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Sustainable Energy & Fuels Accepted Manuscript

Synthesis of high-density and low-freezing-point jet fuel using
lignocellulose-derived isophorone and furanic aldehydes
++++++++++++++++++++++++++++ ab ab ab ab ab ab c
++++++++++++++++++++++++++++ Jiawei Xie, Lei Zhang, Xiangwen Zhang, Peijuan Han, Junjian Xie, Lun Pan, De-Rong Zou,
c ab
++++++++++++Received 00th Song-Hua Liu and Ji-Jun Zou*
January 20xx,
Accepted 00th January 20xx
Biofuels synthesized from lignocellulose-derived platform chemicals are very attractive for sustainable development. Here
Published on 30 June 2018. Downloaded on 7/11/2018 7:20:18 AM.

DOI: 10.1039/x0xx00000x
www.rsc.org/
we reported a new and facile route to synthesize multi-substituted cycloalkanes with high density and low freezing point
using isophorone and furanic aldehydes (furfural and 5-hydroxymethylfurfural), by solvent-free aldol condensation
followed with hydrodeoxygenation. The catalyst was screened and NaOH shows good performance. The reaction
conditions including catalyst dosage, isophorone/furanic aldehydes ratio, temperature and solvent were optimized, and
finally the yield of 70.0% for isophorone/furfural and 72.8% for isophorone/5-hydroxymethylfurfural were obtained.
Pt/HZSM-5 was prepared as the bifunctional catalyst for hydrodeoxygenation of condensed product. The resultant multi-
substituted cyclohexane derived from isophorone/furfural and isophorone/5-hydroxymethylfurfural have density of 0.813
g/mL and 0.846 g/mL respectively and both with freezing point lower than -75°C, which are very promising as stand-alone
fuels or additives of other biofuels.

1. Introduction
High-density jet fuels have higher density than conventional jet
fuels, and thus can provide more propulsion energy to extend
the flight distance, flight speed and increase the payload of
volume-limited aerospace vehicles like military missile and
space exploration1, 2. High-density jet fuels are generally
composed of cycloalkanes to afford high density, like currently
used JP-10, RJ-7 and RJ-53, which are generally synthesized
using feedstock derived from petroleum. As response to the
increasing concern on CO2 emission and depletion of fossil
energy, production of jet fuels or jet fuel range hydrocarbons
from biomass-derived feedstock has attracted increasing
attention4, 5. So far much work has been done on synthesis of
jet fuel range straight and branched paraffins using
lignocellulose-derived platform chemicals including γ-
valerolactone6, furanic aldehyde7, 8, 2-methylfuran9, 10, methyl
isobutyl ketone11, 12, etc. Nonetheless, these hydrocarbons
have relatively low density compared with petroleum derived
and cannot be used as stand-alone fuel13. To get higher
density, cyclic hydrocarbons such as branched
monocycloalkanes and polycycloalkanes have been
synthesized by C-C coupling reactions like alkylation14-17, aldol
18-22 23 24
condensation , Diels-Alder addition , Michael addition ,
25-27 28
oligomerization , Robinson annulation , followed with
hydrodeoxygenation. For example, cyclic molecules have been
synthesized by reductive coupling/pinacol rearrangement of
29
cyclic ketones (cyclopentanone and cyclohexanone) ,
dehydration/oligomerization/rearrangement of cyclopentanol
27
, and alkylation of phenols (phenol, anisole, guaiacol) with
15, 30
benzyl ether or benzyl alcohols .
Another important requirement for jet fuel is the low-
temperature properties, especially the freezing point and
viscosity. A desirable jet fuel must have low freezing point and
low-temperature viscosity because the aerospace vehicles
often work at very low temperature like high altitude or cold
weather. Although polycycloalkane biofuels have relatively
high density, their freezing point and viscosity is relatively
high. Notably, branched cycloalkanes have shown excellent
low-temperature properties. For example, a mixture of
pentylcyclohexane synthesized using aromatic oxygenates and
furfuryl alcohol, or 2-methylfuran and cyclohexane, as
feedstock shows relatively high density (0.804 g/mL) and very
16, 17
low freezing point (-80°C) . And multi-substituted
cycloalkane synthesized using mesityl oxide and 2-methylfuran
as feedstock has higher density (0.82 g/mL) and a little higher
14
but acceptable freezing point (-56°C) , but this synthesis
requires complex procedure including alkylation, hydrolysis,
intramolecular aldol condensation and hydrodeoxygenation.
With these considerations, here we aimed to synthesize jet
fuel range hydrocarbons with structure of multi-substituted
cyclohexane to get both high density and excellent low-
temperature properties by simple synthetic procedure using

