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Applied Energy 92 (2012) 234239

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Hydrothermal liquefaction of cellulose to bio-oil under acidic, neutral


and alkaline conditions
Sudong Yin a, Zhongchao Tan b,
a
b

Centre for Environmental Engineering Research & Education, Schulich School of Engineering, University of Calgary, Calgary, Alberta, Canada
Department of Mechanical & Mechatronics Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, Canada N2L 3G1

a r t i c l e

i n f o

Article history:
Received 2 September 2011
Received in revised form 12 October 2011
Accepted 30 October 2011
Available online 29 November 2011
Keywords:
Hydrothermal liquefaction
Cellulose
Bio-oil
pH

a b s t r a c t
Hydrothermal liquefaction (HTL) of biomass to bio-oil under alkaline or neutral conditions has been
widely reported in literature. However, there has been limited data available in literature on comparing
HTL of biomass to bio-oil under acidic, neutral, and alkaline in terms of chemical compositions and yields
by using the same reaction conditions and reactor. Using cellulose as a feedstock we conducted the comparative studies for pH = 3, 7 and 14 at temperatures of 275320 C with reaction residence times of 0
30 min. Results showed that the chemical compositions of the bio-oils were different for acidic, neutral
and alkaline conditions. Under acidic and neutral conditions, the main composition of HTL bio-oil was 5(Hydroxymethyl)furfural (HMF). Under alkaline conditions, the main compounds became C25 carboxylic
acids. For bio-oil yields, it was observed that high temperatures and long residence times had negative
effects, regardless of the pH levels. However, the corresponding reaction mechanisms are different. Under
acidic conditions, the decrease in the bio-oil yields was mainly caused by polymerization of 5-HMF to solids. Under neutral conditions, the bio-oil yields decreased because 5-HMF was converted to both solid
and gaseous products. Under alkaline conditions, the bio-oil decomposed to gases through the formation
of short chain acids and aldehydes. Therefore, although they were all referred to as HTL bio-oil in literature, they were formed by different reaction pathways and had different properties due to their different
chemical compositions. Given these differences, different strategies are recommended in this study to
further improve HTL of biomass to bio-oil.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Hydrothermal liquefaction (HTL) is one of the promising biofuel
production technologies, which can convert inedible biomass to
bio-oil [1,2]. Because HTL uses hot-compressed water as reaction
medium, wet biomass can be directly converted without predrying processes. To date, HTL has been tested using various
biomass feedstocks including sewage [3], livestock manure [4,5],
algae [6,7], agriculture waste [8,9] and domestic garbage [10]. In
a typical HTL process, biomass is rst liqueed to produce liquid
products. Bio-oil is then extracted from the liquid products by
organic solvents. Since extraction step usually does not involve
chemical reactions, the yields and compositions of HTL bio-oil
are essentially determined by HTL reaction step. Accordingly, the
effects of reaction parameters such as temperature, pressure,
processing gas, residence time and biomass particle size on HTL
have been widely investigated to improve HTL bio-oil yields
[3,5,8,11,12].

Corresponding author. Tel.: +1 519 888 4567/38718; fax: +1 519 885 5862.
E-mail address: tanz@uwaterloo.ca (Z. Tan).
0306-2619/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2011.10.041

Most of the data in HTL literature, however, was obtained at


either alkaline or neutral conditions. Limited data were available
for acidic conditions. On the other hand, fundamental carbohydrate research showed that pH could play an important role in
HTL bio-oil formation [13,14]. The reaction pathways of HTL of biomass change with acidic, neutral and alkaline conditions [1520].
As shown in Fig. 1, under acidic conditions, the main conversion
compounds are 5-(Hydroxymethyl)furfural (5-HMF) and levulinic
acids. Under alkaline conditions, they become carboxylic acids
such as lactic and acetic acids. Under neutral conditions, both the
acidic and alkaline conversion products are formed, due to the
self-disassociation of H2O to H+ and OH at high temperatures.
Our recent study [21] showed that these reaction pathways were
not independent on each other. Under weak alkaline conditions,
the reaction pathway can change gradually from alkaline to acidic
one. The carboxylic acids produced under initial alkaline conditions could neutralize the input alkalis and the aqueous reaction
media become acidic, activating the acidic pathway. Since HTL
bio-oils are extracted from the corresponding aqueous products,
the inuence of acidic, neutral and alkaline conditions on HTL
reaction pathways and liquid products are expected to change
HTL bio-oil yields and compositions.

