Synthesis of high-density liquid fuel via Diels-Alder reaction of dicyclopentadiene and lignocellulose-derived 2-methylfuran

Article abstract of DOI:10.1016/j.cattod.2018.04.053

A process via Diels-Alder reaction of lignocellulose-derived 2-methylfuran and petroleum-derived dicyclopentadiene following by hydrodeoxygenation was proposed to synthesize a new kind high-density liquid fuel. The results show that the catalysts, temperature and reactant ratio can affect the product distribution of Diels-Alder reaction greatly. Among the investigated catalysts, HY zeolite exhibited the best catalytic activity and showed good recycling ability. Over HY zeolite, high conversion of reactants along with acceptable selectivity of the target products was obtained, under the reaction temperature of 150 °C and 2-MF/DCPD ratio of 2:1. After hydrodeoxygenation, the as-obtained fuel has a density of 0.984 g/mL, much higher than that of widely used JP-10 fuel (0.94 g/mL), a low freezing point of ?58 °C and a volumetric neat heat of combustion of 41.96 MJ/L. Furthermore, a blended fuel with 25% JP-10 exhibits high density and excellent cryogenic properties, which is very promising to serve as high-density fuel for advanced propulsion application.

Full text of DOI:10.1016/j.cattod.2018.04.053

CatalysisTodayxxx(xxxx)xxx–xxx
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Synthesis of high-density liquid fuel via Diels-Alder reaction of
dicyclopentadiene and lignocellulose-derived 2-methylfuran
Junjian Xiea, Xiangwen Zhanga,b, Yakun Liua, Zheng Lia, Xiu-tian-feng Ea, Jiawei Xiea,
⁎
⁎
Yong-Chao Zhanga, Lun Pana,b, , Ji-Jun Zoua,b,
a
Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, China
Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
b
A R T I C L E I N F O
A B S T R A C T
Keywords:
A process via Diels-Alder reaction of lignocellulose-derived 2-methylfuran and petroleum-derived dicyclo-
pentadiene following by hydrodeoxygenation was proposed to synthesize a new kind high-density liquid fuel.
The results show that the catalysts, temperature and reactant ratio can affect the product distribution of Diels-
Alder reaction greatly. Among the investigated catalysts, HY zeolite exhibited the best catalytic activity and
showed good recycling ability. Over HY zeolite, high conversion of reactants along with acceptable selectivity of
the target products was obtained, under the reaction temperature of 150 °C and 2-MF/DCPD ratio of 2:1. After
hydrodeoxygenation, the as-obtained fuel has a density of 0.984 g/mL, much higher than that of widely used JP-
10 fuel (0.94 g/mL), a low freezing point of −58 °C and a volumetric neat heat of combustion of 41.96 MJ/L.
Furthermore, a blended fuel with 25% JP-10 exhibits high density and excellent cryogenic properties, which is
very promising to serve as high-density fuel for advanced propulsion application.
High-density fuel
Diels-Alder reaction
2-Methylfuran
Dicyclopentadiene
Biomass
1. Introduction
chemicals via CeC coupling reactions including alkylation, aldol con-
densation, Michael addition and oligomerization [18–22], and they
High-density liquid fuels can greatly improve the flight distance and
aircrafts payload without increasing the volume of fuel tank, owing to
their relatively higher energy density than traditional refined fuels
[1,2]. Besides, the good cryogenic properties including the freezing
point and viscosity are also very important to ensure the proper func-
tion of fuel in a high altitude or cold area [3]. Traditional high-density
fuels are mainly derived from petroleum, including JP-10 (with exo-
tetrahydrodicyclopentadiene, exo-THDCPD, as the major composition,
0.94 g/mL), RJ-4-I (with exo-tetrahydrodimethylcyclopentadiene as the
major composition, 0.91–0.92 g/mL) and RJ-7 or HDF-T1 (with exo-
tetrahydrotricyclopentadiene, exo-THTCPD, as the major composition,
1.02 g/mL) [1,4–9]. To synthesize the above high-density fuels, the
commonly used reagent is dicyclopentadiene (DCPD), which is an
abundant and cheap by-product of naphtha pyrolysis and coal tar
process [10,11]. And the high density of the resulted fuels arises from
the polycyclic structure of DCPD molecules. However, a further cata-
lytic isomerization is needed to convert the fuels from endo-structure to
exo-structure to greatly improve their cryogenic properties [12].