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easily obtained biomass-derived platform chemicals as
feedstock.
Furanic aldehydes including furfural and 5-
hydroxymethylfurfural, are important chemicals which can be
produced on industrial scale by the hydrolysis-dehydration of
5
hemicellulose or cellulose . Isophorone is the cyclic trimer
condensate of acetone from the acetone-butanol-ethanol
31
fermentation of lignocellulose . Considering its multi-
substituted cyclic structure, isophorone should be a good
building brick to synthesize methyl-substituted cyclohexane.
Meanwhile furanic aldehydes are ideal unit to further
introduce branched chain. Therefore in this work, we
presented a new and facile route to synthesize multi-
substituted cycloalkanes using isophorone and furanic
aldehydes as feedstock, by solvent-free aldol condensation
followed with hydrodeoxygenation. Such hydrocarbons have
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both high density and low freezing point, and are promising as
renewable high-density fuels or fuel additives to improve the
density and reduce the freezing point of other biofuels.
2. Experimental section
2.1 Chemicals
Furfural (99%), isophorone (97%) were obtained from Aladdin
Co., China. 5-hydroxymethylfurfural (5-HMF, 98%) was
supplied by Beijing Ouhe Technology Co., Ltd. All the chemicals
used in this work were not further purified, the base catalysts
were all analytical reagents. Pd/C (5 wt%) was obtained from
Shaanxi Rock New Materials Co., Ltd. Palladium dichloride
(PdCl2) was supplied by Tianjin Guangfu Fine Chemical
Research Institute. Chloroplatinic acid (H2PtCl6·6H2O, 99.95%)
was supplied by Beijing HWRK Chem Co., Ltd. HZSM-5
(SiO2/Al2O3=27) and Hβ (SiO2/Al2O3=25) were purchased from
Nankai Catalysts Company.
2.2 Catalyst preparation
Bifunctional hydrodeoxygenation catalysts were synthesized
using the incipient wetness impregnation method. The
supports (HZSM-5, Hβ) were immersed in an aqueous solution
of H2PtCl6·6H2O or PdCl2 and kept overnight at room
temperature to achieve sufficient impregnation. Then drying at
120°C for 12 h and calcination at 580°C for 3 h, the catalysts
were then reduced using hydrogen at 350°C for 4 h.
2.3 Aldol condensation
The aldol condensation was carried out in a round-bottom
flask with reflux condenser and mechanical agitation. Typically,
70 mmol isophorone and 70 mmol furanic aldehyde were
heated to defined temperature (from 10°C to 90°C) and then
defined amount of catalyst (from 6.30 mmol to 15.75 mmol)
was added. During the reaction the liquid mixture was
sampled regularly and the catalyst was removed from the
organic phase by washing. The sampled mixture was dissolved
in dichloromethane for analysis. The organic mixture was
analyzed qualitatively by Agilent 6890/5975 GC-MS equipped
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with HP-5 capillary column (30 m×0.5 mm) and analyzed
quantitatively by gas chromatography (Agilent 7820A).
The conversion and selectivity were calculated as follows:
reactant converted
Conversion
%= ×100
reactant input
mono-condensed product
Selectivity
%= ×100
Sustainable Energy & Fuels Accepted Manuscript
all reactants converted
2.4 Hydrodeoxygenation reaction
The liquid condensed products were purified by washing
before the hydrodeoxygenation reaction. Hydrodeoxygenation
was carried out in a 100 mL batch autoclave (EasyChem E100).
The reactor was loaded with 1 g condensed product, 50 mL
H2O and defined amount of catalyst, purged with H2 for 3
times and then heated to 200°C at 6 MPa of H2. After
hydrodeoxygenation, the organic phase was extracted from
water by ethyl acetate, analyzed qualitatively by Agilent
6890/5975 GC-MS equipped with HP-5 capillary column (30
m×0.5 mm) and analyzed quantitatively by gas
chromatography (Agilent 7820A). Finally, the biofuels were
obtained by vacuum distillation. The yield was calculated as
follows (C14 for isophorone/furfural, C15 for isophorone/5-
HMF):
C14 or C15 HDO product
Yield of HDO product
%= ×100
condensed product input
2.5 Measurements of fuel properties
The density was measured by Mettler Toledo DE40 density
meter according to ASTM D4052. Freezing point was measured
according to ASTM D2386, and kinematic viscosity was
determined using capillary viscometer according to ASTM
D445. The net heat of combustion was measured by the IKA-
C6000 isoperibol Package 2/10 Calorimeter according to ASTM
D240-02.
3. Results and discussion
3.1 Aldol condensation of isophorone and furfural
The aldol condensation of isophorone and furfural under the
catalysis of alkali hydroxides produces mono-condensed 6-(2-
furanylmethylene)-3,5,5-trimethyl-2-cyclohexen-1-one (IF,
mass spectra in Figure S1) as the major product, along with
small amount of di-condensed 2,6-bis(2-furanylmethylene)-
3,5,5-trimethyl-3-cyclohexen-1-one (FIF, mass spectra in Figure
S2) as the byproduct, as shown in Scheme 1. The aldol
condensation is triggered by the proton abstraction from the
