Bioresource Technology 183 (2015) 10–17

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

From lignin to cycloparaffins and aromatics: Directional synthesis of jet

and diesel fuel range biofuels using biomass
Peiyan Bi a, Jicong Wang a, Yajing Zhang a, Peiwen Jiang a, Xiaoping Wu a, Junxu Liu a, He Xue a,
Tiejun Wang b, Quanxin Li a,⇑
a
Department of Chemical Physics, Anhui Key Laboratory of Biomass Clean Energy, University of Science & Technology of China, Hefei 230026, PR China
b
Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A controllable transformation of A novel controllable transformation of lignin into C8–C15 cycloparaffins and aromatics in the jet and die-
lignin into green bio-jet fuels was sel fuel range by catalytic depolymerization of lignin into low carbon aromatics coupled with alkylation
demonstrated. of aromatics using ionic liquid.
 Production of C8–C15 hydrocarbons
was achieved by alkylation using
ionic liquid.
 Lignin-derived biofuels basically met
main technical requirements of jet
fuels.

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

Article history: The continual growth in commercial aviation fuels and more strict environmental legislations have led to
Received 21 December 2014 immense interest in developing green aviation fuels from biomass. This paper demonstrated a controllable
Received in revised form 5 February 2015 transformation of lignin into jet and diesel fuel range hydrocarbons, involving directional production of
Accepted 6 February 2015
C8–C15 aromatics by the catalytic depolymerization of lignin into C6–C8 low carbon aromatic monomers
Available online 13 February 2015
coupled with the alkylation of aromatics, and the directional production of C8–C15 cycloparaffins by the
hydrogenation of aromatics. The key step, the production of the desired C8–C15 aromatics with the selec-
Keywords:
tivity up to 94.3%, was achieved by the low temperature alkylation reactions of the lignin-derived mono-
Lignin
Bio-jet fuels
mers using ionic liquid. The synthetic biofuels basically met the main technical requirements of
C8–C15 aromatics conventional jet fuels. The transformation potentially provides a useful way for the development of
C8–C15 cycloparaffins cycloparaffinic and aromatic components in jet fuels using renewable lignocellulose biomass.
Alkylation Ó 2015 Published by Elsevier Ltd.

1. Introduction in developing new generation (hydrocarbon) bio-fuels, with a par-

The increased demand for commercial traffic fuels combined
with potential environmental benefits have accelerated advances
⇑ Corresponding author. Tel.: +86 551 63601118; fax: +86 551 63606689.
E-mail address: liqx@ustc.edu.cn (Q. Li).
ticular focus on aviation biofuels from renewable biomass (Daroch
et al., 2013; Valle et al., 2012; Yan et al., 2013; Wang et al., 2012).
Aviation fuel is a specific type of fuel oils designed for use in air-
craft and the most commonly used commercial aviation fuels are
jet fuels which are currently produced from petroleum refining
(Liu et al., 2013). The development of aviation biofuels can help