In recent years, the renewable biomass feedstocks have been ex-
plored to synthesize fuels and valuable chemicals [13–17]. Specifically,
many biofuels have been obtained from biomass-derived platform
usually possess low freezing point and viscosity owing to the presence
of abundant alkyl groups [23,24]. However, except for several bicy-
cloalkanes and polycycloalkanes [18,25–27], most of the reported
biofuels are linear hydrocarbons or branched monocycloalkanes with a
density < 0.85 g/mL, which is much lower than that of petroleum-
based fuels [28–35]. To combine the properties of high density and
good cryogenic properties, the fossil-based polycyclic chemicals and
biomass derivatives with alkyl substituents can be simultaneously uti-
lized as the reactants to produce high-performance fuels.
Herein,
a process via Diels-Alder reaction of DCPD and lig-
nocellulose-derived 2-methylfuran (2-MF) following by hydro-
deoxygenation was carried out to synthesize a new kind high-density
liquid fuel. 2-MF can be obtained by the selective hydrogenation of
furfural which has been produced on an industrial scale via the hy-
drolysis–dehydration of the hemicellulose part of forest residues and
agriculture wastes [36,37]. Notably, both the density (0.984 g/mL) and
volumetric neat heat of combustion (NHOC, 41.96 MJ/L) of the ob-
tained fuel are better than that of JP-10 (0.94 g/mL and 39.6 MJ/L),
and the freezing point of the fuel is as low as −58 °C. This would be a
very potential high-density fuel for practical application.
⁎
Corresponding authors at: Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, China.
E-mail addresses: panlun76@tju.edu.cn (L. Pan), jj_zou@tju.edu.cn (J.-J. Zou).
https://doi.org/10.1016/j.cattod.2018.04.053
Received 30 December 2017; Received in revised form 9 March 2018; Accepted 24 April 2018
0920-5861/©2018ElsevierB.V.Allrightsreserved.
Pleasecitethisarticleas:Xie,J.,CatalysisToday(2018),https://doi.org/10.1016/j.cattod.2018.04.053

J. Xie et al.
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2. Experimental section
2.1. Reagents
2-MF (99%) was obtained from J&K Scientific Ltd. DCPD (98%) was
supplied by Shanghai Titan Scientific Co., Ltd. Pd/C (5 wt%) was pur-
chased from Shaanxi Rock New Materials Co., Ltd. All chemicals were
used without further purification. HZSM-5 (SiO2/Al2O3 = 25), Hβ
(SiO2/Al2O3 = 25), HY (SiO2/Al2O3 = 5.4) and LaY were received from
Nankai Catalysts Company and calcined in air at 580 °C for 3 h.
2.2. Diels-Alder reaction of 2-MF and DCPD
The Diels-Alder reaction was carried out in a 100 mL autoclave
(Easy Chem E100) with a mechanical agitation. A certain molar ratio of
DCPD and 2-MF, and 1.2 g acidic zeolite catalyst were sealed in the
reactor and heated under specific temperature and N2 pressure of
0.5 MPa for 5 h. The reaction solution was sampled periodically and
then centrifuged for analysis by a gas chromatography (Agilent-7820A)
equipped with an FID detector and a capillary column HP-1 capillary
column (30 m × 0.53 mm). Products were determined qualitatively
using an Agilent 6890/5975 gas chromatography-mass spectrometry
(GC–MS) equipped with HP-5 capillary column (30 m × 0.5 mm).
The conversion and selectivity were calculated as follows:
Fig. 1. Product distribution in Diels-Alder reaction of DCPD and 2-MF. Reaction
conditions: 0.1 mol 2-MF, 0.05 mol DCPD, 1.2 g HY zeolite, 150 °C.
1H-1,4-epoxy-5,8-methanofluorene and 8-methyl-3a,4,4a,5,8,8a,9,9a-
octahydro-1H-5,8-epoxy-4,9-methanocyclopenta[b]naphthalene
(la-
belled as DCMF), 4-methyl-3a,4,7,7a-tetrahydro-1H-4,7-epoxyindene
(labelled as CPMF) and TCPD while two reaction pathways involves
2-MF (Scheme
1 and the mass spectra in Fig. S2 and S3, SI).
m(reactant converted)
m(original reactant)
However, after 2 h reaction, the side products, 6-methyl-
4,4a,4b,5,5a,6,9,9a,10,10a,11,11a-dodecahydro-1H-6,9-epoxy-1,4:5,10-
dimethanobenzo[b] fluorene, 1-methyl-4,4a,4b,5,5a,6,9,9a,10,10a,11,
Conversion (wt%) =
Selectivity (wt%) =
× 100%
m(target product produced)
× 100%
11a-dodecahydro-1H-1,4-epoxy-5,10:6,9-dimethanobenzo[b]
and 9-methyl-3a,4,4a,5,5a,6,9,9a,10,10a,11,11a-dodecahydro-1H-6,9-
epoxy-4,11:5,10-dimethanocyclopenta[b]anthracene (labelled as
fluorene
∑ m(reactant converted)
TCMF) produced from further Diels-Alder reaction of TCPD and 2-MF,
begins to emerge and increase with TCPD amount gradually decreased
(Mass spectra, Fig. S4 in SI). After 5 h reaction, the DCPD concentration
is as low as 5%, resulting into a concentration balance for the products.
