Fuel Processing Technology 148 (2016) 361–366

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Fuel Processing Technology

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Research article

Efficient synthesis of high-density aviation biofuel via solvent-free aldol

condensation of cyclic ketones and furanic aldehydes
Qiang Deng, Jisheng Xu, Peijuan Han, Lun Pan, Li Wang, Xiangwen Zhang, Ji-Jun Zou ⁎
Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Collaborative Innovative Center of Chemical Science
and Engineering (Tianjin), Tianjin 300072, China

a r t i c l e i n f o a b s t r a c t

Article history: Transferring lignocellulose-derived compounds to cyclic hydrocarbons via aldol condensation has great potential
Received 5 September 2015 in synthesizing high-density biofuel. But current synthesis involves large amount of solvent that inevitably affects
Received in revised form 18 February 2016 the production efficiency. Herein, we synthesized high-density biofuel efficiently using solvent-free condensa-
Accepted 14 March 2016
tion of cyclopentanone/cyclohexanone and furfural/5-hydroxymethylfurfural. It is found that the solvent-free re-
Available online xxxx
action gives much higher conversion than the diluted one does, for example 86.7% vs 62.7% for cyclopentanone/
Keywords:
furfural condensation, and the selectivity of condensed product is above 90.0%. The reaction rate slows down
High-density biofuel when the reactant is changed from cyclohexanone to cyclopentanone or from furfural to 5-
Aldol condensation hydroxymethylfurfural, but can be improved by simply increases the dosage of catalyst or reaction temperature.
Solvent-free As a result, the yield over 85.0% is obtained for the condensation reactions. Subsequently, the condensed products
Cyclic ketones were converted to branched cyclic hydrocarbons with selectivity of about 70–80%. Their density increases from
Furfural 0.815 g/ml to 0.826 g/ml with the increase of carbon number, with the freezing point increasing from −24.6 °C to
5-Hydroxymethylfurfural −9.5 °C. They have very low viscosity and can be used as liquid fuels alone or blended with other fuels.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction metathesis, dehydration reaction and dimerization [21]. However,

High-density aviation fuel, generally consisting of cyclic hydrocar-
bons, can provide more energy than conventional fuel composed of lin-
ear hydrocarbons, and is advantageous in extending the flight range of
volume-limited aircrafts like missile and rocket [1–8]. An critical prop-
erty of this fuel is high density. Generally, high-density fuel can be used
as fuel alone, but many of them have relatively high viscosity and high
freezing point, and a more practical way is blending them with conven-
tional fuel to get high density and acceptable cold temperature proper-
ties. High-density aviation fuel is mainly derived from petroleum, like
JP-10 (with exo-tetrahydrodicyclopentadiene as major component)
[1–3], RJ-7 and HDF-T1 (with exo-tetrahydrotricyclopentadiene as
major component) [1,4–7], but currently the conversion of biomass to
high-density aviation fuel is attracting increasing interest. The synthesis
of aviation biofuel has been widely studied [9–15], but the obtained lin-
ear and branch alkanes have relative low density (b 0.79 g/ml).
Actually, many biomass-derived compounds have cyclic C–C rings
and are ideal feedstock for high-density biofuel because the cyclic struc-
ture brings up higher density than linear structure. For example, liquid
fuel with density close to synthetic fuel JP-10 can be obtained by dimer-
ization of pinene and turpentine followed by hydrogenation [16–20].
Linalool can be used to synthesize high-density fuel RJ-4 via olefin
⁎ Corresponding author.
E-mail address: jj_zou@tju.edu.cn (J.-J. Zou).
these feedstocks are relatively limited because they are obtained only
from specific woods and plants.
An alternative is to use cyclic biomass platform compounds as reac-
tant. Recently, hemicellulose-derived cyclopentanone and lignin-
derived cyclohexanone are converted to bi-cyclic biofuels by aldol self-
condensation followed by hydrodeoxygenation [22–27]. Some monocy-
clic alkanes are obtained through aldol condensation of hemicellulose-
derived furfural (or cellulose-derived 5-hydroxymethylfurfural) and
cyclopentanone [28,29], hydroxyalkylation/alkylation of 2-methylfuran
with cyclopentanone or cyclohexanone [30,31]. Actually, the aldol con-
densation involving furfural/5-hydroxymethylfurfural as reactant has
many advantages because these compounds are primary derivatives of
lignocellulose and thus produced with low-cost. Although solvent-free
condition has been used in aldol reaction of furfural and methyl isobutyl
ketone/3-pentanone [32,33], mostly a lot of water are used as solvent/
diluent in these aldol reactions of furanic aldehydes and cyclic ketones
[28,29], which inevitably affects the production efficiency and cost of
biofuels. Compared with diluted reaction, the solvent-free reaction is
more efficient for scale-up and saves cost for solvent purification and
recycling. In addition, cyclohexanone can also react with furanic alde-
hydes via aldol condensation [34], and produces cycloalkane with den-
sity higher than the case of cyclopentanone due to the increase of
carbon number in molecule.
In this work, we explored the solvent-free aldol condensation of cy-
clic ketones (cyclopentanone, cyclohexanone) and furanic aldehydes