http://dx.doi.org/10.1016/j.biortech.2015.02.023
0960-8524/Ó 2015 Published by Elsevier Ltd.
 P. Bi et al. / Bioresource Technology 183 (2015) 10–17
reduce our dependence on the fossil energy and particularly
release the environmental pressure. In this sense, new or improved
technologies are required to meet the challenges associated with
producing bio-jet fuels from biomass or biomass-derived
feedstocks.
Jet fuels must meet very stringent specifications, which makes
it much more difficult to develop an alternative fuel for the use
of aviation than for automobile applications (Verma et al., 2011).
Several promising routes, especially, hydrotreating of vegetable
oils (Bezergianni et al., 2009; Robota et al., 2013; Wang et al.,
2012), and Fischer Tropsch synthesis (Kumabe et al., 2010; Liu
et al., 2013; Naik et al., 2011; Yan et al., 2013), have been devel-
oped with the aim of producing aviation biofuels from various bio-
mass feedstocks. Numerous feedstocks of edible and non-edible
vegetable oils like soybean oil, Jatropha oil, algae oil and waste
restaurant oils have been intensively investigated for producing
hydrocarbon fuels by the hydrotreating technologies, showing
great potential for the production of alkanes particularly suitable
for diesel and/or jet fuels applications. The synthetic feedstocks
of triglycerides extracted from plant or animal oils are typically
hydrotreated under high hydrogen pressure over noble metals or
metal sulfides supported catalysts. The hydrotreating of triglyc-
erides into hydrocarbons mainly involves the following processes:
(i) the hydrogenation of the unsaturated olefinic bonds in triglyc-
erides; (ii) the formation of free fatty acids along with propane
through breaking the C–O bonds in the saturated triglycerides;
(iii) the formation of linear n-alkanes by hydrodeoxygenation,
decarbonylation and decarboxylation of free fatty acids; and (iv)
the formation of lighter iso-alkanes by hydrogenation cracking
and isomerization. The most representative vegetable oils are
essentially composed of C16 and C18 fatty acids, and consequently,
the typical products obtained from the hydroprocessing of veg-
etable oils at lower temperatures of 300–350 °C are C15–C18 alka-
nes in the diesel range. To produce jet range biofuels (typically
C8–C15 hydrocarbons), the cracking and isomerization at higher
temperatures are generally required (Verma et al., 2011). So far,
American Society for Testing and Materials (ASTM) have adopted
a new specification D7566-14a for a 50:50 blend of the synthetic
paraffinic kerosene’s (SPKs) produced from triglyceride-based veg-
etable oils with conventional jet fuels (ASTM D7566-14a). The
hydrotreating of vegetable oils can offer higher yield of diesel or
jet fuels, which could benefit from the fact that triglycerides con-
tain saturated fatty acids with a moderate chain length of C16–
C18 together with higher H/C ratio.
Fischer–Tropsch synthesis (FTS) is a highly developed and tech-
nically proven route to transform lignocellulose biomass into liq-
uid biofuels (particularly alkanes) (Kumabe et al., 2010; Liu et al.,
2013; Naik et al., 2011; Yan et al., 2013). The biomass-based FTS
process generally includes four main steps: (i) the production of
bio-syngas by means of biomass gasification, (ii) cleaning and con-
ditioning of crude syngas, (iii) high pressure FT synthesis and (iv)
subsequent upgrading of crude fuels for gasoline, diesel and jet fuel
applications. The liquid products from FTS are commonly complex
compounds, mainly consisting of the five families of hydrocarbon
groups (n-paraffins, iso-paraffins, olefins, aromatics and naph-
thenes) alone with oxygenates, which depend on reaction condi-
tions and catalyst types. The raw FTS fuels must be further
upgraded to the acceptable jet range fuels by subsequent
hydrocracking, isomerizing and distillating (Liu et al., 2013; Yan
et al., 2013). Most of the liquid hydrocarbons from FTS are paraffins
and olefins, and thereby, aromatics and naphthenes should be
increased in the FTS-derived fractions to meet the specific require-
ment of jet fuels (Corporan et al., 2011; Dupain et al., 2005; Huber
et al., 2006). FTS-derived SPKs have been also approved for a 50/50
blend with petroleum-derived jet fuels (ASTM D7566-14a (2014);
Corporan et al., 2011; Lobo et al., 2011). Chemically, main compo-
11
sitions of commercial and military jet fuels can be described as
paraffins, naphthenes and aromatics (Vukadinovic et al., 2013;
Yan et al., 2013). As mentioned above, triglycerides- or FTS-derived
SPKs are currently being utilized as the component of alkanes in
commercial jet-fuels. However, another two main compositions
(cyclic alkanes and aromatics) required for the commercial and
military jet fuels seem to be difficult to get from the well developed
hydrotreating of vegetable oils or FTS process (Corporan et al.,
2011; Dupain et al., 2005; Robota et al., 2013).
Lignin, a main constituent of lignocellulosic biomass, has been
proven to potentially produce aromatic chemicals and biofuels by
means of various strategies like hydrogenation, oxidation, pyroly-
sis, and catalytic pyrolysis (Deng et al., 2010; Jiang et al., 2014;
Lou et al., 2010; Mullen and Boateng, 2010; Olcese et al., 2013;
Pandey and Kim, 2011; Shen et al., 2010; Zakzeski et al., 2010).
In view of its structure characteristics (three dimensional amor-
phous polymer containing phenylpropane units), lignin, potential-
ly, can serve as a plentiful renewable resource for producing
aromatics and cyclic alkanes.
Here, we demonstrate the directional transformation of lignin
into jet or diesel fuel range hydrocarbons by a novel route, includ-
ing directional production of C8–C15 aromatics by the catalytic
depolymerization of lignin into C6–C8 low carbon aromatics cou-
pled with the alkylation of aromatics, and the production of C8–
C15 cycloparaffins by the hydrogenation of C8–C15 aromatics.
Owing to the unique properties of ionic liquids (ILs) like having
low vapor pressures, high thermal and chemical stability, non-
flammability and Brønsted and Lewis acidity in some cases, ILs
have attracted wide interest in organic synthesis, catalysis, separa-
tion, extraction, electrochemistry, polymerization reactions
(Blanco et al., 2006; Corma and García, 2003; Han and Row,