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S. Yin, Z. Tan / Applied Energy 92 (2012) 234239


HY: Hydrolysis
LBET: Lorby de Bruyn-Alberda van Ekenstein Transformation
RA: Retro Aldol
Cellulose

DE: Dehydration
BR: Benzilic acid rearragement

HY

HD: Hydration
5-HMF: 5-(Hydroxymethyl)furfural

Glucose
RA

Erythrose

RA

Acetic acid

Alkaline
Pathway

Glycolaldehyde

LBET

Formic acid

RA

Frutose

Glyceraldehyde

HD
DE

5-HMF

DE

Pyruvaldehyde

BR/DE
OH -

Neutral
Pathway

Lactic acid

Formic acid
Levulinic acid
1,2,4 benzentriol

Acidic Pathway

Humins

Fig. 1. General pathways of hydrothermal decomposition of cellulose.

Following up on our previous studies on the effect of alkalinity


on the change of the HTL pathway, the objective of this study is to
better understand the mechanism of HTL of biomass under acidic
and neutral conditions by comparing with HTL under alkaline conditions. Our focus is on the differences between acidic, neutral and
alkaline HTL of biomass to bio-oil using identical biomass feedstock in the same reactor. Then, based on the experimental data
and analyses, different strategies will be recommended for practical applications of acidic, neutral and alkaline HTL. To our best
knowledge, only He et al. [22] mentioned the differences in the
bio-oil yields of HTL of swine manure under all three types of conditions with pH 4, pH 7 and pH 10. However, their research was not
focused on understanding of the mechanisms behind these differences. They only compared the yields of the HTL bio-oils.

2. Materials and methods


Cellulose (Sigma Aldrich Cat No. C6413) was used as a feedstock
in this study. We did not study lignin as feedstock because only alkali lignin was commercially available, which was already the
product of biomass treatment in alkaline solutions. If alkali lignin
was used as a feedstock, the results on acidic and neutral HTL of
lignin to bio-oil would be misleading.
The solutions of pH 3, pH 7 and pH 14 were selected to represent acidic, neutral and alkaline conditions, respectively. The pH
3 acidic solutions were prepared using hydrochloric acid (HCl).
pH 3 was chosen because the rate of hydrolysis of cellulose was
greater than that at pH 47 [23]. In addition, pH 3 solution causes
less corrosion of metal reactor as compared to that with pH 12.
The pH 14 solutions were prepared using sodium hydroxide
(NaOH). Alkali metal hydroxides solutions were widely used for
alkaline HTL of biomass to bio-oil [5,8,24,25] and HTL bio-oil yields
usually increased with solution alkalinities [26]. During the preparation of the above acidic and alkaline solutions, their pH values
were monitored online by a pH meter (Oakton Ion 5) with the
accuracy of 0.01.
All tests were carried out in a 69 ml tubing reactor that was previously reported by Dolan et al. [27] It was made of stainless steel
316 with two reducing unions. One reducing union can be sealed
using a stainless steel cap and the other connected to a needle
valve. The whole reactor system was rated to 320 C and 3000 psig.

In a typical test, 1 g of cellulose with 30 ml of solutions was rst


loaded to the reactor from the end with a stainless steel cap. After
loading and sealing the reactor, air in its headspace was removed
through the needle valve using a vacuum pump and the headspace
then was lled with N2 from a gas cylinder. The reactor was heated
in a mufe furnace (StableTemp Mufe Furnaces, Cole-parmer)
with a preset temperature of 280320 C. These temperatures were
chosen because subcritical water favors bio-oil products [28]. Xu
and Lad [8] and Qian et al. [29] compared sub/supercritical liquefaction of woody biomass using water and both found that more
bio-oil was produced with subcritical water than supercritical
water. Supercritical water usually is employed for bio-gas production by steam forming [30,31].
Although the temperature inside the mufe furnace had
reached the preset value, it was not the same temperature in the
reactor. The temperature inside the reactor was monitored by a
K-type thermocouple. The moment when the temperature inside
the reactor reached the preset value (same as that in the mufe
furnace) was dened as time zero for the residence time. After
heating the reactor with the desired residence time, it was removed from the furnace and submerged into a water bath (at room
temperature) to quench further reactions.
After cooling and opening the reactor, the slurry was collected
and ltered by Whatman No.1 lter paper. The residual solids on
the lter paper were dried at 105 C in an oven until their weight
became constant. The residual solid yield was dened as the mass
ratio of the residual solids to the input cellulose. The ltrate was
measured in terms of mass and volume. Subsequently, the ltrate
was extracted using dichloromethane (CH2Cl2) at the volumetric
ratio of 1 (ltrate) to 1 (CH2Cl2) for 30 min in a 125 ml separation
funnel. The extract was then treated at 40 C in a rotary evaporator
(BUCHI RE-121 Rotavpaor with BUCHI 461 water bath) to remove
dichloromethane. The remaining liquid was bio-oil [3,5]. The biooil yield was calculated as the mass ratio of the bio-oil to the input
cellulose. The mass of produced gases was calculated based on the
mass balance. The gas yield was similarly determined as the mass
ratio of the gases to the input cellulose. The yield of aqueous products from cellulose was also calculated based on the cellulose mass
balance, which was equal to 100% minus the yields of residual solids, bio-oil and gas products.
The chemical compositions of the HTL bio-oils were analyzed
using gas chromatography (GC, Varian 430 equipped with a capillary column (CP 7717) and with a FID detector). The GC had been

