Fuel 179 (2016) 4551

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Hydrotreatment of fast pyrolysis oil: Effects of esterification

pre-treatment of the oil using alcohol at a small loading
Ehsan Reyhanitash a, Matthew Tymchyshyn a, Zhongshun Yuan a, Katherine Albion b, Guus van Rossum a,c,
Chunbao (Charles) Xu a,
a
b
c

Institute for Chemicals and Fuels from Alternative Resources, Faculty of Engineering, Western University, London, Ontario N6A 5B9, Canada
The Bowman Centre, Western Sarnia-Lambton Research Park, Sarnia, Ontario N7W 1B8, Canada
Sustainable Process Technology, University of Twente, 7500 AE Enschede, The Netherlands

h i g h l i g h t s
 Pyrolysis oil was stabilized by esterification with alcohol before hydrotreatment.
 Methanol, ethanol or glycerol was used at a small loading (5 wt% w.r.t. bio-oil).
 The stabilization did not affect yield/composition of the hydrotreated oil product.
 The stabilization could effectively reduce the molecular weight of the feed.
 The stabilization could prevent self-polymerization of the oil in hydrotreatment.

a r t i c l e

i n f o

Article history:
Received 30 November 2015
Received in revised form 17 March 2016
Accepted 19 March 2016
Available online 28 March 2016
Keywords:
Fast pyrolysis oil
Stabilization
Methanol
Ethanol
Glycerol
Hydrotreatment

a b s t r a c t
Aiming to retard the self-polymerization of the reaction intermediates during bio-oil upgrading process, a
large amount of alcohol (e.g., 50 wt% with respect to bio-oil) was used in the stabilization of fast pyrolysis
oil by esterification before hydrotreatment by the authors in a previous work. In order to reduce the
amount of alcohol use and hence improve the process economy, effects of stabilizing fast pyrolysis oil
by esterification with methanol, ethanol or glycerol at a small loading (5 wt% w.r.t. bio-oil) in the presence of Amberlyst-35 DRY a solid acid catalyst on the subsequent hydrotreatment of the oil were investigated. The bio-oil hydrotreatment experiments were carried out at 300 and 350 C in a combined batch
and semi-batch operation mode with Ru/C catalyst. The results demonstrated that, although stabilization
of the pyrolysis oil by esterification with a small alcohol loading had least effects on the mass and carbon
distribution in the hydrotreatment products and the elemental composition of the hydrotreated oil products, it could effectively reduce the molecular weight of the feed, prevent self-polymerization and
decrease the overall molecular weight of the hydrotreated oil products.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
The increased energy demand as well as the concerns about
diminishing petroleum resources and the associated environmental issues, have sparked increasing interest in the use of biomass
as a replacement for fossil fuel resources [13]. Lignocellulosic

Abbreviations: EPO, stabilized fast pyrolysis oil with ethanol; GPC, gel permeation chromatography; GPO, stabilized fast pyrolysis oil with glycerol; MPO,
stabilized fast pyrolysis oil with methanol; MW, molecular weight; NPO, stabilized
fast pyrolysis oil without alcohol; PO, fast pyrolysis oil; TT, thermal treatment.
Corresponding author.
E-mail address: cxu6@uwo.ca (C. (Charles) Xu).
http://dx.doi.org/10.1016/j.fuel.2016.03.074
0016-2361/ 2016 Elsevier Ltd. All rights reserved.

biomass in particular, has been studied because it is a renewable

resource that can be used to produce fuels and chemicals which
are currently derived mainly from petroleum [4].
In order to be used as a fuel, lignocellulosic biomass needs to
undergo a conversion process for energy-content densification
due to its low volumetric energy content. Pyrolysis converts solid
biomass in an oxygen deficient environment at 400800 C, producing pyrolysis oil at a high yield up to 75% [5]. However, pyrolysis oils have much higher oxygen contents than petroleum, in the
form of water and oxygen-containing functional groups, which
result in an elemental composition similar to that of biomass from
which they were derived [6,7]. The oxygenated functional groups
(mainly hydroxyaldehydes, hydroxyketones, carboxylic acids,

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E. Reyhanitash et al. / Fuel 179 (2016) 4551

