]
vious work of Somorjai et al., the hydrogenolysis of ethane
on Pt particles from 1.7–7.1 nm was compared. It was found
that the hydrogenolysis of ethane on Pt particles was structure
sensitive. Smaller particles demonstrated a higher specific ac-
tivity than large particles. According to this result, it was sug-
gested that the coordinatively unsaturated metal atoms pres-
ent in the small particles were more active for CÀC cleavage
than the low index planes that dominate in the large particles.
Analogously, in this work, the higher Pt particle size in the Pt/
ZrP catalyst might be helpful to restrain the unexpected CÀC
cleavage reactions, which might be another reason for the
higher selectivity to C15 alkanes over the Pt/ZrP catalyst.
2
2
3
2
2
3
by Nankai University. Nb O ·xH O was offered from CBMM. Sulfated
2 5 2
active carbon, sulfated CMK-3, and sulfated MC (denoted as AC-
SO H, CMK-3-SO H, and MC-SO H) were prepared according to our
3
3
3
16]
[
previously described method. As the precursor, carbon (2.0 g)
was added to H SO (30 mL, 98%) in a glass tube at room tempera-
2
4
À1
ture. The tube was heated under a N flow (10 mLmin ) at 523 K
2
for 24 h. After cooling to room temperature and filtration, the solid
2À
was washed thoroughly with hot water (353 K) until no SO4 was
detected in the filtrate. The active carbon (AC) used in this work
was supplied by the NORIT Company. CMK-3 and MC were synthe-
[22]
sized by using a previously reported nanocasting method.
In
detail, SBA-15 or commercial silica (1.0 g) was impregnated with
sucrose (1.25 g), concentrated H SO (0.14 g), and H O (5.0 g). The
[
12]
2
4
2
Compared with the method of Corma et al. for the synthe-
resultant mixture was left at ambient temperature overnight, dried
at 373 K for 6 h, and kept at 443 K for 6 h. The above impregnation
procedure was repeated once again with 80% of the amount of
the sucrose and concentrated sulfuric acid used in the first impreg-
sis of 1d, the process used in this work has three advantages:
) solid-acid catalysts (which are easier to separate and reuse)
1
replaced H SO , which is corrosive, an environmental pollutant,
2
4
and may poison downstream hydrogenation catalysts. It was
found that Nafion-212 had excellent activity and stability for
the HAA of 2-MF and furfural, which made it a very promising
catalyst for future applications. 2) In terms of feedstock for the
HAA reaction, furfural is less expensive than 2-MF, which leads
to a lower cost for the synthesis of the 1d precursor by the
HAA of 2-MF with furfural than that prepared by the trimeriza-
tion of 2-MF (i.e., partially replacing 2-MF with furfural). 3) Dif-
ferent from butanal, HMF, and 5-methylfurfural, furfural is the
feedstock for the production of 2-MF, which facilitates industri-
al integration.
nation. The final solid was carbonized at 1173 K in N for 6 h. The
2
silica was removed by etching with 4% HF three times. After filtra-
tion, washing, and drying at 383 K overnight, the CMK-3 or MC
2
À
was obtained. Sulfated zirconia (SO /ZrO ) was prepared accord-
4
2
[23]
ing to the method of Xiao et al. ZrOCl ·8H O and (NH ) SO in
2
2
4 2
4
a molar ratio of 1:6 were ground in a carnelian mortar for 20 min
at room temperature. The product was kept at room temperature
2À
for 18 h and calcined at 873 K for 5 h. Sulfated alumina (SO4
/
Al O ) was prepared according to our previously described
2
3
[24]
method by impregnating the g-Al O with an aqueous solution
2
3
À1
of H SO (2.5 molL ; 15 mL solution per gram of g-Al O ). The slur-
2 4 2 3
ries were stirred slowly for half an hour, filtered without washing,
dried at 383 K overnight, and calcined in air at 873 K for 6 h. ZrP
[25]
was obtained according to the method of Okuhara et al. by the
À1
À1
Conclusions
precipitation of 1.0 molL ZrCl O·8H O and 1.0 molL NH H PO
2 2 4 2 4
aqueous solution at a molar ratio of P/Zr=2.0. The precipitate was
A series of solid-acid catalysts were proven to be effective for
the hydroxyalkylation–alkylation (HAA) of lignocellulose-de-
rived furan and carbonyl compounds. Among the investigated
filtered, washed with water, dried at 373 K overnight, and calcined
at 673 K for 4 h. The Nb O5 was prepared by the calcination of
2
Nb O ·xH O at 673 K for 2 h.