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S. Yin, Z. Tan / Applied Energy 92 (2012) 234239

calibrated for typical HTL bio-oil compounds using standard chemicals such as acetone, methanol, acetic acid, propionic acid, isobutyric acid, butyric acid, iso-valeric acid, n-valeric acid, isocaproic
acid, caproic acid, heptanoic acid, dihydroxyacetone, lactic acid,
levulinic acid, and 5-HMF [32]. In a typical GC analysis, 1 ll of
bio-oil was injected into the GC, and the GC separation program
was set as follows: injection temperature of 230 C, oven temperatures from 30 C to 230 C with heating speed of 10 C/min, and
nal temperature of 230 C for 10 min.
Test under each condition in this study was repeated at least
three times until the error between the results was less than 5%.
The mean value for each condition is reported as follows.

3. Results and discussion


3.1. Chemical compositions of bio-oils
As shown in Table 1, the main compounds of the bio-oils were
greatly inuenced by the acidic, neutral and alkaline conditions. 5HMF was the main compound of the HTL bio-oil produced under
acidic conditions. Under neutral conditions, 5-HMF remained a
major compound, but the yields of carboxylic acids became apparent. Under alkaline conditions, the compounds of the bio-oil were
primarily C25 carboxylic acids (acetic, lactic, propionic, buyric and
caproic acids) and dihydroxyacetone.
The GC results above were consistent with the main reaction
pathways illustrated in Fig. 1. 5-HMF was the main compound of
HTL with cellulose as a feedstock under acidic conditions. And
the carboxylic acids were the main products of HTL of cellulose under alkaline conditions. These similarities between HTL bio-oil and
HTL liquid products conrmed that acidic, neutral and alkaline
conditions inuenced the compositions of not only liquid products
but also HTL bio-oils.
Furthermore, the differences between the compositions of the
HTL bio-oils indicated that sometimes it is misleading to compare
the yields of HTL bio-oils from different research groups without
considering the chemical compositions. Comparison of yields is
supposed to be based on the assumption of the same chemical
compositions. Data in literature with higher yields were usually
obtained under alkaline. However, according to our chemical composition analyses above, the HTL bio-oils from acidic/neutral and
alkaline conditions are quite different in terms of chemical compositions. Therefore, attention ought to be paid to HTL bio-oil compositions, particularly when research focuses on the optimization of
conversion parameters to improve HTL bio-oil yields.