2010; Olivier-Bourbigou et al., 2010) as well as hydrolysis of cellu-
lose to sugars or biomass platform chemical (Liu et al., 2012). Pre-
sent work also demonstrated that the key step, the selective
production of the desired C8–C15 aromatics from lignin was able
to be realized by the low temperature alkylation reactions of the
biomass-derived monomers using ionic liquid, and the end prod-
ucts meet the basic requirements of the conventional jet fuels.
2. Methods
2.1. Materials
The raw material of lignin, purchased from Lanxu Biotechnology
Co. Ltd. (Hefei, China), was a brown and sulfur-free lignin powder
manufactured from wheat straw. The dried lignin contained
63.46 wt.% carbon, 5.61 wt.% hydrogen, 29.23 wt.% oxygen and
1.70 wt.% nitrogen, which were determined by the elemental ana-
lysis with an elemental analyzer (Vario EL-III, Elementar, Ger-
many). All analytical reagents used were purchased from
Sinopharm Chemical Reagent Company Limited (Shanghai, China).
2.2. Catalyst preparation and characterization
The HZSM-5 zeolite with the Si/Al ratio of 25 used for the cat-
alytic cracking of lignin was prepared by the conversion of the
sodium form supplied by Nankai University catalyst Co., Ltd. (Tian-
jin, China) to the protonated form via NH+4 exchange procedure, fol-
lowed by calcination in air at 550 °C for 4 h. For preparation of the
[bmim]Cl-2AlCl3 (1-butyl-3-methylimidazolium chloroaluminate)
ionic liquid (used for alkylation of lignin-derived aromatics),
1-butyl-3-methylimidazolium chloride ([bmim]Cl) was first
prepared by the following procedures: dried and redistilled
N-methylimidazolium and 1-chlorobutane were placed into a dry
round-bottomed flask equipped with a reflux cooler and a magnet-
12 P. Bi et al. / Bioresource Technology 183 (2015) 10–17
ic agitator. The mixture was heated and reacted at the temperature
of 80–85 °C for 24 h. Then the mixture was cooled to room tem-
perature, and the unreacted reactants were removed using a rotary
evaporator. The resulting imidazolium salt was washed using ace-
tonitrile as solvent, and dried in a vacuum drying box to remove
the residual solvent and water. Finally, the [bmim]Cl-2AlCl3 ionic
liquid was prepared by slowly adding the dried aluminum chloride
to the imidazolium salt with a molar ratio of 2.0 between AlCl3 and
[bmim]Cl and stirring overnight. The ionic liquid, once prepared,
was stored in a dry nitrogen atmosphere. The Pd/AC (active carbon)
catalyst used for the hydrogenation of aromatics was prepared by
the incipient wetness impregnation of the HNO3-treated AC with
the H2PdCl4 solution (PdCl2 dissolved in HCl solution). The impreg-
nated product was dried at 110 °C for 24 h, and finally reduced by
H2 (60 mL/min) at 280 °C for 8 h.
Acidity characterizations of the ionic liquids were carried out by
infrared spectroscopy (Bruker Tensor 27 FT-IR spectrometer) using
pyridine as a probe molecule of Lewis and Brønsted acid at room
temperature. The samples were prepared by mixing pyridine and
ionic liquids in a volume ratio of 5:1, and then smeared into liquid
films on KBr windows. The FT-IR spectrum was acquired at 1 cm1
resolution using 16 scans for each sample. The 1H NMR measure-
ments were carried out on a high-resolution liquid nuclear mag-
netic resonance spectrometer (Bruker Avance 300 MHz). The
spectra were obtained at 300.13 MHz with a delay time of 0.5 s.
The HZSM-5 catalysts was characterized by NH3-TPD (temperature
programmed desorption of ammonia), XRD (X-ray diffraction), and
N2 adsorption/desorption isotherms analysis, as described in our
previous papers (Gong et al., 2011). The acidity of HZSM-5(25)
was 575.9 ± 8.9 lmol/gcat, measured by the NH3-TPD tests from
120 °C to 700 °C with a heating rate of 10 °C/min. The metal con-
tents in the 5.0 ± 0.2 wt.% Pd/AC catalysts were measured by ICP/
AES (inductively coupled plasma and atomic emission
spectroscopy).
2.3. Catalytic depolymerization and deoxygenation of lignin
Since the pyrolysis of lignin (non catalytic pyrolysis) mainly
produced various phenolic compounds with small amounts of aro-
matic hydrocarbons, the catalytic pyrolysis of lignin is required to
produce aromatic hydrocarbons. The HZSM-5 catalyst is one of the
most promising candidates for the catalytic conversion of lignin
based on our previous work (Fan et al., 2013). The catalytic depoly-
merization of lignin was performed in the continuous flow pyroly-
sis reactor using the procedures as described before (Huang et al.,
2012). Briefly, the system was mainly composed of a tube reactor, a
feeder for solid reactants, two condensers and a gas analyzer.
Before each run, the reactor was flushed with nitrogen (300 cm3/
min) for 2 h, and was externally heated to a given temperature
by the carborundum heater. Lignin was mixed with the HZSM-5
catalyst with a typical catalyst/lignin weight ratio of 2. Then the
mixture was fed into the reactor by the feeder with a feeding rate
of about 30 g lignin/h. The liquid products in each test were col-
lected by a condenser immersed in the ice/salt bath, and then
weighed. The solid samples collected were sieved and separated
into the catalyst and coke/char, and the gas in each test was col-
lected with air bags and analyzed as described in Section 2.6.
2.4. Alkylation of lignin-derived low carbon aromatic monomers
To produce the C8–C15 aromatic hydrocarbons, in the second
step, the alkylation of the low carbon aromatics produced by cat-
alytic depolymerization of lignin at 500 °C was carried out using
the ionic liquid catalyst of [bmim]Cl-2AlCl3 under the atmospheric
pressure and low temperature. The mixture gas of C2–C4 light ole-
fins (containing 10.3 vol.% C2H4, 16.7 vol.% C3H6 and 3.9 vol.% C4H8)
was used as the alkylating agent, simulating the gas components
produced by the catalytic cracking of bio-oil at 550 °C (Gong
et al., 2011). The [bmim]Cl-2AlCl3 ionic liquid was selected as a
high active catalyst used for the alkylation of lignin-derived low
carbon aromatics, based on the tests using the aromatic models
with different catalysts (Table A.1 in Support information).
The alkylation reactions were run in batch mode in a 50-ml
three-necked flask reactor equipped with a gas-inlet, a reflux cool-
er, sampling exit and a magnetic stirrer. The reaction temperature
