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Fuel 116 (2014) 642649

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Fuel
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Upgrading of bio-oil into advanced biofuels and chemicals. Part III.


Changes in aromatic structure and coke forming propensity during
the catalytic hydrotreatment of a fast pyrolysis bio-oil with Pd/C catalyst
Xiang Li, Richard Gunawan, Yi Wang, Weerawut Chaiwat, Xun Hu, Mortaza Gholizadeh, Daniel Mourant,
John Bromly, Chun-Zhu Li
Fuels and Energy Technology Institute, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia

h i g h l i g h t s
 Coking tendency and aromatic structures of bio-oil change during hydrotreatment.
 Repolymerisation surpasses the hydrogenation of bio-oil at mild conditions.
 Coking tendency is reduced under severe hydrotreating conditions.
 Combined esterication and hydrotreatment can produce more stable biofuel.

a r t i c l e

i n f o

Article history:
Received 24 December 2012
Received in revised form 10 August 2013
Accepted 15 August 2013
Available online 5 September 2013
Keywords:
Bio-oil
Upgrading
Hydrotreatment
Esterication
Coke

a b s t r a c t
This study has investigated the hydrotreatment of bio-oil (derived from the fast pyrolysis of mallee
woody biomass) in a batch reactor under 10 MPa pressure with Pd/C catalyst at temperatures between
150 C and 300 C. Our results indicate that the chemical fractions, coking tendency as well as the aromatic structures are highly inuenced by the hydrotreating conditions such as temperature and time.
The repolymerisation surpasses the hydrogenation of bio-oil at the low hydrotreating temperatures
(e.g. 150200 C) and short hydrotreating durations (e.g. <3 h). On the contrary, high hydrotreating temperatures (e.g. 250300 C) and long reaction durations (e.g. 612 h) can effectively convert the heavier
fractions into lighter fractions, and thus further reduce the coking tendency of the hydrotreated products.
However, these harsh operational conditions cannot decrease the number of large aromatic ring systems.
Most importantly, it is found that the combination of esterication and hydrotreatment can produce
more stable bio-oil with lower coking tendency and less large aromatic ring systems than the direct
hydrotreatment of bio-oil.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The fast pyrolysis of biomass is one of the most promising biofuel technologies to produce liquid bio-oil and solid bio-char.
While the bio-char is returned to the eld as a soil conditioner
and for carbon bio-sequestration, bio-oil can be converted to green
transport biofuels or feedstocks for gasiers/boilers [1]. However,
bio-oil is a complex mixture of hundreds of chemicals. It not only
has high acidity and water content, but also shows high thermal
instability and polymerisation tendency [2]. Therefore, bio-oil
must be upgraded signicantly to improve its physical and chemical properties before it can be used as a liquid fuel [3].

Corresponding author. Tel.: +61 8 9266 1131; fax: +61 8 9266 1138.
E-mail address: chun-zhu.li@curtin.edu.au (C.-Z. Li).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.08.046

Various severe bio-oil upgrading processes have been investigated including hydrodeoxygenation, hydrocracking and high
pressure thermal treatment (HPTT) [310]. However, the major
problem in these upgrading processes is the deactivation of catalysts due to formation of heavy tar and coke from the bio-oil. A
two-stage hydrotreatment process using conventional petroleum
HDS catalysts (such as sulphided NiMo/Al2O3 and CoMo/Al2O3) in
continuous process has been proposed by Elliott et al. [3,5,11],
which appeared to be the most effective process so far to avoid
excessive coking. However, extremely long reaction times and
excessive hydrogen consumption were always required to reach
high deoxygenation levels, indicating the low activity of the
petroleum hydrotreating catalysts. Therefore, some noble-metal
catalysts (such as Ru, Pt and Pd) on various supports (such as alumina, carbon and titanium) were explored for the hydrotreatment
of bio-oil and model compounds [6]. It was found that the Ru/C and