sugars, levoglucosan and phenolics, etc.) make pyrolysis oil chemically unstable [8,9]. Lu et al. [10] concluded that aldehydes are the
most unstable components in a bio-oil since they can react with
many different types of chemicals including water, phenolics,
and alcohols to form condensed products. The lack of chemical stability predominantly expresses itself through self-polymerization
during storage and downstream processing [11]. Selfpolymerization of pyrolysis oil during processing is highly undesirable, as it can lead to reactor clogging and catalyst deactivation
[12,13]. The high oxygen content of a pyrolysis oil lead to lower
calorific values of the oil (LHV = 1418 MJ/kg) which is approximately that of the original biomass and only 1/31/2 of those of
conventional hydrocarbon fuels [14]. It also makes pyrolysis oil
immiscible with conventional hydrocarbon fuels [15].
Thus, the undesirable properties of pyrolysis oils mainly due to
high oxygen content: highly viscous, thermally instable and corrosive, present a great challenge in the use of bio-oils as a substitute
for fossil-derived fuels [16,17]. Further processing or upgrading of
the oil is necessary.
Pyrolysis oil upgrading reduces the oxygen content of the oil,
thereby improving its miscibility with petroleum fractions [18].
Upgraded pyrolysis oil can therefore be blended with a conventional petroleum fraction (e.g. vacuum gas oil) for co-refining
(e.g. via FCC) to produce transportation fuels.
Although pyrolysis oils can be upgraded by thermal or catalytic
cracking, this process is accompanied by significant (up to 40 wt%)
coke production [19], and deep removal of oxygen to below 10 wt%
is very difficult [20].
Catalytic hydroprocessing or hydrotreatment of pyrolysis oil is a
more promising alternative [18,21,22]. In this process, pyrolysis oil
is reacted with hydrogen in the presence of a catalyst to produce a
hydrogenated and deoxygenated oil product with improved physical and chemical properties. The well-known catalysts for
hydrotreatment of pyrolysis oil are conventional hydrodesulfurization catalysts such as sulfided NiMo/Al2O3, CoMo/Al2O3, and NiMo/
Al2O3SiO2 [15,23,24]. Non-sulfided transition metal catalysts, e.g.
MoNi/c-Al2O3 (reduced prior to reaction) and NiCu/d-Al2O3, have
also been tested for the catalytic hydrotreatment of pyrolysis oil,
but to a far lesser extent [25,26]. Noble metal-based catalysts,
which are better known as hydrogenation catalysts, have also been
evaluated as substitutes for sulfided catalysts. Examples of this
include: Pd on zeolite carriers [27], Pd on mesoporous CeO2 and
ZrO2 [28], and Rh on zirconia [29].
The use of carbon-supported catalysts (e.g. Ru/C) has been
widely explored [5,30,31]. Wildschut et al. [14] compared noble
metal catalysts (Ru/C, Ru/TiO2, Ru/Al2O3, Pt/C and Pd/C) and typical
hydrotreatment catalysts (sulfided NiMo/Al2O3 and CoMo/Al2O3),
and they found that Ru/C catalyst exhibited superior oil yields
(up to 60 wt%) and the greatest extent of deoxygenation (up to
90 wt%) as compared to the classical hydrotreatment catalysts.
One approach to limit the extent of coking during pyrolysis oil
upgrading is to stabilize the oil prior to hydroprocessing. As mentioned previously, the condensation reactions that produce coke
are the reactions of compounds containing hydroxyl and carbonyl
functional groups. Thus the stabilization of a pyrolysis oil requires
the removal of these reactive functional groups. Carbohydrates in a
fast pyrolysis oil comprise some of the reactive constituents that
are responsible for molecular weight increase (through polymerization) of fast pyrolysis oil during hydrolysis, hydrotreating, steam
reforming or high pressure thermal treatment [3237]. Carboxylic
acids are amongst the most reactive components found in fast
pyrolysis oil and stabilization of pyrolysis oil with an alcohol (via
esterification) has been described as a promising route to reduce
the reactivity of fast pyrolysis oil [3840].
Increased stability of the pyrolysis oil reduces the likelihood of
self-polymerization both during storage and during processing.

Since self-polymerization and hydro-de-oxygenation (HDO) reactions could co-occur during hydrotreatment, increased pyrolysis
oil stability can increase the selectivity of the HDO reactions
[41,42]. In our previous study [43], glycerol at a relatively high concentration was used to stabilize a fast pyrolysis oil via catalytic
esterification pretreatment, followed by upgrading the stabilized
fast pyrolysis oil via hydrotreatment or thermal treatment. In the
stabilization process in our previous work, a large amount of alcohol (at 50 wt% loading with respect to (w.r.t.) the mass of pyrolysis
oil) was used, where the diluting or free radical-scavenging effects
of the alcohols in the reaction system were believed to play a major
role in retarding the self-polymerization of the reaction intermediates during the upgrading process for the stabilized oil [43].
Aiming to reduce the amount of alcohol use and hence improve
the process economy, effects of stabilizing fast pyrolysis oil with a
small loading (5 wt% w.r.t. bio-oil) of various alcohol, including
methanol, ethanol or glycerol, on the subsequent hydrotreatment
of the oil were investigated in this study.
2. Materials and methods
The hardwood sawdust fast pyrolysis oil (PO) used in this study
was obtained from BTG Biomass Technology Group. It has a water
content of 28 wt% and an HHV of 22.3 MJ/kg (on a dry basis).
Amberlyst-35 DRY (Rohm and Haas) was used without any pretreatment. Ru/C catalyst was purchased from Sigma/Aldrich, with
5 wt% Ru loading, and used as received. ACS reagent grade methanol, ethanol and glycerol were purchased from Caledon.
Fig. 1 illustrates schematic diagram of the experimental setup.
It is a semi-batch reactor designed for continuously supplying
hydrogen into a stirred autoclave batch reactor while maintaining
the pressure of reactor at a desired level. A stirred autoclave reactor was used for both fast pyrolysis oil stabilization and
hydrotreatment of the stabilized oil. The reactor is made of nickel
alloy and has a nominal internal volume of 500 mL (Parr Instrument Company). To produce an alcohol-stabilized pyrolysis oil,
denoted as MPO (methanol-stabilized PO), EPO (ethanolstabilized PO) and GPO (glycerol-stabilized PO), respectively, typically 275 g of wet PO and 13.75 g the respective alcohol (5 wt%
loading w.r.t. to the mass of wet PO) were loaded into the autoclave. Amberlyst-35 DRY at a loading of 3 wt% (w.r.t. the wet liquid
mixture of PO and the alcohol) was added to the reactor. For comparison, NPO (non-alcohol-stabilized PO) was produced by processing PO in the presence of Amberlyst-35 DRY (3 wt%, w.r.t. the
wet PO) without alcohol. The autoclave reactor was then sealed
for and leak proof testing using 20 bar nitrogen for 20 min. After
ensuring leak proof of the reactor, it was flushed twice with
20 bar nitrogen to remove any residual air and filled with 2 bar
nitrogen. The stirrer speed was set at 360 rpm and reactor was
heated to 100 C at an approximate rate of 2 C/min. Retention
time of the reaction was fixed 2 h including the heating time. After
2 h, the heater was switched off and a cold water bath was used to
quench the reactor to room temperature. Gaseous products were
collected in a gas bag for analysis by GC-TCD prior to collection
of the liquid product. The reaction mixture was stirred at
180 rpm during gas collection to promote release of some dissolved gas (such as CO2) in the liquid product. Very small gas yields
were obtained due to the low reaction temperature, therefore analysis of the gases evolved during the stabilization was not reported
in this paper. No phase separation of the reaction mixture was
observed. The spent catalyst was separated from the liquid product
by centrifuge at 4500 rpm for 30 min.
As shown in Fig. 1, high-pressure hydrogen gas was supplied
into the autoclave reactor from a supply vessel (Swagelok, nominal
volume of 300 mL) whose pressure and temperature were
monitored by a PC. The recorded data was used to calculate the