http://dx.doi.org/10.1016/j.fuproc.2016.03.016
0378-3820/© 2016 Elsevier B.V. All rights reserved.
362 Q. Deng et al. / Fuel Processing Technology 148 (2016) 361–366
Scheme 1. Synthesis of biofuel using cyclic ketones and furanic aldehydes as feedstock.
(furfural, 5-hydroxymethylfurfural), simply using NaOH as catalyst, as
shown in Scheme 1. It was found that the solvent-free reaction is
more efficient than the diluted one, and the reaction conditions were
optimized to maximize the yield (over 85%). After hydrodeoxygenation,
four biofuels with density of 0.815 g/ml–0.826 g/ml were obtained.
2. Experimental section
2.1. Materials
Furfural (99%), cyclohexanone (99.5%), cyclohexane (99.5%), mag-
nesium hydroxide, sodium hydroxide and palladium dichloride (99%)
were obtained from Tianjin Guangfu Fine Chemical Research Institute.
Cyclopentanone (99.5%) and sodium carbonate were purchased from
Tianjin Jiangtian Chemical Technology Company. Calcium hydroxide
was supplied by Tianjin Bodi Chemical Engineering Company. 5-
hydroxymethylfurfural (5-HMF, 98%) was obtained from Beijing Ouhe
Technology Company. All the chemicals were used without further pu-
rification. Hβ (SiO2/Al2O3 = 25) was purchased from Nankai Catalysts
Company and calcined in air at 550 °C for 6 h. 5wt% Pd/Hβ was prepared
by the incipient wetness impregnation method.
2.2. Aldol condensation reaction
The aldol reaction was carried out in a round-bottom flask equipped
with a reflux condenser and a mechanical stirrer. Typically, 0.208 mol
furfural (or 5-HMF) and 0.104 mol cyclopentanone (or cyclohexanone)
were heated to defined temperature and then defined amount of cata-
lyst (molar ratio relative to cyclic ketones ranging from 3.6 mol% to
18.0 mol%) was added. The product (FCF, Scheme 1) is not dissolvable,
so the reaction system gradually became slurry with the proceeding of
reaction. The mixture was sampled periodically and dissolved in
DMSO for analysis. The composition was analyzed by a gas chromato-
graphs (Bruker 456GC, Bruker), equipped with FID detector and ZB-
5HT column (60 m × 0.25 mm × 0.25 m). The structure of product
was also determined by 13C and 1H NMR spectra collected on a Varian
Inova 500 MHz NMR.
2.3. Hydrodeoxygenation reaction and fuel property measurements
A reported procedure [30,31] was adopted for the hydrodeoxygenation
of FCF produced via the aldol condensation in a 500 ml batch autoclave re-
actor (Parr Instrument Co.) equipped with mechanical stirring. 15.0 g of
FCF, 300.0 ml of cyclohexane and 4.0 g of Pd/Hβ catalyst were sealed in,
purged with H2 and then heated to 280 °C for 24 h at 8 MPa of H2. Biofuel
was obtained by vacuum distillation of the hydrodeoxygenated product
to remove the cracking byproduct.
The density of fuel was measured by Mettler Toledo DE40 den-
sity 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.
3. Results and discussion
3.1. Aldol condensation of cyclopentanone and furfural
The aldol condensation of cyclopentanone and furfural produces di-
condensed 2,5-bis(2-furylmethylidene)cyclopentan-1-one (FCF), with
small amount of mono-condensed 2-(2-furylmethylidene)cyclopentan-
1-one (FC), as shown in Scheme 1. The structure of FCF and FC is well il-
lustrated by NMR spectra, see Fig. 1a, e. Although cyclopentanone may
take place self-condensation under acid and base catalysis [22,23,27], it
does not happen in the present work because furfural reacts more
quickly with carbon anion formed by cyclopentanone due to the smaller
steric hindrance. Neither 2-furanic acid nor furfuryl alcohol presents in
detectable amount, indicating furfural does not react with itself under
these conditions although it is also a base catalytic reaction [35].
Fig. 2 compares the reaction behavior under solvent-free and diluted
conditions. Compared with the diluted reaction, the solvent-free one
precedes more quickly due to the high concentration of reactant. Both
cyclopentanone and furfural are converted almost equally, and the con-
version of cyclopentanone reaches 87.7% at 2 h, whereas the diluted re-
action gives a conversion of only 62.7%. And the selectivity of solvent-
free reaction (87.9%) is just slightly lower compared with the case of di-
luted reaction (91.9%), which indicates that the reaction equilibrium
can be easily reached in the solvent-free reaction. In previous literature,
the use of solvent is aimed to improve the product separation [28]. Ac-
tually, the condensed product, namely FCF, is non-polar and not dis-
solved in either the reactant or in-situ produced water. After the
reaction, FCF in form of yellow solid can be easily separated, see Table 1.
Several base catalysts including NaOH, Mg(OH)2, Ca(OH)2 and
Na2CO3 were tested in the solvent-free reaction. NaOH is very good cat-
alyst but the others are nearly inactive (with conversion b2.0%). The al-
kalinity order of these catalysts is NaOH N Mg(OH)2 N Ca(OH)2 N Na2CO3,
and weak base cannot activate cyclopentanone to form carbanion which
is necessary for the condensation. Table 2 shows that both the catalyst
dosage and temperature have considerable effect on the reaction. The
conversion increases from 12.4% to 96.5% when the catalyst dosage
rises from 3.6 mol% to 10.8 mol% at 30 °C. Actually, the conversion ap-
proaches 94.0% in 30 min. Also, the selectivity of FCF increases slightly
with the increase of catalyst dosage. As a result, after 2 h-reaction at
30 °C with 10.8 mol% catalyst, the conversion of cyclopentanone, selec-
tivity and yield of FCF reach 96.5%, 95.3% and 92.0%, respectively. Alterna-
tively, increasing the temperature can also improve the conversion and
 Q. Deng et al. / Fuel Processing Technology 148 (2016) 361–366 363