X. Li et al. / Fuel 116 (2014) 642649

Pd/C catalysts presented much higher oil yields and the deoxygenation levels compared with other noble-metal catalysts. Unfortunately, various quantities of coke/solid were unavoidably formed
during the hydrotreatment of bio-oil with the noble-metal catalysts, though this was highly dependent on the operational
conditions.
To date insufcient study has been carried out on the mechanism of coke formation on catalyst during the hydrotreatment of
bio-oil [12,13]. Especially, little is known about the relationship between the coking tendency and the transformation of aromatic
compounds as well as the high molecular weight species in the
bio-oil, which are believed to be the most important precursors
of coke formation. UV-uorescence spectroscopy has been successfully used to analyse the concentration and relative size of aromatic ring structures in bio-oil. Thermogravimetric analysis
(TGA) has been widely employed as a good indicator of the distribution of chemical fractions in bio-oil based on their different volatility [1420]. The combination of these two instrumental
techniques is believed to be greatly benecial in understanding
the formation of coke on catalysts by elucidating the formation
of aromatic structures and the fate of high molecular weight species in the bio-oil.
According to our recent study, the polymerisation of lignin-derived oligomers during the pyrolysis of bio-oil can be greatly enhanced by the cellulose/hemicelluloses-derived species in the
bio-oil [18]. Interestingly, we also found that highly reactive species in bio-oil such as carboxylic acids, aldehydes and even simple
sugars (which are typical cellulose/hemicelluloses-derived species)
can be easily stabilised by catalytic esterication under mild conditions [20,21]. In order words, the esterication can effectively reduce the number of reactive species in the bio-oil and thus should
decrease coke formation on catalyst during the further hydrotreatment of esteried bio-oil. To our best knowledge, no one has conducted such two-step upgrading of bio-oil (including initial
esterication and nal hydrotreatment) to investigate the changes
in chemical fractions, aromatic structures as well as coking tendency during the upgrading process.
The objective of this study is to investigate the changes in cokeforming propensity and aromatic structures during the catalytic
hydrotreatment of fast pyrolysis bio-oil under various upgrading
temperatures and durations. Especially, the esteried bio-oil was
hydrotreated under the same conditions as the raw bio-oil for
exploring more effective upgrading technology to minimise the
coking problem. We have chosen the Pd/C catalyst that has shown
good activities for the hydrotreatment of bio-oil [6]. Screening the
performance of various catalysts is beyond the scope of this study.
While the different chemical fractions and coking tendency of
hydrotreated bio-oil were characterised with TGA, UV-uorescence spectroscopy was employed to trace the overall changes in
aromatic ring systems in the hydrotreated products.

2. Material and methods


2.1. Chemicals and materials
The raw bio-oil was obtained from the fast pyrolysis of mallee
wood biomass in a uidised bed reactor at approximately 500 C.
A detailed description of the reactor and experimental procedure
can be found elsewhere [17]. The catalyst used in this study was
palladium on activated carbon (Sigma Aldrich #205680, 5 wt% Pd
supported on dry carbon powder). Hydrogen (high purity) and
nitrogen (high purity) were obtained from BOC Gases Australia.
For the esterication of bio-oil, GC-grade methanol (>99.98%,
Merck Australia) and solid acid catalyst Amberlyst-70 (Rohm &
Haas) were used directly without any pre-treatment.

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2.2. Experimental procedures