was controlled by a thermostatic water bath with a temperature
controller. For a typical run, the ionic liquid and the lignin-derived
bio-oil with the ratio of 0.2 was added into the reactor, and flushed
with nitrogen (300 cm3/min) under the room temperature for
60 min. When reaching to the given temperature, the mixture
gas of light olefins with a flow rate of 200 cm3 min1 was fed into
the reactor, which was controlled by a mass-flow controller. Then,
the reaction mixtures were stirred at 500 rpm and reacted at 20–
80 °C for a given time (30–240 min). Finally, the alkylated products
on the upper layer were separated from the ionic liquid at the bot-
tom of the flask by decantation, weighted and measured by GC–MS
and other analysis.
2.5. Hydrogenation of aromatics
To produce the C8–C15 cyclic alkanes, the hydrogenation of the
alkylated products was further performed in a 100 mL Parr reactor
in the range of 90–180 °C for 6 h (named as the third step). For
each run, the Pd/AC catalyst and the alkylated products with a ratio
of 1:10 were used for the hydrotreating. During the reaction, H2
was added continuously to keep the total pressure at 5 MPa. After
the hydrogenation treatment, the catalyst was removed by filtra-
tion, and the resulting liquid products were weighted and further
analyzed as described below.
2.6. Analytical techniques
The liquid products collected in each test were weighed to
obtain the mass of liquid product. The total carbon content in the
liquid product was measured by a Vario EL III elemental analyzer,
and the water content was analyzed by a moisture analyzer (Model
ZSD-1, Shanghai, China). The main components of the organic liq-
uid products were analyzed by GC–MS (Thermo Trace GC/ISQ MS,
USA; FID detector with a TR-5 capillary column). The moles of main
organic compounds were determined by the normalization
method with standard samples. For gas product analysis, the gas
in each test was collected with air bags, and analyzed using a gas
chromatograph (GC-SP6890, Shandong Lunan Ruihong Chemical
Instrument Co., Ltd., Tengzhou, China) with two detectors, a TCD
(thermal conductivity detector) for analysis of H2, CO, CH4 and
CO2 separated on TDX-01 column, and a FID (flame ionization
detector) for gas hydrocarbons separated on Porapak Q column.
The moles of gas products were determined by the normalization
method with standard gas. For the analysis of solid products pro-
duced during catalytic depolymerization of lignin, the solid residue
after each run was weighed, and then measured by the TGA analy-
sis (Q5000IR thermogravimetric analyzer, USA). Overall weight
yields (Yi (wt.%)), overall carbon yields (Yj (C-mol%)) of the gas, liq-
uid and solid products, weight yield (Yk (wt.%)) and carbon yield (Yl
(C-mol%)) of a specific product, conversion (Cconv. (C-mol%)) of a
specific organic compound, the product selectivity (Si (C-mol%))
and the resulting organic distribution (Di (wt.%)) were calculated
based on the following Eqs. (1–7).
Mass of gas; liquid or solid products
Y i ðwt:%Þ ¼  100% ð1Þ
Mass of feed
 P. Bi et al. / Bioresource Technology 183 (2015) 10–17
Carbon moles in gas; liquid or solid products
Y j ðC-mol%Þ ¼
Carbon moles fed in
 100%
Mass of a product
Y k ðwt:%Þ ¼  100%
Mass of feed
Carbon moles in a product
Y l ðC-mol%Þ ¼  100%
Carbon moles fed in
Carbon moles in an organic compound reacted
C conv: ðC-mol%Þ ¼
Carbon moles in an organic compound fed in
 100%
Carbon moles in a product
Si ðC-mol%Þ ¼  100%
Carbon moles in all products
Mass of an organic liquid
Di ðwt:%Þ ¼  100%
Total mass of organic liquid
Moreover, the specific fuel properties of the synthesized avia-
tion biofuels from biomass were evaluated based on the method
described in the literature (Corporan et al., 2011). All the tests were
repeated three times and the reported data are the mean values of
three trials. The analysis of carbon balance and the standard devia-
tions (or relative standard deviations) were also carried out for all
tests.
3. Results and discussion
3.1. Catalytic transformation of lignin into low carbon aromatic
hydrocarbons
To produce C8–C15 hydrocarbons, first of all, the transforma-
tion of lignin into aromatic monomers is required. As shown in
Fig. 1(a), higher temperatures favored the catalytic depolymeriza-
tion and deoxygenation of lignin, resulting in an improvement in
the aromatic hydrocarbon yield up to 500 °C. At temperatures over
500 °C, however, the formation of aromatics obviously decreased
due to the secondary cracking of organics. The organic products
consisted primarily of the C6–C8 low carbon aromatic hydrocar-
bons (Table A.2 in Support information), originating from the
depolymerization of lignin along with further decarbonylation,
decarboxylation and dehydration of phenolic oxygenates over the
zeolite catalyst. The total C6–C8 aromatics selectivity reached
about 82.9 C-mol% at 550 °C (Fig. 1(b)). The lighter aromatics
increased with increasing temperature alone with a decrease in
the heavier aromatics, attributed to the removal of the alkyl groups
in the heavier aromatics at higher temperatures. Smaller amounts
of polycyclic aromatics like naphthalene and methylnaphthalene
produced by the oligomerization reactions of lighter aromatics
were also formed. To maximize the production of aromatic hydro-
carbons, the lignin-derived bio-oil obtained at 500 °C was used in
the subsequent alkylation step.
3.2. Production of C8–C15 aromatic hydrocarbons by low-temperature
alkylation
Since the hydrocarbons produced by the catalytic depolymer-
ization of lignin consist primarily of C6–C8 low carbon aromatics,
controllable adjusting the carbon numbers of hydrocarbons is
required to meet the requirements of jet fuels. In the second step,
we demonstrated for the first time that the directional production
13
ð2Þ
ð3Þ
ð4Þ
ð5Þ
ð6Þ
ð7Þ
Fig. 1. Catalytic depolymerization of lignin into low carbon aromatics over HZSM-
5(25). Reaction conditions: T = 400–550 °C, f(N2) = 200 cm3 min1, ratio of catalyst
to lignin = 2. The values reported are averages of three trials and relative standard
deviations were <10.2%. The carbon balance ranged from 89.2% to 94.3%.
of C8–C15 aromatics can be realized by low temperature alkylation
of aromatics using the ionic liquid.