α-carbon of isophorone, then the formed carbanion attacks
the carbonyl group of furfural to form β-hydroxy ketone that
32, 33
finally dehydrates to mono-condensed product (IF) .
Similarly, FIF is formed by the further cross-condensation of IF
with furfural. Figure 1 presents the product distribution in the
aldol condensation of isophorone and furfural. The conversion
of both reactants increases with the increase of reaction time.
Since the formation of FIF requires two furfural molecules
while the IF only needs one furfural molecule, the formation of
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FIF is more difficult than IF. Especially at longer reaction time,
the concentration of feedstock (especially furfural) decreases
to a very low level, which suppress the formation of FIF. As one
can see the selectivity of IF increases slightly but that of FIF
decreases after 2 hours. Besides, neither 2-furanic acid nor
furfuryl alcohol presents in detectable amount, suggesting the
Cannizzaro disproportion of furfural does not occur under this
34
condition although it is a base-catalyzed reaction . Also the
self-condensation of isophorone is not seen because it is hard
35
to take place under basic catalysis . Therefore in this work we
can consider the selectivity of IF and FIF only.
Aldol condensation
O O
O
OH-
R O
+ R
H 2O
IF
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Side reaction
O O O
OH - OH -
R O
+
H 2O
R FIF
R = H, furfural; R = CH 2OH, 5-hydroxymethylfurfural
Scheme 1. Aldol condensation of isophorone and furanic
aldehydes.
Fig. 1 Product distribution in the aldol condensation of
isophorone and furfural. Reaction condition: 70 mmol
isophorone, 70 mmol furfural, 30°C, 9.45 mmol NaOH.
Since the generation of carbanion is the first step for the
base-catalyzed aldol condensation and the basicity of the
21
catalyst may has strong influence on the reaction , several
catalysts including KOH, NaOH, Ba(OH)2 and Ca(OH)2 were
tested in this work. As shown in Figure 2, among the tested
catalysts KOH shows the highest activity due to the strongest
basicity, but the selectivity of IF is not the highest. Because the
catalysis of KOH promotes the isomerization of isophorone to
β-isophorone and then condenses with furfural to form di-
condensed FIF. NaOH exhibits a little lower conversion but the
selectivity of IF is the highest, because the basicity is not so
strong as KOH. Ba(OH)2 shows very low activity and Ca(OH)2 is
nearly inactive even with prolonged time and higher
temperature, indicating the basicity is not strong enough to
generate carbanion species. Overall NaOH shows the best
performance to produce IF, so its dosage is further optimized
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to improve the reaction. As shown in Figure 3, the conversion
of both furfural and isophorone gradually increases when
more catalyst is added, but the effect is limited when the
dosage of NaOH exceeds 12.60 mmol. The selectivity of IF goes
up first with the increase of NaOH dosage and then goes down
when the dosage of NaOH exceeds 9.45 mmol, but overall the
Sustainable Energy & Fuels Accepted Manuscript
effect of catalyst dosage is not so obvious as compared with
the conversion.
O
O
O
R
O
Fig. 2 Activity of different catalyst on the aldol condensation of
isophorone and furfural. Reaction condition: 70 mmol
isophorone, 70 mmol furfural, 9.45 mmol catalyst, 30°C and 4
h for NaOH (KOH), 90°C and 24 h for Ba(OH)2 and (Ca(OH)2).
Fig. 3 Effect of NaOH dosage on the aldol condensation of
isophorone and furfural. Reaction condition: 70 mmol
isophorone, 70 mmol furfural, 30°C, 4 h.
Furthermore, the effect of temperature and molar ratio of
feedstock on the aldol condensation of isophorone and
furfural was investigated. As shown in Figure 4, with the
temperature increasing from 10°C to 70°C, the conversion of
furfural and isophorone rises from 39.0% and 21.5% to 99.6%
and 76.5%, respectively. However, the selectivity of IF keeps
nearly unchanged as the temperature increases. The
conversion of furfural, isophorone and the selectivity of IF can
reach 99.6%, 76.5% and 84.2% within 4 h at 70°C, respectively.
Since the by-product (FIF) is generated from di-condensed
between two furfural molecules with one isophorone
molecule, it is expected that reducing the concentration of
furfural in the feedstock could inhibit the side reaction.
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Unfortunately, as shown in Figure 5, the selectivity of mono- reaction is used in this work, and under the optimal reaction
condensation product does not change with the ratio of conditions (9.45 mmol NaOH, 70°C, 0.5 h), the conversion of
furfural/isophorone. The reason may be that the formation of furfural, isophorone and the selectivity of IF can reach 99.6%,
FIF requires two α-H in the ring of isophorone to condense 76.5% and 84.2%, respectively.
with two furfural molecules at the same time, and isophorone
36
has to be isomerized β-isophorone first to produce FIF . In this