The catalytic hydrotreating experiments were performed in a
batch autoclave reactor (Autoclave Engineers, Division of Snap-Tite
Inc.) comprising of a 130 mL Hastalloy pressure reactor vessel, a
high speed magnetic agitator, a ceramic band heater and a universal reactor controller. In a typical experiment, 4.5 g Pd/C catalyst
(5 wt% on the basis of bio-oil) was rstly activated by hydrogen
gas at pressure 4 MPa and temperature 300 C for 2 h. After cooling
down and venting of gases, raw bio-oil (90 g) was drawn into the
vessel using an external vacuum pump. The reactor was ushed
with nitrogen to displace residual air, and subsequently pressurised with hydrogen to 4 MPa at room temperature. The reactor
was heated to the required temperature while the reactants were
strongly agitated at a stirring rate of 1000 rpm. After the reactor
reached the required temperature, the hydrogen pressure was increased to 10 MPa and remained at that pressure throughout the
experiment. After completion of the reaction, the reactor was
quickly cooled to room temperature using a cooling water coil.
The hydrotreated products normally consisted of an aqueous
phases (on the top), oil phases (on the bottom) and wet solids (catalyst and coke at the bottom). Each phase was separated by a centrifuge for further analysis. The reactor was rinsed with acetone.
The acetone-washed liquid with suspended solid was ltered and
then combined with wet solids separated from the liquid products
after centrifuging. A mixture of solvents (chloroform/methanol
4:1) was used to wash the organics in the solid during ltration until the ltrate was colourless. After drying the lter paper at 105 C
for overnight, the amount of solids/coke formed during the
hydrotreating process was calculated by the differences between
the original catalyst and the total solid on the dried lter paper.
During the two-step bio-oil upgrading process including initial
esterication and nal hydrotreatment, the raw bio-oil was rstly
esteried with methanol using a commercial solid acidic catalyst at
temperatures 70 C, 130 C and 170 C to stabilise the reactive oxygen-containing functional groups. Then, the reaction mixtures
(including esteried bio-oil and methanol) were vacuum distilled
at 2040 C (<50 Torr) for 30 min to remove excessive amounts
of methanol and some volatile fractions. A more detailed description of esterication and distillation procedures can be found elsewhere [20]. After the hydrotreatment of the esteried and distilled
bio-oil at 300 C for 3 h, the nal products were designated as
EDH-70, EDH-130 and EDH-170, respectively, where 70, 130
and 170 referred to the esterication temperatures of 70 C,
90 C and 170 C.
2.3. Product analyses
Thermogravimetric analysis of the hydrotreated products was
conducted over the temperature range 25500 C at a heating rate
of 10 C/min in nitrogen (ow rate 100 mL/min) using a TA Instruments Q600. In a TGA run, 510 mg of sample was loaded into an
alumina crucible in the TGA. For a better comparison of the chemical compositions of hydrotreated products, the differential thermogravimetric (DTG) curves were multiplied by the sample yield
to present the DTG data on the same basis of per gram of raw
bio-oil. The potential coke formation data (derived from weight
loss curve at 500 C) were also converted onto the same basis for
comparison with raw bio-oil. In this way, all the thermogravimetric data of hydrotreated samples can be directly compared with
each other in a manner that has been established previously
[16,17,19,20].
In this study, the aromatic structures of the hydrotreated products were analysed using a PerkinElmer LS50B UV-uorescence
spectrometer. Prior to test, each oil sample was diluted with methanol (Uvasol for spectroscopy, purity >99.9%) to 4 ppm for avoiding

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X. Li et al. / Fuel 116 (2014) 642649

the self-absorption effect [14,17,18]. The synchronous spectra


were recorded with a constant energy difference of 1400 cm 1
or 2800 cm 1 with a slit width of 2.5 nm and a scan speed of
200 nm/min. Each spectrum shown in this paper represents the
average of four scans. The data were recorded and analysed using
the FL Winlab software. In order to compare the spectra on the
same basis, the uorescence intensity was multiplied by the yield
of products to display on the basis of per gram of raw bio-oil
[17,18].

3. Results and discussion


3.1. Hydrotreated product yields and distributions
In this study, the effects of hydrotreating temperature were
investigated in the range of 150300 C with the same reaction
time of 3 h. The effects of reaction time of hydrotreating were
investigated in the range of 112 h at temperature of 250 C and
300 C. As is shown in Fig. 1, the liquid products after hydrotreating
bio-oil normally were present in two liquid phases, including a
light yellow aqueous phase on the top and a dark brown oil phase
at the bottom. However, the hydrotreatment of bio-oil at 150 C
produced only one single oil phase, which is a similar result to
other reports on the mild-hydrotreatment of bio-oil at 175 C
[6,7]. While the exact roles of the Pd/C catalyst during the hydrotreatment remain unclear, the data in Fig. 1 (and those shown below), in broad agreement with the literature [6], appear to indicate