E. Reyhanitash et al. / Fuel 179 (2016) 4551

47

Fig. 1. Schematic diagram of the experimental setup.

hydrogen consumption for each test. In a typical hydrotreatment

run, 150 g of the stabilized wet feed was loaded into the autoclave
reactor and 5 g Ru/C catalyst at a loading of 3.33 wt% (w.r.t. wet
feed) was added to the feed. The reactor was sealed and stirred
at 360 rpm for pre-mixing, and was then subject to leak proof testing using 150 bar hydrogen for 20 min. If leak proof of the reactor
was confirmed, the hydrogen inside was vented from the reactor,
and the residual air was completely removed from the reactor, supply vessel and the entire inlet gas lines using a vacuum pump.
Admittedly, in these vacuuming-purging cycles some high volatiles
of the pyrolysis oil could be lost by evaporation. Nevertheless, the
amount of the high volatiles in the pyrolysis oil is believed to be
low and can be neglected in this work. All hydrotreatment runs
were performed at 300 C on various feeds, i.e., PO, MPO, EPO,
GPO and NPO, respectively. These hydrotreatment tests were first
operated in a batch mode for 1 h including the heating time with
100 bar hydrogen (initial pressure) charged from the supply vessel
pre-filled with up to 250 bar hydrogen. After the reactor was filled
with 100 bar hydrogen, it (in batch mode with V2 and V1 valves
closed) was heated to 300 C at 12 C/min. During this time, the
supply vessel was refilled to 250 bar H2. After 1 h, R1 was set to
150 bar and V1 was opened to increase the pressure of lines to
150 bar. Afterwards, V2 was opened and the hydrogen pressure
inside the reactor was increased to 150 bar. The hydrogen pressure
was maintained at constant pressure of 150 bar for the subsequent
2 h (V2 and V1 valves open) to continuously compensate for the
hydrogen consumed during the hydrotreatment reaction.
After an overall retention time of 3 h, V2 and V1 valves were
closed, the heater was switched off, and the autoclave reactor
was cooled by running cold water into the reactors internal cooling coils for 30 min under stirring. After the temperature of autoclave reactor reached 75 C, the reactor was immersed in an
ice-water bath to further quench it to room temperature. After
cooling, the gaseous products inside the reactor were collected into
a gas bag while remaining the stirring at 180 rpm to facilitate
release of any dissolved gas in the reactor mixture. After the gases

were collected, the liquid product and spent catalyst were decanted from the reactor. Phase separation was now observed in
the liquid product. To improve phase separation, the liquid product
was transferred into centrifuge vials and centrifuged for 30 min
and 4500 rpm. Afterwards, two phases were obtained: a heavier
organic phase (oil fraction, OF) containing the spent catalyst
(recovered by filtration), and an aqueous phase (aqueous fraction;
AF) which contained water and hydrophilic products. Due to the
unavoidable loss of the solid particles upon the recovery operations, in most cases the recovered spent catalyst after drying was
even less than the amount of the fresh catalyst (i.e., 5 g) added into
the reactor before the HDO treatment. Thus, the amount of coke
formation or carbon deposit over the Ru/C catalyst is considered
negligibly small.
Elemental composition and water content analyses of the oil
and aqueous fractions were performed on a CHNS-O analyzer
(Thermo Electron Corporation, Flash-EA-1112 series) and a volumetric Karl Fischer titrator (Mettler Toledo V20), respectively.
The residual alcohol contents in the alcohol stabilized feeds were
measured by GC-FID (Gentech GC-2010). The molecular weights
and distribution of the feeds and the hydrotreated oil products
were analyzed on a Waters Breeze GPCHPLC (gel permeation
chromatographyhigh performance liquid chromatography)
instrument (1525 binary pump, UV detector at 270 nm; Waters
Styrylgel HR1 column at a column temperature of 40 C) using
THF as the eluant at a flow rate of 1 mL/min. Gas composition of
the gas products collected from the tests was measured by GCTCD (Agilent Micro-GC 3000).
3. Results and discussion
3.1. PO stabilization
The elemental composition, water content and high heating
value (HHV) of the PO, mixtures of PO and various alcohols and
alcohol-stabilized POs are shown in Table 1.