The alkylation of aromatics is related with alkylation catalyst,
electrophilic substitution reactivity of aromatics as well as reaction
conditions. As shown in Fig. 2(a) and (b), the [bmim]Cl-2AlCl3 ionic
liquid shows an excellent catalytic activity and selectivity of C8–
C15 aromatics for the low temperature alkylation of the lignin-
derived aromatics. Even at the room temperature (20 °C), the con-
versions of the monocyclic aromatic hydrocarbons (MAHs) and
polycyclic aromatic hydrocarbon (PAHs) reached about 63.8% and
82.5% respectively, alone with a high C8–C15 aromatics selectivity
of 91.0%. The conversion of PAHs like naphthalene and methyl-
naphthalene is obviously higher than the conversion of MAHs,
which could be attributed to the fact that PAHs have higher elec-
tron density, and thereby, show higher electrophilic substitution
reactivity as compared with MAHs.
Reaction temperature has an important impact on the alkyla-
tion of lignin-derived monomers into the C8–C15 aromatic hydro-
carbons. As can be seen from Fig. 2(a) and (b), the conversion of
MAHs and PAHs gradually increased with increasing temperatures.
From the point of view of chemical equilibrium, since the aromatic
alkylation is an exothermic reaction, increasing temperature will
result in the decrease of equilibrium constants and therefore is
not beneficial to the aromatic alkylation. From the point of kinetics,
on the other hand, increasing temperature is conducive to over-
come the activation energy required for the alkylation reactions.
Meanwhile, the collision probability between ionic liquid and reac-
tants will be enhanced at higher temperatures, and thereby,
increasing the reaction rates of the low carbon aromatics with light
olefins. Accordingly, the positive temperature dependence
observed at the lower temperatures suggested that the kinetic fac-
tors were predominant for the alkylation process. Moreover, the
main alkylation products were dominated by the C8–C15 hydro-
carbons and increased from 76.4 wt.% to 79.1 wt.% with increasing
14 P. Bi et al. / Bioresource Technology 183 (2015) 10–17
Fig. 2. Low temperature alkylation of aromatics for producing C8–C15 aromatics using [bmim]Cl-2AlCl3 ionic liquid at different reaction conditions. (a)–(b): 20–80 °C,
60 min; (c)–(d): 60 °C, 30–240 min. The values reported are averages of three trials and relative standard deviations were <8.9%. The carbon balance ranged from 93.5% to
98.7%.
temperatures from 20 °C to 60 °C (Table 1). The alkylation of aro-
matics is a consecutive reaction process, and the primary alkyla-
tion products was multiply alkylated to form high carbon
number aromatics, leading to a rise in the heavier aromatics with
increasing temperature.
Apart from the reaction temperature, the reaction time is
another crucial factor that affects the alkylation degree of the
low-carbon aromatics (Fig. 2(c) and (d)) as well as the product dis-
tribution (Table A.3 in Support information). After the alkylation
reactions at typical temperature of 60 °C for 120 min, about
96.7% of low carbon aromatics were converted to higher carbon
number aromatics. Especially, the distribution of the carbon num-
ber in the resulting products prominently shifted towards the
heavier hydrocarbons with increasing reaction time, indicating
that the secondary alkylations of aromatics were enhanced for
longer reaction duration. Accordingly, the final carbon number dis-
tribution of hydrocarbons was able to be efficiently tuned into the
desired range of C8–C15 by the reaction temperature and time dur-
ing the alkylation of aromatics using the ionic liquid catalyst. The
resulting biofuel after the alkylation of low carbon aromatics under
the optimal condition (at 60 °C for 60 min) contains 79.1 wt.% C8–
C15 aromatic hydrocarbons with a weight yield of 0.173 ±
0.012 kg/(kg lignin).
3.3. Production of C8–C15 cyclic alkanes through hydrogenation of
aromatics
Cyclic alkanes is the second most abundant components
required in the commercial and military jet fuels with the mass
percent of 20–50 wt.% (Corporan et al., 2011; Dagaut and
Cathonnet, 2006; Vukadinovic et al., 2013). In the third step, the
production of the C8–C15 cyclic alkanes using lignin was accom-
plished by the hydrogenation of the C8–C15 aromatics. The hydro-
genation of aromatics is a thermodynamically controlled process.
As shown in Fig. 3, the conversion of the monocyclic aromatic
hydrocarbons (MAHs) at the lower temperature of 90 °C was about
20.2%. Increasing the reaction temperatures up to 180 °C sig-
nificantly improved the hydrogenation efficiency of aromatics,
and nearly all of the lignin-derived C8–C15 aromatics were con-
verted into the saturated cyclic alkanes after the hydrogenation
at 180 °C. The conversion of PAHs was higher than that of MAHs,
suggesting that the activation energy for the hydrogenation of
PAHs was less than that for the hydrogenation of MAHs. Moreover,
no significant change in the carbon number distribution after the
hydrogenation treatment was found (Fig. 3(b)), as compared with
the carbon number distribution before the hydrogenation of aro-
matics (Fig. 2(b)). This implies that the hydrogenation of aromatics
enables the saturation of C8–C15 aromatics to form C8–C15 cyclic
alkanes, and the cracking reactions seem to be neglectable during
the low temperature hydrogenation process. The resulting biofuel
after the hydrogenation of aromatics under the optimal condition
(at 180 °C for 6 h) contains 79.9 wt.% C8–C15 cyclic alkanes with
a weight yield of 0.175 ± 0.015 kg/(kg lignin).
3.4. Stability and reusability of catalysts
As shown in Fig. 4(a) and (b), the catalyst stability during the
catalytic cracking of lignin over the HZSM-5 (25) catalyst was test-
ed at a typical temperature of 500 °C, and the regeneration cycles
of catalyst were carried out by the method of coke burn-off. After
the catalyst was continuously used for three rounds (R1–R3) with-
out regeneration treatment, the formation of C6–C8 aromatics was
obviously decreased due to the catalyst deactivation. Taking into
account that the activity of the used catalysts was able to be almost
recovered by treating the used catalyst with oxygen at 550 °C for
4 h, the catalyst deactivation should be mainly caused by the
 P. Bi et al. / Bioresource Technology 183 (2015) 10–17 15