that the catalyst was active even at very low temperature (e.g.
150 C). In particular, the catalyst must have been able to activate
hydrogen to produce active hydrogen at these low temperatures.
The active hydrogen could then react with the bio-oil molecules
(or fragments) adsorbed on the catalyst to cause their hydrogenation, including hydrodehydrogenation.
It was found that the overall liquid mass balance closure was
more than 80 wt%, and the difference between the liquid products
and the raw bio-oil was mainly due to the formation of gases, solids/cokes and unavoidable losses during the collection of products.
It was clearly shown that the liquid phase distribution remained
relatively stable with increasing hydrotreating temperature and
time [see Fig. 1ac]. However, the amounts of oil and aqueous
phases gradually declined with increasing esterication temperature from 90 C to 170 C as shown in Fig. 1d. This is possibly
caused by the loss of bio-oil fraction during esterication and distillation process. According to our previous study, some medium or
heavy fractions in bio-oil can be converted into lighter fractions
during esterication, which were subsequently removed during
vacuum distillation [20]. Although the direct gas yield was not
measured during the experiment, it may indirectly be deduced that
the gas yield increased gradually with increasing hydrotreating
temperature and time, since the difference between the total liquid
product yields and the raw bio-oil present a similar increasing
trend. A possible explanation is the occurrence of catalytic decarboxylation/decarbonylation to produce gaseous components (such
as CO2, CO and CH4) at higher temperatures and longer reaction
times, as reported previously [3,6]. The direct coke formation

Fig. 1. Phase distribution of liquid products after the hydrotreatment of bio-oil as a function of (a) temperature, (b) time at 250 C, (c) time at 300 C and (d) effects of
esterication.

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X. Li et al. / Fuel 116 (2014) 642649

during hydrotreatment was only determined for duplicated experiments at 250 C and 300 C, which are 1.20 wt% and 1.22 wt%,
respectively. This is in good agreement with literature reporting
that a Pd/C catalyst gave a low coke yield during the hydrotreatment of bio-oil [6].

3.2. Effects of hydrotreating temperature on the coking propensity and


aromatic structure of hydrotreated products
It is known that differential thermogravimetric (DTG) curves
can be used for quantifying the chemical compositions of bio-oil
based on their evaporation (including reaction at high temperature) characteristics [16,17,19,20]. For example, the light fractions
normally represent volatile organic compounds (such as formic
acid, simple esters and alcohols), water and organic compounds
with boiling points close to water (such as acetic acid and acetol).
The medium fractions mainly represent phenolic compounds, furans and simple sugars (such as levoglucosan). The heavy fractions
are mostly attributed to the oligomeric compounds from cellulose,
hemicelluloses and lignin, which are also regarded as the most
important precursors of coke formation in TGA. The heavy components may have high tendency to form coke during hydrotreatment. TGA provides a surrogate measure of the presence of these
heavy components. Moreover, the potential coke yield (considered
as the residuals in the weight loss curves in TGA at 500 C) can be
regarded as an important indicator for the coke-forming propen-

sity of bio-oil, which was ascribed to the polymerisation of various


fractions in bio-oil under a mimic pyrolysis process in TGA.
Fig. 2 compares the DTG curves and potential coke yield for the
raw bio-oil and hydrotreated bio-oils as a function of hydrotreating
temperature. It is shown in Fig. 2a that the aqueous phase mainly
contained the light fractions and a small amount of medium fractions (with TGA temperature below 300 C). On the contrary, the
oil phase products were dominated by medium and heavy fractions besides signicant amounts of light fractions, as shown in
Fig. 2b. As expected, less than 1 wt% (on the base of raw bio-oil)
of the potential coke formation occurred in the TGA for the aqueous phase products at different hydrotreating temperatures in
Fig. 2d. However, large amounts of coke (around 1.59.5 wt%) were
produced from the oil phase, implying the heavy and medium fractions present more signicant coking tendency than the light fractions. It is noteworthy that Fig. 2c has combined the DTG curves of
aqueous phase [Fig. 2a] and oil phase [Fig. 2b] together presented
on the same basis of per gram of raw bio-oil. In this way, the overall chemical fractions and coking propensity can be compared with
each other to clarify the effects of hydrotreating temperature on
the hydrotreated products.
In Fig. 2c, we can see that the amount of light fractions in the
150 C hydrotreated product decreased, while both medium and
heavy fractions slightly increased compared with those of raw
bio-oil. In addition, more than 1 wt% of potential coke produced
in the 150 C sample than that of raw bio-oil in Fig. 2d. These data
suggest that the hydrotreated bio-oil at 150 C has high thermal

(a)

(b)

(c)

(d)

Fig. 2. Effects of hydrotreating temperature on (a) the DTG curves of aqueous phase, (b) the DTG curves of oil phase, (c) the DTG curves of sums of all phases and (d) the
potential coke yield of the bio-oil after hydrotreatment for 3 h.