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E. Reyhanitash et al. / Fuel 179 (2016) 4551

The elemental compositions of the PO and mixtures of the PO

with various alcohols and various alcohol-stabilized POs are similar either on wet-and-residual-alcohol-included basis or on waterand-residual-alcohol free basis. Thus, the alcohol stabilization
treatment of PO with a small amount of alcohol loading (5 wt%
w.r.t. PO) did not alter the elemental composition of the PO. While
methanol and ethanol conversions were almost the same on mole
basis, the molar conversion of glycerol was higher than that of
methanol and ethanol, indicating that higher reactivity of glycerol
in catalytic esterification of the PO likely due to glycerols multiple
hydroxyl functional group.
Fig. 2 shows molecular weight distributions of the original PO
feed and the stabilized POs with various alcohols. The figure relates
the weight fraction W (log M) vs. molecular weight (M), obtained in
a method as described elsewhere [45]. Compared with the original
PO feed, all stabilized feeds with or without alcohol show obviously lower molecular weights, suggesting that the stabilization
pretreatment of PO over a solid acid with or without alcohol could
effectively reduce the molecular weight of the feed. The reduction
in molecular weight of the PO feed during the stabilization treatment might be owing to both esterification reactions that convert
carboxylic groups into esters and the solid acid catalyzed dehydration reactions that removes hydroxyl groups of the oil, hence lowering the inter-molecular aggregation forces in the oil (mainly
caused by hydrogen bonds) [43]. When an alcohol was used, the
solvent dilution spacing effects might also contribute to the lowering of the inter-molecular aggregation forces, leading to reduced
molar mass of the pre-treated oil.

1.25
PO
MPO
EPO
GPO
NPO

W(LogM) [-]

1
0.75
0.5
0.25
0
100

1000

10000

M [g/mol]
Fig. 2. Molecular weight distribution of various PO feeds with and without alcohol
stabilization treatement.

Table 2
Analyses of the oil fractions from hydrotreatment at 300 C.

Elemental composition
C (wt%)
H (wt%)
O (wt%)a
C (wt%, alcohol free)
H (wt%, alcohol free)
O (wt%, alcohol free)a
H/Ceff (alcohol free)
HHV calculated by Milne
formula (MJ/kg)

3.2. Hydrotreatment of alcohol-stabilized PO

PO

MPO

EPO

GPO

NPO

71.2
8.4
20.4
71.2
8.4
20.4
0.99
33.0

69.3
8.4
22.3
70.0
8.3
21.7
0.95
32.2

68.6
8.4
23.0
69.0
8.3
22.7
0.94
31.7

69.2
8.1
22.7
70.0
8.1
21.9
0.93
32.0

71.0
8.3
20.7
71.0
8.3
20.7
0.97
32.7

Residual alcohol in oil fractions and aqueous fractions

Initial alcohol in feed (mol/

0.209
150 g of feed)
Residual alcohol in aqueous

0.138
fraction (mol/150 g of feed)
Residual alcohol in oil fraction
0.043
(mol/150 g of feed)
Consumed alcohol (mol/150 g
0.028
of feed)

Table 2 shows the properties of oil fractions (OFs) produced via

the hydrotreatment of PO, MPO, EPO, GPO and NPO at 300 C and
150 bar H2 in semi-batch mode operation. The residual alcohol
contents in the feeds and in the obtained oil fractions and aqueous
fractions are also shown in the Table. Since the water content of
the oil fractions was found to be within the error range of the volumetric Karl Fischer titrator used for this study, the oil fractions
were considered water-free.
As shown in Table 2, the elemental composition of the hydrotreated oil fractions from all feeds is very similar, irrespective of
whether or not it was catalytically treated with an alcohol. As also
shown in the Table, alcohol consumption during the hydrotreament
of any an alcohol-stabilized PO was much low (normally <1015%),
and the residual alcohol in the feed was retained almost completely
in the aqueous and oil fractions. During the hydrotreatment of the
alcohol-stabilized PO feeds (MPO, EPO and GPO), consumption of
the residual methanol or ethanol, likely through steam gasification/reforming reaction to form CO/CO2 and H2, appeared to be
more than that of glycerol, which could be explained by the relatively lower reactivity of glycerol than methanol and ethanol.

a
b

0.144

0.028

0.087

0.039

0.042

0.021

0.015

0.032b

Calculated by difference.
The small negative value was likely due to the analytical error.