Sustainable Energy & Fuels Accepted Manuscript

case, it is the basicity of the catalyst, rather than the molar
ratio or temperature, determining the isomerization of
isophorone to β-isophorone and thus the formation of FIF.
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Fig. 6 Effect of solvent on the aldol condensation of

isophorone and furfural. Reaction condition: 70 mmol
isophorone, 70 mmol furfural, 70°C, 0.5 h, 9.45 mmol NaOH,
15 mL solvent.

Fig. 4 Effect of temperature on the aldol condensation of 3.2 Aldol condensation of isophorone and 5-
isophorone and furfural. Reaction condition: 70 mmol hydroxymethylfurfural
isophorone, 70 mmol furfural, 4 h, 9.45 mmol NaOH.
We further explored the aldol condensation of isophorone and
5-HMF. In this reaction, 6-(5-hydroxymethyl-2-
furylmethylidene)-3,5,5-trimethyl-2-cyclohexen-1-one (mass
spectra in Figure S3) is the mono-condensed product, and the
selectivity can approach over 90% under optimized reaction
condition. In comparison with furfural, 5-HMF is more
promising because it can be easily produced using glucose and
fructose which is more abundant lignocellulose, moreover a
longer carbon chain can be obtained that may increase the
density of the final product. Similar to the reaction of
isophorone and furfural, NaOH shows good activity and
selectivity in this reaction, and the conversion of both
feedstock increases with the increasing of catalyst dosage and
temperature, see Table 1. But a higher selectivity of mono-
Fig. 5 Effect of furfural/isophorone ratio on the aldol condensed product (93%) can be approached because the
condensation of isophorone and furfural. Reaction condition: hydroxymethyl group in 5-HMF brings up steric hindrance that
70 mmol isophorone, 70°C, 0.5 h, 9.45 mmol NaOH. makes the di-condensation reaction difficult to occur. Also
water is unfavorable for the condensation. Under optimized
Subsequently, we studied the effect of solvent on this conditions (9.45 mmol NaOH, 50°C, 2 h), the conversion of 5-
reaction, as shown in Figure 6. It is found that adding strong HMF, isophorone and the selectivity of IF can reach 100%,
polar solvents like DMF slightly promotes the conversion of 68.6% and 93.0%, respectively.
feedstock and the selectivity of IF. In water, the selectivity of IF
is also slightly promoted, however, the conversion of furfural Table 1 Results of aldol condensation of isophorone and 5-
and isophorone decreases obviously because the presence of HMF.
water (the product of aldol condensation) suppresses the
21 Temperature NaOH Conversion of Conversion of Selectivity
reaction equilibrium . Although the organic alcohols Run
(°C) (mmol) isophorone (%) 5-HMF (%) of IF(%)
(methanol, ethanol) accelerate the reaction, the selectivity of 1 30 6.30 55.8 100 89.6
IF becomes extremely low due to the formation of 2 30 9.45 57.5 85.5 91.3
considerable FIF. Low reaction activity is observed in the
3 30 12.60 67.0 100 86.1
presence of THF and hexane solvents due to the insolubility of
4 30 15.75 74.4 97.5 92.8
the catalyst. Overall the use of solvent can not improve the
reaction significantly but increases the cost, so solvent-free 5 50 9.45 68.6 100 93.0