Table 1
Effect of temperature on the alkylation reactions of the lignin-derived low carbon
aromatic monomers using the ionic liquid catalyst of [bmim]Cl-2AlCl3.a

Temperature 20 °C 40 °C 60 °C 80 °C
Distribution of MAHs (wt.%)
C6 aromatics 9.6 7.6 4.8 3.6
C7 aromatics 7.1 4.3 3.4 2.4
C8 aromatics 4.2 2.9 1.8 1.0
C9 aromatics 10.3 8.2 7.0 3.9
C10 aromatics 16.1 15.5 16.0 14.7
C11 aromatics 11.1 9.8 10.0 11.9
C12 aromatics 5.1 6.8 9.3 8.1
C13 aromatics 10.1 14.9 16.9 18.0
C14 aromatics 7.0 8.2 8.6 10.1
C15 aromatics 2.9 4.1 4.1 4.4
C16 aromatics 0.7 1.1 1.9 2.8
C16+ aromatics 0.2 0.4 0.9 1.8
Distribution of PAHs (wt.%)
C10 naphthalenes 1.6 1.1 0.7 0.6
C11 naphthalenes 0.6 0.5 0.3 0.2
C12 naphthalenes 0.1 0.2 0.2 0.1
C13 naphthalenes 4.0 3.1 1.7 2.1
C14 naphthalenes 2.2 2.0 2.1 2.1
C15 naphthalenes 1.1 1.4 0.4 0.6
C16 naphthalenes 2.1 3.6 3.4 3.9
C16+ naphthalenes 3.9 4.3 6.5 7.7
Overall property
C8–15 aromatics (wt.%) 76.4 78.7 79.1 77.8
Conversion of typical monomers (C-mol%)
Benzene 64.2 71.6 82.0 86.4
Toluene 69.2 81.3 85.2 89.3 Fig. 3. Production of C8–C15 cyclic alkanes by the hydrogenation of lignin-derived
Naphthalene 80.3 86.0 90.9 91.8 C8–C15 aromatics over the 5.0 wt.% Pd/AC catalyst at 5 MPa for 6 h. The values
Methylnaphthalene 86.5 89.4 92.7 93.4 reported are averages of three trials and relative standard deviations were <9.5%.
The carbon balance ranged from 94.2% to 100.9%.
a
The reactions were conducted using the low-carbon aromatics (produced by
catalytic depolymerization of lignin at 500 °C) and the [bmim]Cl-2AlCl3 ionic liquid
for 60 min at 20–80 °C, the flow rate of light olefins of 200 cm3 min1 and the IL/
(lignin-derived oil) ratio of 0.2. MAHs: monocyclic aromatic hydrocarbons; PAHs:
polycyclic aromatic hydrocarbons. The values reported are averages of three trials
and relative standard deviations were <7.5%. The carbon balance ranged from 93.5%
to 97.3%.