Fig. 3 is the Van Krevelen plot comparing the hydrogen and oxygen contents of feeds with those of the oil fractions obtained from
300 C hydrotreatment of various PO feeds with and without alcohol stabilization.
It shall be noted that Van-Krevelen plot data the point of GPO
feed does not seem to be plausible (with a similar O/C value as
the other feeds, but a much higher H/C, while glycerol has a lower
H/C than methanol and ethanol). Thus, the elemental analysis of
the GPO feed might be questionable. Unfortunately no GPO sample
was remained, hence redoing of the element analysis on this

Table 1
Properties of PO and mixtures of PO and various alcohols and the alcohol-stabilized POs.

a
b

PO

PO + 5 wt% methanol

MPO

PO + 5 wt% ethanol

EPO

PO + 5 wt% glycerol

GPO

C (wt%)
H (wt%)
O (wt%)a
C (wt%, residual alcohol and water free)
H (wt%, residual alcohol and water free)
O (wt%, residual alcohol and water free)a
Water (wt%)
HHVb (residual alcohol/water free, MJ/kg)

39.6
7.6
52.8
55.0
6.2
38.8
27.9
22.3

39.5
7.8
52.7
Same as PO

40.2
7.8
52.0
Same as PO

38.6
7.6
53.8
52.8
5.9
41.3
26.7
20.8

39.6
7.6
52.8
Same as PO

26.5
22.3

38.3
7.6
54.1
53.2
5.9
40.9
26.7
21.1

38.3
7.8
53.9
53.1
6.4
40.5
27.4
21.8

Alcohol in the feed (mol/150 g of feed)

Converted alcohol (mol/150 g of feed)

0.43

0.011

Calculated by difference.
Milne formula [44]: HHV = 0.341C + 1.322H

0.12(O + N) + 0.0686S

26.5
22.3
0.30

0.012

0.0153Ash; C, H, O, N and Ash in wt% on dry basis.

26.5
22.3
0.15

0.063

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E. Reyhanitash et al. / Fuel 179 (2016) 4551

0.7

0.6

EPO

MPO

GPO

Molar O/C [-]

0.5

PO, NPO

0.4

0.3

0.2

PO
EPO
MPO
+ NPO
GPO

Hydrotreated oil
fractions

0.1

0.0
1.30

1.35

1.40

1.45

1.50

Molar H/C [-]

Fig. 3. Van Krevelen plot of various PO feeds and their hydrotreated oil products at
300 C.

75
CO 2 production
H 2 consumption

g/kg feed

50

25

PO

MPO

EPO

GPO

NPO

Fig. 4. CO2 production and H2 consumption during hydrotreatment of various feeds

at 300 C.

1.25
OF-PO
OF-MPO
OF-EPO
OF-GPO
OF-NPO

W(LogM) [-]

sample is not possible. To draw the attention of the readers to its

possible mistake in the elemental analysis on the GPO feed, the
data point is shown with a question mark in Fig. 3. From Fig. 3, it
is clear that although differing much in the composition of the different feeds, the composition (either O/C or H/C) of the hydrotreated oil fractions is similar, although the EPO-derived
hydrotreated oil fraction has slightly higher H/C value than the
other oil fractions.
Fig. 4 presents the hydrogen consumption and CO2 production
during hydrotreatment of various feeds at 300 C. It shows that
H2 consumption is generally higher from hydrotreatment of various alcohol-stabilized PO feeds than that from the original or
non-alcohol pretreated PO, suggesting enhanced HDO or hydrocracking reactions with the alcohol-stabilized PO feeds. The hydrogen consumption was the highest with the ethanol-stabilized feed
(EPO) which is in good agreement with the highest H/C molar
ration for the oil fraction derived from EPO (Fig. 3). On the other
hand, that CO2 formation from hydrotreatment of all alcoholstabilized PO feeds is consistently lower than that from the original
or non-alcohol pretreated PO. The reduced CO2 production from
alcohol-stabilized PO feeds suggest less decarboxylation during
hydrotreatment of these alcohol-esterified feeds. Reduction in
decarboxylation reaction or reduction in CO2 formation was likely
due to a decrease in the carboxylic acids content of the PO by esterification reactions between the carboxylic acids and an alcohol in
the stabilization treatment [43,37].
Fig. 5 shows molecular weight distributions of the 300 C
hydrotreated oil fractions (OF) from various feeds with or without
alcohol stabilization treatment. As shown in the figure, alcohol stabilization treatment of the PO feed (even at a small alcohol loading)
could produce oil products with reduced molecular weights during
the hydrotreatment at 300 C, compared with the oil products from
the non-stabilized feeds (PO and NPO). Thus it can be concluded
that esterification of the feed with a small amount of alcohol,
together with the presence of a low content of residual alcohol in
the alcohol-stabilized feed as a solvent or radical-scavenger, could
prevent self-polymerization and decrease the overall molecular
weight of the hydrotreated oil products [45,46].
Fig. 6 shows mass and carbon balance closures (on dryand-residual-alcohol free basis) obtained in hydrotreatment of
the various feeds at 300 C. In all tests, the overall mass and carbon
balances are in the reasonable ranges of 8590 wt% and
105110 wt%, respectively. In all tests, the oil fraction contains

0.75
0.5
0.25
0
100

1000

10000

M [g/mol]
Fig. 5. Molecular weight distribution of the 300 C hydrotreated oil fractions (OF).