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X. Li et al. / Fuel 116 (2014) 642649

instability and polymerisation tendency, which is in good agreement with other reports [6,22]. For the bio-oils hydrotreated at
200 C and 250 C, a signicant increase in light fractions with boiling points around 100 C is observed, implying large amounts of
water and volatiles were produced via hydrodeoxygenation of oxygen-containing compounds. The medium fractions in these two
hydrotreated samples, however, decreased in TGA temperature
range of 150300 C and then increased rapidly in the temperature
range of 320420 C. Moreover, their heavy fractions and total potential coke yields [56 wt% in Fig. 2d] both reduced to a similar level, which implies that the hydrotreatment of bio-oil at mild
temperature (between 200 C and 250 C) would only marginally
reduce the polymerisation tendency and improve the thermal stability. Although the DTG curve of bio-oil hydrotreated at 300 C is
similar to the lower hydrotreating temperature samples, the higher
magnitude of light fractions and medium fraction (with TGA temperature below 250 C) were observed in this sample. Surprisingly,
the total potential coke yield decreased to 2 wt%, which suggests
that a higher hydrotreating temperature (such as 300 C) would
effectively convert the heavy fractions into lighter ones through
hydrodeoxygenation and/or hydro-cracking and thus reduce the
coking tendency in the hydrotreated product.
Due to the negligible uorescence intensity in the aqueous
phase of hydrotreated bio-oil, Fig. 3 only compares the synchronous spectra of oil phase products at various hydrotreating temperatures. The raw bio-oil clearly shows three broad peaks
centred at 270280 nm, 320330 nm and 350360 nm in the synchronous spectra. Especially, the peak at 350360 nm is always
more intense than the other two peaks, implying the presence of
abundant large aromatic ring systems (e.g. two or more fused benzene rings) in the raw bio-oil which are normally originated from
lignin-derived oligomers [14,17,18]. The synchronous spectra for
the hydrotreated bio-oil samples, however, mainly present two
peaks centred around 270280 nm and 320330 nm. With increasing hydrotreatment temperature from 150 C to 300 C, the rst
peak (around 270280 nm) showed negligible change at temperature lower than 250 C, but it increased signicantly to a large value at a hydrotreating temperature of 300 C. In contrast, the
second peak (around 320330 nm) tended to increase monotonically with hydrotreating temperature. It is also interesting to see
that hydrotreated samples between 150 C and 200 C presented
relatively low uorescence intensity compared with the spectrum
of raw bio-oil, possibly due to the polymerisation of small ring systems into extremely large ring systems and/or cokes which are beyond the detection limit of the current synchronous spectral
method. However, the hydrotreated samples at 300 C not only
showed almost double the uorescence intensity of raw bio-oil,

Fig. 3. Effects of hydrotreating temperature on the synchronous spectra (with a


constant energy of 2800 cm 1) of the bio-oil after hydrotreatment for 3 h.

but also gave comparably high intensity at wavelength higher than


360 nm. The results appear to suggest that abundant ring systems
with various sizes can be produced via cracking of extremely
large aromatic systems (such as large oligomers) during the
hydrotreatment at 300 C.
3.3. Effects of hydrotreating time on the coking propensity and
aromatic structure of hydrotreated products
Fig. 4 shows the DTG curves and potential coke yields for the
bio-oils hydrotreated at 250 C for varying lengths of reaction time.

Fig. 4. Effects of hydrotreating time on (a) the DTG curves of aqueous phase, (b) the
DTG curves of oil phase and (c) the potential coke yield of bio-oil after
hydrotreatment at 250 C.