3.2. Bio-oil yields


The effects of conversion temperature on the HTL bio-oil yields
at acidic, neutral and alkaline conditions are shown in Fig. 2. It is
noted that regardless of pH levels, the HTL bio-oil yields all rst increased and then decreased with temperatures in the range of
275320 C. And, the maximum bio-oil yields under acidic, neutral
and alkaline conditions were all obtained at 300 C.
The effects of residence time on the yields of HTL bio-oils are
presented in Fig. 3. It can be seen that the trends of the bio-oil
yields against residence time were similar. The bio-oil yields under
acidic, neutral and alkaline conditions all decreased with increasing residence time, ranging from 0 to 30 min. With a residence
time of 0 min, the bio-oil yields under acidic, neutral and alkaline
conditions were 34.0 wt.%, 28.2 wt.% and 5.8 wt.%, respectively.
But, as the residence time was extended to 30 min, the corresponding bio-oil yields decreased to 7.9 wt.%, 3.6 wt.% and 3.0 wt.%,
respectively.
Despite the similar trends of HTL bio-oil yields against the conversion temperature and the residence time, the mechanisms behind were quite different. Under acidic HTL conditions, the
decrease in bio-oil yields at high temperature and long residence
time were mainly attributed to the formation of residual solids
as evidenced in Fig. 4A. At pH = 3, the yields of HTL bio-oil and
residual solids at 300 C were 34.0 wt.% and 17.4 wt.%, respectively. At 320 C, however, the yield of residual solids increased
to about 50 wt.% and the corresponding bio-oil yield decreased to
only 6.1 wt.%. Similarly, when the bio-oil yield decreased from
34.0 wt.% (with a residence time of 0 min) to 7.9 wt.% (with a residence time of 30 min) at 300 C, the corresponding yield of the
residual solid increased from 17.4 wt.% to 31.7 wt.% (Fig. 4B).
Under acidic conditions, the main component of acidic HTL biooil (5-HMF) is an active chemical and tends to form hydrothermal
char/solid by polymerization. Titirici et al. [33] compared the solid
hydrothermal carbon materials from starch, sucrose, maltose and
glucose by using 13C solid-state CP-MAS NMR and showed that
5-HMF was the core structure of hydrothermal carbon. Baccile
et al. [34] further applied a combination of advanced solid-state
13
C NMR techniques to characterize hydrothermal carbon from
glucose and found that 65% of hydrothermal carbon existed in
the form of HMF ring structure. Therefore, it mainly was the formation of residual solids from 5-HMF that caused the decrease in the
yields of bio-oil under acidic conditions.
Under neutral conditions, the decrease in HTL bio-oil yields at
high temperatures and long residence times was a result of increased residual solids as well as gaseous products. As shown in

Table 1
Main components of acidic, neutral and alkaline HTL bio-oil.
Concentrations (mM)
No

Retention time (min)

Compounds

pH = 3

pH = 7

pH = 14

1
2
3
4
5
6
7
8
9
10
11
12
Total peak area (%)

5.50
6.39
6.68
7.35
7.78
9.18
10.68
12.10
12.10
12.85
14.22
15.70

Acetic acid
Propionic acid
Isobutyric acid
Butyric acid
Iso-valeric acid
Isocaproic acid
n-Caroic acid
Heptanoic acid
Dihydroxyacetone
Lactic acid
Levulinic acid
HMF

9.34

0.87

3.50
38.38
93.9

0.67
0.21

0.93
0.18

0.67

17.82
88.30

0.31
0.04
0.20
0.43
0.17
0.04
0.06
0.02
0.93
0.03

74.76

(HTL conditions: 1 g cellulose, 30 ml solutions, 300 C, and 0 min reaction residence time).

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S. Yin, Z. Tan / Applied Energy 92 (2012) 234239

100%

50%
Acidic HTL: pH=3

30%

20%

10%

0%
270

280

290

300

310

320

330

Temperatures ( C)
Fig. 2. Effect of conversion temperature on bio-oil yields under acidic, neutral and
alkaline conditions. (Conditions: 1 g cellulose, 30 ml solutions, 300 C, and 0 min
reaction residence time).

40%

80%

Residual solids

Aqueous products

Bio-oil

Gas

(A)

HMF

40

60%

30

40%

20

20%

10

0%

0
o

Temperatures ( C)
100%

Acidic HTL: pH=3

50
pH=3

80%

Residual solids
Bio-oil
HMF

Aqueous products
Gas

40

(B)

60%

30

40%

20

20%

10

0%

The concentrations of HMF in liquid phase (mM)

Bio-oil yields (wt. %)

Alkaline HTL: pH=14

Product yields of HTP of cellulose (wt.% based on input cellulose)

Neutral HTL; pH=7

40%

50
pH=3

Bio-oil yields (wt. %)

Neutral HTL: pH=7

30%

Alkaline HTL: pH=14

Residence time (min)


20%

Fig. 4. Product distributions of acidic (pH = 3) hydrothermal liquefaction of


cellulose (Conditions: (A): 1 g cellulose, 30 ml HCl solution, 0 min residence time
and the temperatures of 275 to 320 C; (B): 1 g cellulose, 30 ml HCl solution, the
temperature of 300 C and the residence time of 0 to 30 min.).