the greatest mass or carbon contents indicating good energy recovery into the oil product during bio-oil hydrotreatment, which is
highly desirable. The carbon content of the aqueous fraction (AF)
of MPO, EPO or GPO (1115 wt% C) is slightly higher than that of
PO or NPO (approx. 9 wt% C), suggesting that presence of more
hydrophilic compounds. However, alcohol stabilization treatment
of the PO feed did not significantly affect the mass or carbon distribution in the products during the 300 C hydrotreatment.
The effects of PO stabilization on its subsequent hydrotreatment
were further examined at a higher temperature and pressure, i.e.,
350 C and in semi-batch mode with 200 bar H2 for 3 h using
MPO and PO as the feeds comparatively. The amount of CO2 produced in hydrotreatment of MPO at 350 C was significantly greater
than that from the PO hydrotreatment at the same temperature.
Methanol conversion at 350 C was measured also higher than that
at 300 C, suggesting the increase in CO2 formation might partially
from methanol conversion. Increasing the hydrotreatment temperature from 300 C to 350 C resulted in reduction of the residual
methanol content in the MPO-derived hydrotreated oil fraction,
likely due to the enhanced gasification reaction of methanol to form
more CO2 at a higher temperature. Increase in hydrotreatment temperature promoted oxygen removal too, and increased the carbon
content of the oil fraction, hence producing an oil fraction with
much higher HHV (3637 MJ/kg at 350 C vs. 3233 MJ/kg at
300 C, calculated using the Milne formula). Thus, esterificationsta
bilization of bio-oil with a small alcohol loading had significant
effects on the subsequent hydrotreatment upgrading with respect
to the heating values of the hydrotreated oil products.

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E. Reyhanitash et al. / Fuel 179 (2016) 4551

120
AF

OF

GF

100

wt%

80

60

40

20

0
Mass

PO

Mass

Mass

EPO

MPO

Mass

GPO

Mass

NPO

Fig. 6. Mass and carbon distributions in the hydrotreatment products from various feeds at 300 C.

Whereas, at 350 C the effect of alcohol stabilization treatment of

the feed on the molecular weight of the hydrotreated oil products
was negligible, suggesting that in hydrotreatment at a higher temperature, the reaction temperature plays a more prominent role in
determining the overall molecular weight of the hydrotreated oil
products.
Fig. 8 shows the mass and carbon distributions in the
hydrotreatment products from PO and MPO feeds at 300 C and
350 C. Again, the results show that the alcohol stabilization treatment of the PO feed with a small alcohol loading (5 wt% w.r.t. PO)
had insignificant effects on mass and carbon distributions in the
hydrotreatment products at both 300 C and 350 C.

1.4
OF-PO-300C
OF-MPO-300C
OF-PO-350C
OF-MPO-350C

W(LogM) [-]

1.2
1
0.8
0.6
0.4
0.2
0
100

1000

10000

M [g/mol]
Fig. 7. Molar mass distribution of PO and MPO HDO oil fractions at 300 and 350 C.

Fig. 8. Mass and carbon distributions in the hydrotreatment products from PO and
MPO feeds at 300 C and 350 C.

As expected, the 350 C hydrotreatment produced oil fractions

of a lower molar mass due to the promoted hydrocracking reactions at a higher temperature (Fig. 7). As shown in both Figs. 5
and 7, the alcohol stabilization treatment of the feed could effectively prevent self-polymerization and decrease the overall
molecular weight of the hydrotreated oil products at 300 C.

4. Conclusions
In this study, effects of esterification pre-treatment of fast
pyrolysis oil using alcohol at a small loading on the subsequent
hydrotreatment of the oil were investigated experimentally, from
which the following conclusions can be drawn:
(1) The reduction in molecular weight of the PO feed during the
stabilization treatment might be owing to both esterification
reactions that convert carboxylic groups into esters and the
solid acid catalyzed dehydration reactions that removes
hydroxyl groups of the oil, hence lowering the intermolecular aggregation forces in the oil. When an alcohol
was used, the solvent dilution spacing effects might also
contribute to the lowering of the inter-molecular aggregation forces, leading to reduced molar mass of the pretreated oil.
(2) Alcohol stabilization of the PO feed did not significantly
affect the mass or carbon distribution in the products during
the 300 C hydrotreatment. The elemental composition (and
O/C molar ratio) of the hydrotreated oil fractions from all
feeds is very similar, irrespective of whether or not it was
catalytically treated with an alcohol.
(3) There is appreciable difference in H/C between the hydrotreated oil fractions from different alcohol-stabilized PO
feeds, and the EPO-derived hydrotreated oil fraction has
slightly higher H/C value than the other oil fractions. H2 consumption is generally higher from hydrotreatment of various alcohol-stabilized PO feeds than that from the original
or non-alcohol pretreated PO, suggesting enhanced HDO or
hydro-cracking reactions with the alcohol-stabilized PO
feeds.

E. Reyhanitash et al. / Fuel 179 (2016) 4551

(4) Esterification of the feed with a small amount of alcohol,

together with the presence of a low content of residual alcohol in the alcohol-stabilized feed as a solvent or radicalscavenger, could prevent self-polymerization and decrease
the overall molecular weight of the hydrotreated oil
products.
(5) In higher-temperature hydrotreatment (i.e., at 350 C), the
reaction temperature was found to play a more prominent
role than the alcohol-stabilization of the feed, in determining the overall molecular weight of the hydrotreated oil
products and the mass and carbon distributions in the
hydrotreatment products.