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6* 50 9.45 55.7 90.0 97.0 2wt% Pt/HZSM-5(1 g)* 71.0

7 70 9.45 88.2 98.8 85.9 5wt% Pt/HZSM-5(5 g) 79.4
5wt% Pt/Hβ(5 g) 74.4
Reaction condition: 70 mmol isophorone, 70 mmol 5-HMF, 2 h.
*10 mL H2O was added. Reaction condition: 1 g condensed product, 200°C, 12 h, 50 mL
H2O, 6 MPa H2.

Sustainable Energy & Fuels Accepted Manuscript

*The reaction was conducted for 40 h.

To further promote the HDO reaction we prepared

3.3 Hydrodeoxygenation of mono-condensed product
The mono-condensed products of furfural (or 5-HMF) and
isophorone were further hydrodeoxygenated to C14-C15
multi-substituted cyclohexane in aqueous phase, as shown in
Scheme 2. Based on the GC-MS analysis, the predominate
product is 1,1,5-trimethyl-2-pentyl-cyclohexane (mass spectra
in Figure S4) and 1,1,5-trimethyl-2-hexyl-cyclohexane (mass
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Pt/HZSM-5 because it is reported that Pt is more active than
Pd in hydrogenation of α,β-unsaturated aldehydes41. It can be
seen that the yield increases from 44.9% for 0.5wt% Pd/HZSM-
5 to 68.1% for 0.5wt% Pt/HZSM-5. In addition, both HZSM-5
and Hβ zeolite supports perform well in the HDO. Among the
prepared catalysts, 2wt% Pt/HZSM-5 shows the highest yield
(82.7%) in the HDO of isophorone/furfural aldol condensation

spectra in Figure S5), respectively. The major side-reaction is
the cracking of chain on the C6 ring, which produces small
molecular alkanes and C12-C13 naphthenes. As suggested in
the literature, hydrogenation of the carbonyl in IFs produces
alcohols, which undergo dehydration to alkenes on the acid
site and then a fast C=C hydrogenation will happen
37, 38
. 71.0% yield of C14). Finally the 2wt% Pt/HZSM-5 was chosen as
Meanwhile, the furan ring in the IFs can be effectively
hydrolyzed and deoxygenated with the presence of acid .
39
Therefore this process requires catalyst with both
deoxygenation and hydrogenation functions.
product, and further increase the loading of metal (5 wt%)
does not promote the HDO performance, probably due to the
formation of larger Pt particles. Moreover, lower amount of
HDO catalyst shows acceptable activity (45.8% yield of C14),
and a better result can be obtained with prolonged time (40 h,
the catalyst in the subsequent HDO of isophorone/5-HMF
condensed product, resulting in 85.4% yield of C14+C15.
3.4 Properties of obtained biofuels