X. Li et al. / Fuel 116 (2014) 642649

It is necessary to point out that around 40 wt% of the total hydrotreated products has been transferred into aqueous phase [see
Fig. 1b] due to the polarity change after hydrotreatment. Based
on the DTG curves in Fig. 4a, it is believed that most of the aqueous
phase products are light and medium fractions. Therefore, it is
understandable that the oil phase products in Fig. 4b might contain
much smaller amounts of light and medium fractions in comparison to the raw bio-oil. With increasing reaction time, only a
slightly increasing trend was displayed in the aqueous phase samples, as shown in Fig. 4a. In the oil phase [see Fig. 4b], however, the
amount of light fractions gradually increased while the medium
and heavy fractions reduced comparably with the reaction time.
As expected, the potential coke yields greatly declined with
increasing reaction time, as shown in Fig. 4c, which conrms that
a longer reaction time would effectively reduce the heavy fractions
and coking tendency of hydrotreated product. However, the potential coking yields for the rst 3 h are fairly constant at around
5 wt%, which was almost three times higher than the samples in
the period 612 h (about 1.5 wt%). A closer examination of the
DTG curves of the samples after the rst 3 h also reveals that the
medium and heavy fractions (with TGA temperature higher than
300 C) rose to a higher level compared against other samples, possibly due to the formation of intermediate components (e.g. low
molecular oligomer) via the breakdown of heavy fractions (e.g.
high molecular oligomer).
In Fig. 5, the synchronous spectra for hydrotreated bio-oil samples (oil phase only) at 250 C are shown as a function of reaction
time with an energy difference of 2800 cm 1. The major peaks of
hydrotreated samples are centred around 270280 nm and 320
330 nm, and the latter shows much higher intensity than the former. Compared with the raw bio-oil, the hydrotreated samples
show slightly higher intensity at both peaks. However, the peak
centred around 350360 nm in the raw bio-oil is scarcely present
in the hydrotreated samples, except for the sample obtained after
a reaction time of 3 h. This trend coincides with the changes in
the shape of DTG curves after rst 3 h as shown in Fig. 4b, indicating some intermediate aromatic ring systems could be derived
from the cracking/hydrogenation of large ring systems at the initial
stage (e.g. rst 3 h) of hydrotreatment at 250 C. With increasing
reaction time between 6 h and 12 h, both peaks in hydrotreated
samples gradually increased to an identical (maximum) intensity.
This result is also consistent with the coke tendency data in
Fig. 4c, where the potential coke yield of oil phase was stable
around 1 wt% at hydrotreating period from 6 to 12 h.

Fig. 5. Effects of hydrotreating time on the synchronous spectra (with a constant


energy of 2800 cm 1) of the bio-oil after hydrotreatment at 250 C.

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The DTG curves and coking tendency of the bio-oils hydrotreated at 300 C are shown as a function of reaction time in Fig. 6. Since
the aqueous phase showed almost identical DTG curves in Fig. 6a
and the similar potential coke yields in Fig. 6c for each other, only
the oil phase products will be compared in details in this section.
Similar to the bio-oil hydrotreated at 250 C in Fig. 4, the amount
of light fraction in oil phase slightly increased along with reaction
time, while the medium and heavy fractions gradually decreased.

Fig. 6. Effects of hydrotreating time on (a) the DTG curves of aqueous phase, (b) the
DTG curves of oil phase and (c) the potential coke yield of bio-oil after
hydrotreatment at 300 C.

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X. Li et al. / Fuel 116 (2014) 642649

(a)
Fig. 7. Effects of hydrotreating time on the synchronous spectra (with a constant
energy of 2800 cm 1) of bio-oil after hydrotreatment at 300 C.

As expected, the potential coke yield in oil phase kept decreasing


until below 1 wt%, which was the lowest value from any hydrotreated products. It is also found that the hydrotreated bio-oil at
300 C contained lesser amounts of light and medium fractions
than the 250 C samples. In addition, the potential coke yield of
the 300 C samples reduced to less than half of 250 C samples during the rst 3 h of reaction. These results further conrm that higher hydrotreating temperatures and longer hydrotreating times will
tend to more readily crack the heavier fractions into lighter fractions and thus decrease the coking tendency.
Fig. 7 summarises the synchronous spectra of hydrotreated biooil samples (oil phase only) at 300 C with reaction time ranging
from 1 to 12 h. It is fairly similar to the previous data in that two
main peaks can be observed at around 270280 nm and 320
330 nm in all hydrotreated samples. Furthermore, both peaks increased substantially with reaction time and the highest peaks
were found at 12 h which are more than twice of those of the
raw bio-oil. Interestingly, the second peak slightly shifted to higher
wavelengths with increasing reaction time, and thus led to a broad
and weak peak showing round 370420 nm. Compared with the
raw bio-oil, the peak at round 370420 nm of the hydrotreated
samples represented unusually large ring systems that may not
have existed in the raw bio-oil. In other words, longer hydrotreating time might lead to the formation of additional larger ring systems via cracking of extremely heavy fractions in raw bio-oil,
which is consistent with the DTG and coking tendency data in
Fig. 6.