Acknowledgements
The authors are grateful for the financial support from NSERC/
FPInnovations Industrial Research Chair Program in Forest
Biorefinery and the Ontario Research Fund-Research Excellence
(ORF-RE) from Ministry of Economic Development and Innovation.
Support from the industrial partners including FPInnovations,
Arclin Canada, BioIndustrial Innovation Centre is also acknowledged. The author (C. Xu) also acknowledges the funding from
NSERC via the Discovery Grant Program.
References
[1] Czernik S, Bridgwater AV. Overview of applications of biomass fast pyrolysis
oil. Energy Fuels 2004;18:5908.
[2] Huber GW, Iborra S, Corma A. Synthesis of transportation fuels from biomass:
chemistry, catalysts, and engineering. Chem Rev 2006;106:404498.
[3] Wang C, Du Z, Pan J, Li J, Yang Z. Direct conversion of biomass to bio-petroleum
at low temperature. J Anal Appl Pyrol 2007;78:43844.
[4] Ibez M, Valle B, Bilbao J, Gayubo AG, Castao P. Effect of operating conditions
on the coke nature and HZSM-5 catalysts deactivation in the transformation of
crude bio-oil into hydrocarbons. Catal Today 2012;195:10613.
[5] Venderbosch RH, Ardiyanti AR, Wildschut J, Oasmaa A, Heeres HJ. Stabilization
of biomass-derived pyrolysis oils. J Chem Technol Biotechnol 2010;85:67486.
[6] Mohan D, Pittman Jr CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: a
critical review. Energy Fuels 2006;20:84889.
[7] Vitolo S, Seggiani M, Frediani P, Ambrosini G, Politi L. Catalytic upgrading of
pyrolytic oils to fuel over different zeolites. Fuel 1999;78:114759.
[8] Bridgwater AV. Biomass fast pyrolysis. Therm Sci 2004;2:2149.
[9] Fisk CA, Morgan T, Ji Y, Crocker M, Crofcheck C, Lewis SA. Bio-oil upgrading
over platinum catalysts using in situ generated hydrogen. Appl Catal A
2009;358:1506.
[10] Lu Q, Li WZ, Zhu XF. Overview of fuel properties of biomass fast pyrolysis oils.
Energy Convers Manage 2009;50:137683.
[11] Hu X, Gunawan R, Mourant D, Lievens C, Li X, Zhang S, et al. Acid-catalysed
reactions between methanol and the bio-oil from the fast pyrolysis of mallee
bark. Fuel 2012;97:51222.
[12] Elliott DC, Neuenschwander GG. Liquid fuels by low-severity hydrotreating of
biocrude. In: Bridgwater AV, Boocock DGB, editors. Developments in
thermochemical biomass conversion, vol. 1. London: Blackie Academic &
Professional; 1996. p. 61121.
[13] Mortensen PM, Grunwaldt JD, Jensen PA, Knudsen KG, Jensen AD. A review of
catalytic upgrading of bio-oil to engine fuels. Appl Catal A 2011;407:119.
[14] Wildschut J, Mahfud FH, Venderbosch RH, Heeres HJ. Hydrotreatment of fast
pyrolysis oil using heterogeneous noble-metal catalysts. Ind Eng Chem Res
2009;48:1032434.
[15] Joshi N, Lawal A. Hydrodeoxygenation of pyrolysis oil in a microreactor. Chem
Eng Sci 2012;74:18.
[16] Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties and
upgrading research. Energy Convers Manage 2007;48:8792.
[17] Brems A, Dewil R, Baeyens J, Seville JPK, Prayogo C, Bending G. The future of
biomass pyrolysis in the production of value-added products. In: Proceedings
of the SDEWES conference, Dubrovnik; September 2629, 2011.
[18] Elliott DC. Historical developments in hydroprocessing bio-oils. Energy Fuels
2007;21:1792815.