10%

0%
0

10

15

20

25

30

35

100%

Reaction residence time (min)

Residual solids
Bio-oil
HMF

Aqueous products
Gas

(A)

60%
40%
20%
0%

Temperatures ( o C)
100%

50
pH=7

80%

Residual solids

Aqueous products

Bio-oil

Gas

HMF

(B)

40

60%

30

40%

20

20%

10

0%

The concentrations of HMF in liquid phase (mM)

Fig. 5A, when bio-oil yield decreased from 28.4 wt.% at 300 C to
3.0 wt.% at 320 C, the yields of residual solids and gas products increased to 64.1 wt.% and to 6.0 wt.%, respectively. Similarly, as the
bio-oil yields decreased with the residence time of from 0 min to
30 min at 300 C (Fig. 5B), the corresponding yields of residual solids and gases increased to 30.9 wt.% and to 3.0 wt.%, respectively.
The bio-oil yields were likely to be reduced by the polymerization of HMF to residual solids because 5-HMF was one main compound of the bio-oil produced under neutral conditions [35]. Fig. 5
does show that the yields of residual solids increased as both yields
of HMF and bio-oil decreased with the increase of temperature and
the reaction residence time. High temperature and long residence
time can also promote the decomposition of HMF to gases, resulting in the decrease in the yields of HTL bio-oil under neutral conditions. Chuntanapum and Matsumura [36] studied the
decomposition of 5-HMF in pure water and found that the corresponding gas yield increased with temperature (300, 350, 400
and 450 C) as well as residence time (07 min). Another means
for the production of gases may originate from the decomposition
of short chain acid and aldehyde components formed under neutral conditions. Kruse and Gawlik studied hydrothermal conversion
of biomass at the temperatures of 350410 C with the pressures of
3050 MPa, and they found that low molecular weight acids and
aldehydes from cellulose can be easily converted to gases [37].

80%

Yields of production products (wt.% based on input cellulose)

Fig. 3. Effect of residence time on bio-oil yields under acidic, neutral and alkaline
conditions (Conditions: 1 g of cellulose, 30 ml solutions and 300 C).

pH=7

Residence time (min)


Fig. 5. Major compounds of hydrothermal liquefaction of cellulose under neutral
conditions (pH = 7) (Conditions: (A): 1 g cellulose, 30 ml water, 0 min residence
time and the temperatures of 275320 C; (B): 1 g cellulose, 30 ml water, the
temperature of 300 C and the residence time of 0 to 30 min.).

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S. Yin, Z. Tan / Applied Energy 92 (2012) 234239

Under alkaline conditions, it was mainly the formation of gases


from the decomposition of HTL compounds that led to the decrease
in bio-oil yields at high temperatures (>300 C). As shown in
Fig. 6A, when the yields of the HTL bio-oil under alkaline conditions decreased from 5.8 wt.% at 300 C to 0% at 320 C, the corresponding yields of gaseous products increased from 0 to 10.1 wt.%.
Meanwhile, the yields of the aqueous products and the residual
solids remained nearly constant. This indicates that HTL bio-oils
under alkaline conditions at high temperatures were unstable
and could be easily decomposed to gases. This observation was
consistent with the literature on subcritical hydrothermal gasication (HTG) of biomass. For example, Fang et al. [38] studied hydrothermal gasication (HTG) of cellulose with and without alkali and
found that the yields of gases under alkaline conditions were
approximately 50% higher than those under neutral conditions
on a carbon basis and that the gas yields in the presence of alkalis
apparently increased with the temperatures (220340 C). Onwudili and Williams also investigated the role of alkali in HTG of different biomass and found that the intermediates (bio-oil
compounds) produced under alkaline conditions were more easily
gasied to gases than those produced under neutral conditions
[39].
The yields of HTL bio-oil under alkaline conditions also decreased with the increase of residence time. As shown Fig. 6B, as
the bio-oil yields decreased from 5.8 wt.% with 0 min residence
time to 3.1 wt.% with a residence time of 30 min at 300 C, the corresponding yields of gases increased from 5.0 wt.% to 18.2 wt.%. In
our previous study on HTL of cattle manure under alkaline conditions, a similar correlation between the yields of bio-oil and gas
products was reported [5]. This is because acids and aldehydes
were the key intermediates for gas products from HTG [37,39]
They were also the main components of HTL bio-oil under alkaline
conditions. It was likely that a long residence time allowed more of