Fig. 1. 13C (a, b, c, d) and 1H (e, f, g, h) NMR spectrum of four FCFs.

selectivity, with the conversion of cyclopentanone, selectivity and yield
of FCF being 98.7%, 97.3% and 96.0%, respectively, under condition of
50 °C with 3.6 mol% catalyst.
3.2. Aldol condensation of cyclohexanone and furfural
As shown in Table 2, similar to cyclopentanone, the solvent-free aldol
condensation of cyclohexanone and furfural have similar advantage over
diluted reaction. This reaction produces di-condensed 2,5-bis(2-
furylmethylidene)cyclohexan-1-one (Table 1, Fig. 1b, f). The conversion
and selectivity can be optimized by increasing the catalyst dosage or re-
action temperature. Compared with cyclopentanone, the reaction of cy-
clohexanone has to take place with higher catalyst dosage or higher
temperature to achieve considerable FCF yield, because cyclohexanone
is relatively less active in aspect of carbanion formation [36]. After 2 h-
reaction at 30 °C with 18.0 mol% catalyst or at 60 °C with 3.6 mol% cata-
lyst, the conversion of cyclohexanone, selectivity and yield of FCF reach
95.1% and 98.2%, 94.6% and 94.2%, 90.0% and 92.5%, respectively.
364 Q. Deng et al. / Fuel Processing Technology 148 (2016) 361–366

3.3. Aldol condensation of cyclic ketones and 5-hydroxymethylfurfural

Aldol condensation of cyclic ketones (cyclopentanone, cyclohexa-

none) and 5-HMF leads to molecule with 17/18 carbon atoms. 5-HMF
can be obtained from glucose and fructose by acid catalytic transforma-
tion, [9,10,11,28] and this route is very promising because the potential
amount of glucose and fructose in lignocellulose is higher than xylose
that is the precursor of furfural. The aldol condensation of
cyclopentanone and 5-hydroxymethylfurfural forms red solid di-
condensed 2,5-bis(5-hydroxymethyl-2-furylmethylidene)cyclopentan-
1-one (Table 1, Fig. 1c, g). As shown in Table 3, compared with the reac-
tion of cyclopentanone and furfural, a higher catalyst dosage or a higher
temperature must be applied to achieve considerable yield of FCF prod-
uct. The hydroxymethyl group in 5-HMF transfers electron to the car-
bonyl group and decreases the positive charge on which, which thus
reduces the ability to attack carbanion derived from cyclic ketones. More-
over, the hydroxymethyl group brings up steric hindrance that also
makes the reaction difficult. After 2 h-reaction at 30 °C with 14.4 mol%
catalyst or at 70 °C with 3.6 mol% catalyst, the yield of FCF is 83.4% and
87.1%, respectively.
The aldol condensation of cyclohexanone and 5-HMF produces 2,5-
bis(5-hydroxymethyl-2-furylmethylidene)cyclohexan-1-one (Table 1,
Fig. 1d, h), but the reaction rate is slowest among the four reactions
studied, due to the relatively inertness of cyclohexanone and 5-HMF,
see Table 3. Therefore, relatively severe reaction conditions are neces-
sary to achieve high yield. For example, after 2 h-reaction at 30 °C
with 18.0 mol% catalyst or at 70 °C with 3.6 mol% catalyst, the conver-
sion of cyclohexanone, selectivity and yield of FCF are 94.2% and
85.1%, 90.6% and 89.6%, 85.3% and 76.2%, respectively.