carbon deposition on the catalyst during catalytic cracking of lig-

nin. Accordingly, a cyclic reaction–regeneration configuration
was assembled for the catalytic cracking of lignin (Fig. 4). More-
over, no significant changes in the catalytic activity of the [b-
mim]Cl-2AlCl3 ionic liquid was found after the alkylation
reactions of the low-carbon aromatics at 60 °C for five rounds.
The Pd/AC catalyst also showed good stability during the hydro-
genation of C8–C15 aromatics at 180 °C for 24 h. The higher sta-
bility of the ionic liquid catalyst and the Pd/AC catalyst should
mainly benefit from the mild operation conditions and thereby a
negligible coke-deposition both in the alkylation and hydrogena-
tion processes.

3.5. Evaluation of biofuel properties

Typically, the commercial and military jet fuels are a mixture of

three main components of paraffins, cycloalkanes and aromatics,
and their ratios depend on different jet fuels like Jet-A1, Jet A
and JP-8 (Corporan et al., 2011; Dagaut and Cathonnet, 2006;
Vukadinovic et al., 2013). Jet fuel must meet very stringent specifi-
cations, and three basic technical requirements are fuel heat of
combustion (>42.8 MJ/kg), freeze point (<47 °C) and viscosity Fig. 4. Catalyst stability and reaction-regeneration cycles during the catalytic
(<8.0 mm2/s) among the numerous specifications (ATSM D7566- cracking of lignin over the HZSM-5 catalyst (reaction conditions: T = 500 °C,
f(N2) = 200 cm3 min1, catalyst/lignin = 2; regeneration conditions: T = 550 °C,
14a; Corporan et al., 2011;Verma et al., 2011). Table 2 summarized f(O2) = 300 cm3 min1, t = 4 h). The values reported are averages of three trials
some important fuel properties of the biofuels synthesized in this and relative standard deviations were <11.6%. The carbon balance ranged from
work and several commercial and military jet fuels. Two typical 89.5% to 101.3%.
16 P. Bi et al. / Bioresource Technology 183 (2015) 10–17

Table 2
Comparison of fuel properties in two lignin-derived biofuels and commercial/military jet fuels.

Specification tests Commercial/military jet fuels Biofuels (this work)

a a b
Jet A Jet-A1 JP-8 ABFc CABFd
Heat of combustion (MJ/kg) 43.3 43.3 43.0 42.5 ± 1.0 45.9 ± 0.8
Freezing point (°C) 40 47 49 670 670
Kinetic viscosity
@ 20 °C (mm2/s) 5.78 4.27 4.10 6.22 ± 0.28 7.46 ± 0.31
Specific gravity
@ 15 °C (g/ml) 0.803 0.797 0.799 0.865 ± 0.017 0.817 ± 0.013
Carbon content (wt.%) 86.4 86.3 86.2 89.5 ± 0.5 85.8 ± 0.7
Hydrogen content (wt.%) 13.6 13.7 13.7 10.4 ± 0.5 14.2 ± 0.7
Total oxygen (wt.%) 0 0 – 0.096 ± 0.007 u.d.
Total sulfur (wt.%) <0.3 <0.3 0.064 u.d. u.d.
Average carbon number 11.6 11.0 10.9 11.2 ± 0.3 11.2 ± 0.5
H/C (mol ratio) 1.90 1.91 1.92 1.40 ± 0.07 1.98 ± 0.11
Average molecular formula C11.6H22 C11H21 C10.9H20.9 C11.2H15.7 C11.2H22.2
a
References: ASTM D7566-14a (2014); Dagaut and Cathonnet (2006) and Lobo et al. (2011).
b
References: Corporan et al. (2011) and Dagaut and Cathonnet (2006).
c
ABF: aromatic biofuel, produced by catalytic depolymerization of lignin over HZSM-5 at 500 °C coupled with the alkylation of aromatics using the [bmim]Cl-2AlCl3 ionic
liquid at 60 °C for 60 min.
d
CABF: cyclic alkane biofuel, produced by hydrogenation of ABF over 5.0 wt.% Pd/AC catalyst at 180 °C for 6 h. u.d. = undetected.