Therefore, the main products of Diels-Alder reaction of 2-MF and DCPD
are DCMF, CPMF and TCPD, which should be the promising precursor
for high-performance high-energy-density fuels because DCMF and
TCPD will contribute to the high density and volumetric NHOC owing
to the polycyclic structures while CPMF and DCMF will lead to good
cryogenic properties attributed to the branched substitution.
2.3. Hydrodeoxygenation (HDO) reaction
After Diels-Alder reaction, the fuel precursors were purified by fil-
tration and vacuum distillation. Then, the HDO reaction was performed
in the autoclave with 2 g fuel precursors, 50 mL water, 0.2 g Pd/C and
2 g HY zeolite loaded. The reactor was first flushed with N2 gas for 3
times. After that, the HDO reaction was conducted under H2 pressure of
6 MPa and temperature of 150 °C for 5 h. Finally, the target fuels were
purified by vacuum distillation.
Based on the results of Fig. 1, the pathways for Diels-Alder reaction
of DCPD and 2-MF are proposed in Scheme 1. DCPD can decompose to
CPD (Mass spectra, Fig. S5 in SI) at high temperature [39]. Meanwhile,
2-MF, DCPD and CPD will react with each other to form DCMF, CPMF
and TCPD. Then, a side reaction from TCPD and 2-MF will happen to
produce TCMF. To achieve the high yield of target products and good
fuel properties, the reaction parameters (catalyst, temperature, and 2-
MF/DCPD molar ratio) were then modulated to optimize the products
distribution.
2.4. Measurements of fuel properties
The fuel density was measured by a Mettler Toledo DE40 density
meter according to ASTM D4052. Freezing point was measured in ac-
cordance with ASTM D2386. Kinematic viscosity was determined using
capillary viscometer (ASTM D445). The NHOC was measured by the
IKA-C6000 isoperibol Package 2/10 Calorimeter according to ASTM
D240-02 [4].
3. Results and discussion
3.1.2. Optimization of reaction conditions for Diels-Alder reaction
3.1. Diels-Alder reaction of 2-MF and DCPD
Many kinds of molecular sieves, including HY, HZSM, Hβ and alkali
metal or transition metal modified zeolites, etc. have been applied for
Diels-Alder reaction of furan because Diels-Alder reaction can be pro-
moted by microporous materials and Lewis acidic sites [40–44]. Con-
sidering the relatively large molecular size of the side-product TCMF
(average diameter 13.3 Å), several commonly used microporous acidic
zeolites were used as the catalyst to suppress the production of TCMF.
As shown in Fig. 2, the DCPD conversion is much higher than that of 2-
MF under all applied catalysts. Over HY catalyst, the high conversion of
DCPD (88.5%) and 2-MF (56.4%) are achieved with relatively high
selectivity of DCMF (30.2%, average diameter 10.9 Å), CPMF (30.9%,
average diameter 9.3 Å) and TCPD (23.0%, average diameter 10.8 Å).
The high selectivity of DCMF and CPMF is attributed to the large mi-
cropore volume and appropriate average pore diameter of HY zeolite.
3.1.1. Reaction pathway for Diels-Alder reaction
Firstly, the blank reaction with pure raw material (2-MF or DCPD)
was carried out, and there are no products generated using pure 2-MF
as reactant, while DCPD exhibits a relatively high reactivity to produce
tricyclopentadiene (TCPD) and higher oligomers with the selectivity of
90.9% and 9.1%, respectively (Fig. S1 and Scheme S1 in Supporting
information, SI) [38]. Then, 2-MF and DCPD are used together to par-
ticipate in the Diels-Alder reaction. According to the time-dependent
product distribution in Fig. 1, the substrates are converted continuously
with the extension of the reaction time. The consumption rate of DCPD
is much faster than that of 2-MF, because DCPD participates in three
reaction pathways to produce 4-methyl-4,4a,4b,5,8,8a,9,9a-octahydro-
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Scheme 1. Reaction pathway for Diels-Alder reaction of DCPD and 2-MF.
surface area guarantees the high conversion of DCPD (83.6%) and
Lewis acidic sites improve the selectivity of Diels-Alder adducts (total
selectivity of DCMF, CPMF and TCPD is 88.6%), the selectivity of CPMF
is far more than that of DCMF (35.1% vs 11.8%). That is because the
small pore size of LaY catalyst (Table S1, SI) will suppress the formation
of DCMF. Thus, we will discuss Diels-Alder reaction of DCPD and 2-MF
over HY zeolite in the following experiments.