100%
pH=14

Aqueous products
Gas

(A)

Acids

60%
40%
20%
0%
Temperatures (oC)
100%
pH=14

80%

Residual solids
Bio-oil
Acids

Aqueous products
Gas

60%

(B)

The concentrations of acids in liquid phase (mmole)

Yields of production products (wt.% based on input cellulose)

80%

Residual solids
Bio-oil

40%
20%
0%

Residence time (min)


Fig. 6. Products of neutral (pH = 14) hydrothermal liquefaction of cellulose
(Conditions: (A): 1 g cellulose, 30 ml NaOH solution, 0 min residence time and
the temperatures of 275320 C; (B): 1 g cellulose, 30 ml NaOH solution, the
temperature.

these intermediates to be decomposed to gases. Our experiment


data (Fig. 6B) showed that the concentrations of carboxylic acids
in the liquid products decreased as the bio-oil yields under alkaline
conditions decreased with the long residence time.
Note that the highest HTL bio-oil yields were always obtained under acidic conditions, followed by neutral and alkaline conditions, as
shown in Figs. 3 and 4. The main reason behind this difference was
related to the extraction efciency of major compounds of the HTL
bio-oils. Carboxylic acids were the main compounds in the HTL
bio-oils under of alkaline conditions. These acids are polar chemicals
and are less likely to be extracted by non-polar solvents. On the other
hand, the primary component of acidic and neutral HTL bio-oils,
5-HMF, is a less polar chemical and can be easily extracted by
non-polar solvents such as dichloromethane, diethyl ether and
supercritical CO2 [40]. As supported by our experiment data, the
mass ratios of the bio-oil to the total liquid products under acidic
and neutral conditions were between 0.34 and 0.69, while the ratios
under alkaline conditions were only 0.020.08.
4. Conclusions
In this paper we compared hydrothermal liquefaction (HTL) of
cellulose to bio-oil under acidic, neutral and alkaline conditions
using identical feedstock in the same reactor. All experimental
data obtained in this study led to one conclusion that HTL of
biomass to bio-oil under acidic, neutral and alkaline conditions
are different in terms of bio-oil chemical composition and yield.
Based on the results above, the following specic conclusions
can be made.
(1) The! compositions of HTL bio-oil depend on the acidic,
neutral and alkaline conditions. The bio-oil produced from
cellulose under acidic and neutral conditions, was mainly
composed of 5-HMF. However, the main compounds of
the bio-oil produced under alkaline conditions were C25
carboxylic acids. The difference in chemical composition
indicated that it is necessary to clarify the pH conditions
for HTL bio-oil formation. Although they were all referred
to as HTL bio-oil in literature, they actually had different
properties due to their different chemical compositions.
(2) Different reaction mechanisms were involved for HTL under
acidic, neutral and alkaline conditions, although HTL bio-oil
yields showed similar trends against conversion temperatures and reaction residence time. The decrease in the yield
of HTL bio-oil under acidic conditions was mainly caused by
the polymerization of HMF to solids. Under neutral conditions, bio-oil yields decreased because of the conversion of
5-HMF to both solids and gases. Under alkaline conditions,
HTL bio-oil was mainly decomposed to gases through short
chain acids and aldehydes in the bio-oil.
5. Implications
(1) Since HTL of biomass to bio-oil under acidic, neutral and
alkaline conditions followed different reaction pathways,
different approaches need to be taken in order to improve
HTL bio-oil yields. For HTL processes under acidic and neutral conditions, HTL bio-oil yields can be increased by preventing polymerization of HMF. For HTL process under
alkaline conditions, this can be done by inhibiting the
decomposition of bio-oil to gases. One practical method that
may help in this regard is consideration of reactor material.
Common reactor materials, such as nickel, are known to be
effective catalysts for hydrothermal gasication [38]. Glass
reactors or reactors with different coatings may decrease
the decomposition of bio-oil to gases.

S. Yin, Z. Tan / Applied Energy 92 (2012) 234239

(2) Because short residence time favors the yields of HTL bio-oil,
equipment size can be reduced for a given throughput. However, given that hydrothermal solids are formed during the
acidic and neutral HTL processes, more research would be
needed to prevent the plugging of reactors. In addition, for
HTL processes under alkaline conditions, corrosion resistant
materials are required for reactor due to the relatively high
concentrations of carboxylic acids in HTL bio-oil.

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