O
O isophorone/furfural-derived biofuel (C14) contains 1,1,5-
H2
O Catalyst
OH
O
Scheme 2. Hydrodeoxygenation of mono-condensed product.
Series of catalysts were prepared and test in the HDO of
IFs, as shown in Table 2. First, a physical mixture of commercial
Pd/C and HZSM-5 were tested, unfortunately the yield is very
low because most of the products are uncompleted HDO
compounds. This indicates the synergy of deoxygenation and
hydrogenation is not strong enough. To enhance the synergy
we loaded Pd on HZSM-5 and obtained obviously higher HDO
yield. This can be rationalized because the loading provides
more intimate proximity between the metal and the acid sites,
which will greatly increase the possibility of dehydration on
40
acid sites followed by hydrogenation on metal sites .
After hydrodeoxygenation and vacuum distillation, the
trimethyl-2-pentyl-cyclohexane and its isomers (95.4%), 1,1,5-
trimethyl-2-butyl-cyclohexane (1.5%), 1,1,5-trimethyl-2,4-
dipentyl-cyclohexane (1.3%), and the isophorone/5-HMF-
derived biofuel (C15) contains 1,1,5-trimethyl-2-hexyl-
cyclohexane and isomers (64.2%), 1,1,5-trimethyl-2-pentyl-
cyclohexane and its isomers (29.1%), 1,1,5-trimethyl-2-butyl-
cyclohexane (3.6%). The properties of obtained hydrocarbons
were assessed using ASTM methods, as shown in Table 3.
Notably, the density of these hydrocarbons (0.813 g/mL for
C14 and 0.846 g/mL for C15) is higher than pentylcyclohexane
(0.804 g/mL). This result indicates the presence of methyl
groups and/or longer chain groups can increase the density.
Moreover, the C14 and C15 biofuels have very low freezing
point (< -75°C), although their viscosity increases to some
degree. Overall they show very good low-temperature
properties. Therefore the hydrocarbons synthesized here show
good potential as high-density biofuels or fuel additives.

Table 2 Results for hydrodeoxygenation of isophorone/furfural Table 3 Properties of hydrocarbons synthesized using
aldol condensation product. isophorone and furanic aldehydes.
Catalyst Yield of C14 (%)
Molecular
Pd/C(0.5 g)+HZSM-5(5 g) 12.3 structure

0.5wt% Pd/HZSM-5(5 g) 44.9 Furfural and 5-HMF and Aromatic oxygenates

Feedstock
isophorone isophorone and furfural alcohol
0.5wt% Pt/HZSM-5(5 g) 68.1 Density at
0.813 0.846 0.804
1wt% Pt/HZSM-5(5 g) 77.9 20°C (g/mL)
Freezing
< -75 < -75 < -80
2wt% Pt/HZSM-5(5 g) 82.7 point (°C)
Kinematic
2wt% Pt/HZSM-5(1 g) 45.8 3.4 (25°C) 5.3 (25°C) 2.0 (25°C)
viscosity

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(mm2/s)
26.1 (-30°C) 68.7 (-30°C) 7.5 (-30°C)
Heating
value 43.0 42.9 43.3
(MJ/kg)
Ref. This work This work 16
4. Conclusions
We have developed a facile way to synthesize multi-
substituted cyclohexane via aldol condensation of isophorone
and furanic aldehydes, followed by hydrodeoxygenation.
NaOH shows excellent performance in the aldol condensation
with the conversion of 76.5%/99.6% for isophorone/furfural
and 68.6%/100% for isophorone/5-HMF under optimized
conditions. The yield of mono-condensed product reaches
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70.0% and 72.8% for isophorone/furfural and isophorone/5-
HMF, which is determined by the basicity of the catalyst and
almost unchanged with the molar ratio of feedstock or
reaction temperature. After hydrodeoxygenation, the obtained
hydrocarbons derived from isophorone/furfural and
isophorone/5-HMF have density of 0.813 g/mL and 0.846 g/mL
(20°C) and freezing point less than -75°C, which have good
potential as high-density biofuels or additives of other
biofuels.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (U1462119, 21476168) and the Tianjin
Municipal Natural Science Foundation (16JCQNJC05200).
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