Using HY as catalyst, the reaction temperature was further opti-
mized because Diels-Alder reaction is very sensitive to temperature
[46,47]. The increase of reaction temperature will enhance the effective
collision between reactant molecules, significantly improving the con-
version of the reactants (as shown in Fig. 3). However, the difference
between the conversion of DCPD and 2-MF enlarges obviously with the
rising temperature, owing to the intensified self-aggregation of DCPD at
high temperature [48]. At the temperature of 130 °C, the selectivity of
DCMF (33.6%) and TCPD (35.3%) are very high and the selectivity of
TCMF is as low as 5.6%, but the conversion of the substrates is too low.
At high temperature of 170 °C, the conversions of 2-MF and DCPD are
60.9% and 94.4%, respectively, however, TCMF is the major product
Fig. 2. Effect of catalyst types on Diels-Alder reaction of DCPD and 2-MF.
Reaction conditions: 0.1 mol DCPD, 0.2 mol 2-MF, 1.2 g catalyst, 150 °C, 5 h.
Compared with HY, Hβ zeolite shows a relatively lower DCPD conver-
sion (82.2%) and lower selectivity of DCMF (22.3%) and CPMF (22.4%)
with higher selectivity of TCPD (35.9%) and TCMF (18.3%). For HZSM-
5 zeolite, both the conversion of DCPD and 2-MF are the lowest (31.0%
of DCPD and 14.4% of 2-MF) while the selectivity of DCMF is only
10.8%, and a large amount of TCPD (50.5%) is obtained by Diels-Alder
reaction of CPD and DCPD, which further leads to the production of
TCMF (18.2%). The reason should be that the smaller pore diameter of
HZSM-5 (5.0 Å) makes DCPD (9.0 Å) polymerize outside the pore. Dif-
fusion limitation and the smaller surface area of HZSM-5 zeolite limits
the conversion of the reactants (Table S1, SI). The surface area, average
pore diameter and micropore volume of these catalysts decrease in the
order HY > Hβ > HZSM-5 (Table S1, SI), and the conversion of DCPD
and the selectivity of DCMF and CPMF also decrease in the order of
HY > Hβ > HZSM-5, implying that the bigger surface area and sui-
table average pore diameter can strengthen the conversion of reactant
and the larger micropore volume and appropriate average pore size can
lead to a higher selectivity of DCMF and CPMF. Compared with HY, LaY
zeolite has more Lewis acid sites [45]. Over LaY, although the large
Fig. 3. Effect of reaction temperature on Diels-Alder reaction of DCPD and 2-
MF. Reaction conditions: 0.1 mol DCPD, 0.2 mol 2-MF, 1.2 g HY zeolite, 5 h.
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selectivity of DCMF is as high as 30.2% with a low TCMF selectivity of
13.5%. Therefore, 150 °C is the most suitable temperature for Diels-
Alder reaction of 2-MF and DCPD.
Since the side product TCMF is resulted from Diels-Alder reaction of
TCPD and 2-MF, the molar ratio of 2-MF/DCPD was then optimized.
Fig. 4 shows the selectivity of DCMF and CPMF increase significantly
with the rising molar ratio while that of TCPD and TCMF decrease. At
the ratio of 1:1, although the conversion of 2-MF (67.5%) and DCPD
(88.4%) are relatively high, the selectivity of DCMF is 22.3% and the
proportion of TCPD and TCMF are the highest. At the ratio of 4:1, al-
though the selectivity of DCMF is the highest (34.0%) and that of TCPD
reaches 15.0%, the excessive 2-MF will increase the production costs.
Accordingly, the molar ratio of 2:1 is optimal, and the selectivity of
DCMF and TCMF are 30.2% and 13.5%, respectively, with acceptable
conversion of the reactants.