3.4. Hydrodeoxygenation of FCF and fuel properties

Hydrodeoxygenation was further conducted to transfer the four

Fig. 2. Product distribution in aldol condensation of cyclopentanone and furfural under
(a) solvent-free and (b) diluted conditions. Reaction conditions: 30 °C, 0.208 mol
furfural, 0.104 mol cyclopentanone, and 7.2 mol% NaOH, 100 ml H2O added in (b).
FCFs to hydrocarbon fuels. As summarized in Table 1, the FCFs are con-
verted to C15–C18 naphthenes, with selectivity of about 70–80%. The
major side-reaction is the cracking of chains on the C5–C6 rings, which
produces small molecular alkanes and C7–C17 naphthenes. A vacuum
distillation was conducted to remove the small molecular alkanes, and
the final biofuel contains C7–C18 branched naphthenes.

Table 1
Properties of biofuel synthesized using cyclic ketones and furanic aldehydes.

Feedstock Cyclopentanone and furfural Cyclohexanone and furfural Cyclopentanone and 5-HMF Cyclohexanone and 5-HMF

Condensed product

Hydrodeoxygenated product C15 (75.3%) C16 (70.7%) C17 (72.3%) C18 (69.5%)
C7–C14 (16.8%) C7–C15 (20.5%) C7–C16 (19.4%) C7–C17 (23.3%)
Cb6 (7.9%) Cb6 (8.8%) Cb6 (8.3%) Cb6 (7.2%)
Final biofuel

Composition of fuel C15 (86.7%) C16 (81.2%) C17 (79.5%) C18 (75.4%)
C7–C14 (12.4%) C7–C15 (17.5%) C7–C16 (22.9%) C7–C17 (22.9%)
Density at 20 °C (g/ml) 0.815 0.822 0.819 0.826
Freezing point (°C) −24.6 −21.7 −14.3 −9.5
Kinematic viscosity (mm2/s) 3.8 (25 °C) 4.7 (25 °C) 5.3 (25 °C) 6.7 (25 °C)
10.8 (−20 °C) 18.9 (−20 °C) 14.3 (−10 °C) 13.5 (−5 °C)
 Q. Deng et al. / Fuel Processing Technology 148 (2016) 361–366 365

Table 2 hydroxymethylfurfural N cyclohexanone/5-hydroxymethylfurfural,

Effect of catalyst dosage and temperature on the aldol condensation of cyclic ketones and but the conversion and yield can be improved by simply tuning the
furfural.
catalyst (NaOH) dosage (3.6 mol%–18.0 mol%) and reaction tempera-
Run Cyclic ketone Temperature NaOH Conversion Selectivity ture (30 °C–70 °C). And the optimal yield for the four reactions is
(°C) (mol%) (%) (%) 96.0%, 92.5%, 87.1% and 85.3%, respectively. The condensed products
1 Cyclopentanone 30 3.6 12.4 88.8 are converted to branched cyclic hydrocarbons after
2 Cyclopentanone 30 7.2 87.7 89.9 hydrodeoxygenation, which have density of 0.815 g/ml–0.826 g/ml
3⁎ Cyclopentanone 30 7.2 62.7 91.9
and freezing point ranging from −24.6 °C to −9.5 °C.
4 Cyclopentanone 30 10.8 96.5 95.3
5 Cyclopentanone 40 3.6 25.1 87.5
6 Cyclopentanone 50 3.6 98.7 97.3
7 Cyclohexanone 30 3.6 6.1 80.4 Acknowledgments
8 Cyclohexanone 30 7.2 28.5 82.9
9 Cyclohexanone 30 10.8 33.5 84.5
10 Cyclohexanone 30 14.4 71.2 94.8
The authors appreciate the support from the National Natural Sci-
11 Cyclohexanone 30 18.0 95.1 94.6 ence Foundation of China (U1462119, 21476168).
12⁎ Cyclohexanone 30 18.0 67.5 94.4
13 Cyclohexanone 40 3.6 25.5 73.4
14 Cyclohexanone 50 3.6 73.5 81.0
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