(b)

3.4. Effects of esterication on the coking propensity and aromatic


structure of hydrotreated products
The effects of esterication on the thermogravimetric property
of bio-oil during hydrotreatment at 300 C for 3 h are shown in
Fig. 8. After the esterication of bio-oil at 70 C, 90 C and 170 C,
the amount of each fraction and the potential coke yield after
hydrotreatment decreased slightly compared with the directly
hydrotreated sample. This trend is expected since the reactive Ocontaining functional groups in the raw bio-oil could be effectively
stabilised through esterication. As a result, the fractions with
higher boiling points could be converted into lower boiling point
fractions via esterication, which further enhanced the efciency
of the following hydrotreatment process and decreased the coking
propensity of nal products. With increasing esterication temperature, the changes in heavy fractions as well as the potential coke
yield were not signicant. Based on our previous investigation, the
light and medium fractions are more easily upgraded than the hea-

(c)
Fig. 8. Effects of esterication on (a) the DTG curves of aqueous phase, (b) the DTG
curves of oil phase and (c) the potential coke yield of bio-oil after hydrotreatment at
300 C for 3 h.

vy fractions during the esterication of bio-oil [20]. In other words,


esterication temperature only shows minor effect on upgrading of
heavy fractions compared with the effect of hydrotreatment temperature, as discussed in Section 3.2.
Fig. 9 compares the effects of esterication on the changes in
the aromatic structures of hydrotreated bio-oil (oil phase only) at
300 C for 3 h. Similar to the directly hydrotreated bio-oil, all esteried samples had two major peaks centred around 270280 nm
and 320330 nm, which were slightly more intense than those in

X. Li et al. / Fuel 116 (2014) 642649

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tendency and less large aromatic ring systems than the directly
hydrotreated bio-oil.
Acknowledgments
Australian Government funding through the Second Generation
Biofuels Research and Development Grant Program supports this
project. The study also received support from the Government of
Western Australia via the Centre for Research into Energy for Sustainable Transport (CREST).
References

Fig. 9. Effects of esterication on the synchronous spectra (with a constant energy


of 2800 cm 1) of bio-oil after hydrotreatment at 300 C for 3 h.

the raw bio-oil. Further compared with the directly hydrotreated


sample, esteried samples after hydrotreatment showed a
signicantly lower intensity peak at around 320330 nm, though
they had similar spectra at wavelengths around 270280 nm. In
addition, the directly hydrotreated sample showed a peak at round
360420 nm that was absent in the three pre-esteried samples,
implying the concentration of large aromatic ring systems could
be effectively reduced by combining esterication and hydrotreatment together. With increasing esterication temperature, however, there was a minor increasing trend of the peak around
320330 nm for the three esteried samples. This further conrms
the limited inuence of esterication temperature on changing the
aromatic structure during the hydrotreatment of bio-oil, which is
in good agreement with thermogravimetric data in Fig. 8.
4. Conclusions
In this study, we have investigated the hydrotreatment of a typical fast pyrolysis bio-oil (derived from Western Australia mallee
woody biomass in a uidised-bed reactor) in a batch reactor at
temperatures ranging from 150 C to 300 C under 10 MPa
pressure with Pd/C catalyst. The detailed characterisation of the
hydrotreated liquid products with thermogravimetry and UV-uorescence spectroscopy revealed that the chemical fractions and
coking tendency as well as the aromatic structures were highly
inuenced by the hydrotreating conditions such as temperature
and time duration. Our results showed that the bio-oil hydrotreated at low temperatures (e.g. 150 C) and short reaction times (e.g.
<3 h) had high coking tendency because the repolymerisation of
reactive fractions and small aromatic rings surpassed the hydrogenation of heavy fractions and/or large aromatic rings. On the contrary, high hydrotreating temperatures (e.g. 250300 C) and long
reaction durations (e.g. 612 h) could effectively convert the heavier fractions into lighter ones and thus further reduce the coking
tendency of the hydrotreated products. However, harsh operational conditions in this study including the higher temperature
and longer reaction time cannot decrease the concentration of
large aromatic ring systems. A likely explanation of the increasing
number of the large ring systems would be the cracking of large
oligomers under the severe hydrotreating conditions. Most importantly, we found that the combination of esterication and hydrotreatment could produce more stable bio-oil with lower coking

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