The recycling stability of HY zeolite was further evaluated in Diels-
Alder reaction. After the reaction, the catalyst was centrifuged, washed
with ethanol for 3 times, calcined at 580 °C for 3 h to remove the coke
deposition, and used for next run. As shown in Fig. 5, after 4 runs, the
selectivity of DCMF is almost unchanged, but the conversion of 2-MF
and DCPD are slightly decreased by 13% and 16%, respectively. It is
caused by the collapse of partial mesoporous channels and reduction of
surface area during the thermal calcination (Table S1, SI). In addition,
considering that HY zeolite is commercially available and relatively
thermal stable, it is a suitable catalyst for the Diels-Alder reaction of
DCPD and 2-MF.
Fig. 4. Effect of 2-MF/DCPD molar ratio on the Diels-Alder reaction of DCPD
and 2-MF. Reaction conditions: 0.1 mol 2-MF, 1.2 g HY zeolite, 150 °C, 5 h.
3.2. Hydrodeoxygenation (HDO) reaction
In order to improve the energy density and thermal stability of the
final fuels, HDO was further carried out to transfer Diels-Alder adducts
to hydrocarbon fuels by physical mixture of acidic zeolite HY and Pd/C,
because acidic support can catalyze the dehydration of biomass derived
oxygenates followed by catalyzing hydrogenation with the metals
[49–51]. As illustrated in Scheme 2, the Diels-Alder adducts, i.e. CPMF,
DCMF and TCPD, can be converted to the saturated C10 and C15
naphthene completely (Mass spectra, Fig. S6, S7 and S8 in SI) under the
reaction temperature of 150 °C and H2 pressure of 6 MPa. After filtra-
tion and vacuum distillation, the obtained fuel contains 13.04% C10 (4-
methyloctahydro-1H-indene, obtained from CPMF), 61.71% DCMF-de-
rived C15 (8-methyldodecahydro-1H-1,4-methanofluorene and 5-methyl-
dodecahydro-1H-4,9-methanocyclopenta[b]naphthalene) and 24.73%
TCPD-derived C15 (dodecahydro-1H-1,4:5,8-dimethanofluorene and do-
decahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene).
Fig. 5. Recycling performance of HY zeolite in Diels-Alder reaction of DCPD
and 2-MF.
3.3. The properties of produced high-density fuel
The properties of the obtained fuel were tested and summarized in
Table 1. This fuel possesses a high density of 0.984 g/mL, which is
higher than the reported biofuels and the widely used JP-10 (0.94 g/
mL), and comparable to THTCPD (1.02 g/mL) [10]. Importantly, the
freezing point of the fuel is −58 °C, which is much lower than that of
THTCPD (a solid at room temperature) [5,6,12]. The fuel has a high
volumetric NHOC of 41.96 MJ/L, which is 2.36 MJ/L higher than that
of JP-10. Besides, the viscosity of the obtained biofuel is 15.5 mm2/s
and 166.5 mm2/s at 20 °C and −20 °C, respectively.
Scheme 2. HDO of Diels-Alder adducts to high-density-fuel molecules.
with a high selectivity of 37.5% and the resulted reaction solution be-
comes black and viscous. Further higher temperature leads to more
oligomer TCMF, which will not only accelerate the consumption of raw
materials DCPD, but also make it difficult for the subsequent by-product
separation. Under moderate temperature of 150 °C, the conversion of
DCPD and 2-MF reaches 88.5% and 56.4%, respectively, and the
Since high viscosity at low temperature will affect the transporta-
tion of fuel in the tank, we studied the potential of this fuel as additive
Table 1
Properties of fuel synthesized by Diels-Alder reaction of DCPD and 2-MF.
Properties
Fuel
Density (g/mL)
Viscosity (mm2/s)
Freezing point (oC)
NHOC (MJ/kg)
42.64
volumetric NHOC (MJ/L)
41.96
20 °C
0.984
20 °C
15.5
0 °C
40.0
−20 °C
166.5
−58
4

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Fig. 6. (a) Viscosity (20 °C, 0 °C, −20 °C) and (b) density (20 °C) of the fuel blending with JP-10.
of conventional fuel by blending with JP-10. As exhibited in Fig. 6, the
viscosity of the blended fuel has been greatly improved (especially
under low temperature of −20 °C) without obvious decrease in density
and the density of the blended fuel has a good linear correlation with
the content of JP-10. Notably, when the composition of JP-10 is 25%,
the blended fuel has a density of 0.972 g/mL, volumetric NHOC of
41.31 MJ/L, a viscosity of 57.8 mm2/s at −20 °C and a freezing point
lower than −75 °C, which is very promising to serve as high-density
fuel for practical applications.
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We gratefully appreciate the financial support from the National
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