51

[19] Vispute TP, Zhang HY, Sanna A, Xiao R, Huber GW. Renewable chemical
commodity feedstocks from integrated catalytic processing of pyrolysis oils.
Science 2010;330:12227.
[20] Gollakota ARK, Reddy M, Subramanyam MD, Kishore N. A review on the
upgradation techniques of pyrolysis oil. Renew Sust Energ Rev
2016;58:154368.
[21] Elliott DC, Hart TR, Neuenschwander GG, Rotness LJ, Zacher AH. Catalytic
hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon
products. Environ Progr Sustain Energy 2009;28:4419.
[22] Rep M, Venderbosch RH, Assink D, Tromp W, Kersten SRA, Prins W, et al. Deoxygenation of bio-oils. In: Bridgwater AV, Boocock DGB, editors. Science in
thermal and chemical biomass conversion. Chippenham: CLP Press; 2006. p.
152635.
[23] Ferrari M, Delmon B, Grange P. Influence of the impregnation order of
molybdenum
and
cobalt
in
carbon-supported
catalysts
for
hydrodeoxygenation reactions. Carbon 2002;40:497511.
[24] Maity SK, Rana MS, Srinivas BN, Bej SK, Murali Dhar G, Prasada Rao TSR.
Characterisation and evaluation of ZrO2 supported hydrotreating catalysts. J
Mol Catal A: Chem 2000;153:1217.
[25] Xu Y, Wang T, Ma L, Zhang Q, Liang W. Upgrading of the liquid fuel from fast
pyrolysis of biomass over MoNi/c-Al2O3 catalysts. Appl Energy
2010;87:288691.
[26] Ardiyanti AR, Venderbosch RH, Heeres HJ. Process-product studies on
pyrolysis oil upgrading by hydrotreatment with Ru/C catalysts. In:
Proceedings of the 2009 AIChE spring national meeting, Tampa; 2009.
[27] Horne P, Williams PT. Reaction of oxygenated biomass pyrolysis compounds
over a ZSM-5 catalyst. Renewable Energy 1996;2:13144.
[28] Senol OI, Viljava TR, Krause AOI. Hydrodeoxygenation of methyl esters on
sulfided NiMo/Al2O3 and CoMo/Al2O3 catalysts. Catal Today 2005;100:3315.
[29] Gutierrez A, Kaila RK, Honkela ML, Slioor R, Krause AOI. Hydrodeoxygenation
of guaiacol on noble metal catalysts. Catal Today 2009;147:23946.
[30] Wildschut J, Melin-Cabrera I, Heeres HJ. Catalyst studies on the
hydrotreatment of fast pyrolysis oil. Appl Catal B 2010;99:298306.
[31] Wildschut J, Iqbal M, Mahfud FH, Melian Cabrera I, Venderbosch RH, Heeres HJ.
Insights in the hydrotreatment of fast pyrolysis oil using a Ru on C catalyst.
Energy Environ Sci 2010;3:96270.
[32] Hu X, Lievens C, Larcher A, Li C. Reaction pathways of glucose during
esterification: effects of reaction parameters on the formation of humin type
polymers. Bioresour Technol 2011;102:1010413.
[33] Megawati A, Wahyudi BS, Hary S, Muslikhin H. Kinetics of sequential reaction
of hydrolysis and sugar degradation of rice husk in ethanol production: effect
of catalyst concentration. Bioresour Technol 2011;102:20627.
[34] Li N, Tompsett GA, Zhang T, Shi J, Wyman CE, Huber GW. Renewable gasoline
from aqueous phase hydrodeoxygenation of aqueous sugar solutions prepared
by hydrolysis of maple wood. Green Chem 2011;13:91101.
[35] Wildschut J, Arentz J, Rasrendra CB, Venderbosch RH, Heeres HJ. Catalytic
hydrotreatment of fast pyrolysis oil: model studies on reaction pathways for
the carbohydrate fraction. Environ Progr Sustain Energy 2009;28:45060.
[36] Marquevich M, Czernik S, Chornet E, Montane D. Hydrogen from biomass:
steam reforming of model compounds of fast-pyrolysis oil. Energy Fuels
1999;13:11606.
[37] de Miguel Mercader F, Groeneveld MJ, Kersten SRA, Venderbosch RH,
Hogendoorn JA. Pyrolysis oil upgrading by high pressure thermal treatment.
Fuel 2010;89:282937.
[38] Zhang Q, Chang J, Wang T, Xu Y. Upgrading bio-oil over different solid
catalysts. Energy Fuels 2006;20:271720.
[39] Lohitharn N, Shanks BH. Upgrading of bio-oil: effect of light aldehydes on
acetic acid removal via esterification. Catal Commun 2009;11:969.
[40] Hilten RN, Bibens BP, Kastner JR, Das KC. In-line esterification of pyrolysis
vapor with ethanol improves bio-oil quality. Energy Fuels 2010;24:67382.
[41] de Miguel Mercader F, Koehorst PJJ, Heeres HJ, Kersten SRA, Hogendoorn JA.
Competition between hydrotreating and polymerization reactions during
pyrolysis oil hydrodeoxygenation. AIChE J 2011;57:316070.
[42] de Miguel Mercader F, Groeneveld MJ, Kersten SRA, Geantet C, Toussaint G,
Way NWJ, et al. Hydrodeoxygenation of pyrolysis oil fractions: process
understanding and quality assessment through co-processing in refinery units.
Energy Environ Sci 2011;4:98597.
[43] Reyhanitash E, Tymchyshyn M, Yuan Z, Albion K, van Rossum G, Xu C.
Upgrading fast pyrolysis oil via hydrodeoxygenation and thermal treatment:
effects of catalytic glycerol pretreatment. Energy Fuels 2014;28:11328.
[44] Milne TA, Brennan AH, et al. Sourcebook of methods of analysis for biomass
and biomass conversion processes. New York: Elsevier Applied Science; 1990.
[45] Hoekstra E, Kersten SRA, Tudos A, Meier D, Hogendoorn KJA. Possibilities and
pitfalls in analyzing (upgraded) pyrolysis oil by size exclusion chromatography
(SEC). J Anal Appl Pyrol 2011;91:7688.
[46] Ardiyanti AR, Khromova SA, Venderbosch RH, Yakovlev VA, Heeres HJ.
Catalytic hydrotreatment of fast-pyrolysis oil using non-sulfided bimetallic
NiCu catalysts on a d-Al2O3 support. Appl Catal B 2012;117118:10517.