lignin-derived products (aromatic biofuel (ABF) and cyclic alkane
biofuel (CABF)), basically met the carbon number range (see
Fig. A.1 in Support information) and the main technical specifica-
tions of jet fuels (Table 2), as compared with the values of the typi-
cal commercial and military jet fuels. ABF possesses average
combustion heat of 42.5 MJ/kg, viscosity of 6.22 mm2/s and freeze
point of 670 °C. CABF also meets the basic technical requirements
based on its average combustion heat (45.9 MJ/kg), viscosity
(7.46 mm2/s) and freeze point (670 °C). Moreover, sulfur and oxy-
gen content in the resulting products were very low. The above
results clearly show that the C8–C15 aromatics and cyclic alkanes
in the jet fuel range can be directionally synthesized using lignin
under the mild reaction conditions, which are generally difficulty
to be produced by the hydrotreating of triglyceride-based oils or
the FTS process (Corporan et al., 2011; Dupain et al., 2005;
Robota et al., 2013).
3.6. Reactions pathways
The purpose of this work is to directionally produce two main
components of jet fuels (cycloparaffins and aromatics in the jet fuel
range) using renewable lignin. We demonstrated a transformation
route of biomass into the desired jet (or diesel) fuel range hydro-
carbons via three reaction steps: (1) the catalytic cracking of lignin
into the low-carbon aromatic monomers, (2) the directional pro-
duction of C8–C15 aromatics by the alkylation of the aromatic
monomers, and (3) the production of the C8–C15 cycloparaffins
by the hydrogenation of the lignin-derived C8–C15 aromatics
(see Fig. A.2 in Support information). In the first step, the catalytic
cracking of lignin into the low-carbon aromatic monomers was
carried out using the HZSM-5 catalyst, mainly involving: the for-
mation of oxygenated organic compounds like phenols and other
oxygenates by the depolymerization of lignin through the disrup-
tion of the C–C bonds and the C–O bonds in the lignin polymer
(Shen et al., 2010); along with the formation of the low-carbon
aromatic monomers (mainly C6 to C8 aromatics) by further deoxy-
genation, catalytic cracking, aromatization as well as the formation
of smaller amounts of polycyclic aromatics like naphthalene and
methylnaphthalene over the acidic sites of the zeolite.
The second step involves the selective production of C8–C15
aromatic hydrocarbons by a series of alkylation reactions of low
carbon aromatics with C2–C4 light olefins using the ionic liquid
catalyst. The [bmim]Cl-2AlCl3 ionic liquid was proved to be a high
active catalyst for producing the aromatic hydrocarbons in the jet
or diesel range from the lignin-derived low carbon aromatics, and
the carbon number distribution of aromatics was adjustable by
changing reaction temperature and time. The designed control
experiments in the case without adding the ionic liquid confirmed
that no alkylation reactions occurred (Table A.1 in Support infor-
mation). Chemically, the [bmim]Cl-2AlCl3 ionic liquid consists of
1-butyl-3-methylimidazolium cation and Al2Cl-7 anion. The FT-IR
spectra of [bmim]Cl-2AlCl3 show two bands at 1454 cm1 and
1540 cm1 (Fig. A.3 in Support information), corresponding to the
characteristic peaks of Lewis acid and Brønsted acid, respectively,
when pyridine was used as a probe molecule (Yang and Kou,
2004). Based on the comparison of 1H NMR spectra before and after
titrated with KOH solution (Fig. A.4 in Support information), the
absence of H in the star site after titrated with KOH solution sug-
gests that the ionic liquid can provide protons from the ionic liquid.
Accordingly, the FT-IR and 1H NMR characterizations support that
the ionic liquid posses the properties of both Brønsted acid and
Lewis acid. The ionic liquid should enhance the olefin protonation
(Zhao et al., 2005), leading to the enhancement of the alkylation of
low carbon aromatics with light olefins. Base on the products iden-
tified, the main reaction pathways involved in the alkylation of the
lignin-derived aromatics are illustrated in Fig. A.2 (in Support
information), in which the typical alkylation reactions can be
described by the following stoichiometric expressions.
C6 H6 þ Cn H2n ! C6 H5 -Cn H2nþ1 ðn ¼ 2  4Þ ð8Þ
C6 H5 -CH3 þ Cn H2n ! CH3 -C6 H4 -Cn H2nþ1 ðn ¼ 2  4Þ ð9Þ
CH3 -C6 H4 -CH3 þ Cn H2n ! ðCH3 Þ2 -C6 H3 -Cn H2nþ1 ðn ¼ 2  4Þ ð10Þ
C10 H8 þ Cn H2n ! C10 H7 -Cn H2nþ1 ðn ¼ 2  4Þ ð11Þ
Finally, the subsequent hydrogenation of the alkylated aromat-
ics in the third step resulted in the saturation of the unsaturated
aromatic hydrocarbons over the Pd/AC catalyst, and thereby,
achieving the selective production of the C8–C15 cyclic alkanes
from the lignin-derived C8–C15 aromatics.
4. Conclusions
We demonstrated that lignin can be directionally converted
into jet and diesel fuel range hydrocarbons with a controlled
 P. Bi et al. / Bioresource Technology 183 (2015) 10–17
reaction pathway. The C6–C8 aromatics, produced by catalytic
depolymerization of lignin, were further converted to C8–C15 aro-
matics with a yield of 0.173 ± 0.012 kg/(kg lignin) by low tem-
perature alkylation reactions using the ionic liquid. After
hydrogenation of aromatics, C8–C15 cyclic alkanes with a yield
of 0.175 ± 0.015 kg/(kg lignin) were formed. Two lignin-derived
products, C8–C15 cycloparaffins and aromatics, basically met the
main requirements of jet fuels. The transformation potentially pro-
vides a useful way for development of green aviation biofuels using
biomass.
Acknowledgements
We acknowledge the support from National Key Basic Program
of China (973 Program, 2013CB228105), National Sci-Tech Support
Plan (2014BAD02B03), National Natural Science Foundation of Chi-
na (51161140331), Program for Changjiang Scholars and Innova-
tive Research Team in University and the Fundamental Research
Funds for the Central Universities (wk 2060190040).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2015.02.
023.
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