2
5
2
ChemSusChem 0000, 00, 1 – 10
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
&
7
&
ÞÞ
These are not the final page numbers!

T. Zhang et al.
2À
2À
The CMK-3-SO H, MC-SO H, AC-SO H, ZrP, SO /ZrO , SO4 /Al O ,
6890N GC. The CO in the gaseous product was analyzed by a ther-
3
3
3
4
2
2
3
2
H-ZSM-5, H-Y, and Nb O ·xH O catalysts used in this work were
mal conductivity detector (TCD) equipped with an Alltech HAYESEP
DB 100/120 column [30 feet, 1/8 inch outer diameter (OD), 2.0 mm
inner diameter (ID)]. The alkanes in the gaseous product were ana-
lyzed by using a flame ionization detector (FID) equipped with an
Rt-Q-BOND capillary column (30 m, 0.32 mm ID, 10 mm film). Liquid
products were drained periodically from the gas–liquid separator
and analyzed by using an Agilent 6890N GC equipped with a HP-
INNOWAX capillary column (30 m, 0.25 mm ID, 0.5 mm film) and
FID detector.
2
5
2
powders with particle sizes of less than 0.4 mm. The Amberlyst-15
and -36 resins used in this work were beads with diameters of ap-
proximately 0.7 and 0.4 mm, respectively. The Nafion resins used in
this work were films (thickness: 51 mm for Nafion-212, 127 mm for
Nafion-115, and 89 mm for Nafion-1135), which were cut into 2ꢁ
5
mm pieces with scissors before the reaction.
The Pd/C catalyst used for low-temperature hydrogenation was
prepared by the incipient wetness impregnation of the HNO -treat-
3
ed AC with an aqueous solution of PdCl (PdCl dissolved in dilute
2
2
HCl solution). The product was dried at room temperature for 24 h
À1
À1
Acknowledgements
and then reduced by H (60 mLmin gcat ) at 623 K for 2 h. After
2
cooling in H2 to room temperature, the catalyst was passivated
with 1% O in N .
2
2
This work was supported by the Natural Science Foundation of
China (No. 21106143), 100 talent project of the Dalian Institute of
Chemical Physics (DICP), and the Independent Innovation Foun-
dation of State Key Laboratory of Catalysis (No. R201113) of the
DICP.
Pt-loaded SiO -Al O , TiO , Nb O , and ZrP catalysts utilized in the
2
2
3
2
2
5
hydrodeoxygenation were prepared by the incipient wetness im-
pregnation of the corresponding supports with and aqueous solu-
tion of H PtCl ·6H O. The products were dried at room tempera-
2
6
2
ture for 24 h and calcined in air at 773 K for 2 h.
Keywords: renewable resources · zirconium · heterogeneous
catalysis · platinum · biomass
Hydroxyalkylation–alkylation (HAA)
The HAA reaction was carried out in a round-bottomed flask
equipped with a reflux condenser and a magnetic stirrer. The reac-
tion temperature was controlled with a water bath. Typically, cata-
lyst (0.15 g), 2-MF (3.28 g), and furfural (1.93 g) were used for each
reaction. The mixture was stirred at the set temperature for 2 h, fil-
tered, and analyzed by using an Agilent 1100 HPLC equipped with
a ZORBAX SB-C18 (4.6ꢁ150 mm, 5 mm) column and refractive
index detector (RID). A mixture of methanol and water (12:1 v/v)
was used as the eluent.
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À1
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9.
Published online on && &&, 0000
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ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
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ÞÞ
These are not the final page numbers!

FULL PAPERS
G. Li, N. Li, Z. Wang, C. Li, A. Wang,
X. Wang, Y. Cong, T. Zhang*
&& – &&
Synthesis of High-Quality Diesel with
Furfural and 2-Methylfuran from
Hemicellulose
Furfural for all: High-quality diesel is
obtained from hemicellulose-derived
furfural and 2-methylfuran in a satisfac-
tory yield by the combination of hy-
droxyalkylation–alkylation and hydro-
deoxygenation technologies.
&10
&
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ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemSusChem 0000, 00, 1 – 10
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