Fuel 109 (2013) 225233

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Fuel
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Catalytic upgrading of crude algal oil using platinum/gamma alumina

in supercritical water
Peigao Duan , Xiujun Bai, Yuping Xu, Aiyun Zhang, Feng Wang, Lei Zhang, Juan Miao
College of Physics and Chemistry, Department of Applied Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454003, PR China

h i g h l i g h t s

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

" Pt/c-Al2O3 catalyzed the upgrading

"

"
"

"

of crude algal oil to produce

hydrocarbons in SCW.
Lower water density and formic acid
loading produced higher quality
treated oil.
SCW + HCOOH effectively controlled
the coke formation.
Reduction in surface area and
micropore volume of Pt/c-Al2O3 did
not inuence its activity.
Hydrogenation, hydration, and
oxygenation reactions occurred
simultaneously.

a r t i c l e

i n f o

Article history:
Received 31 October 2012
Received in revised form 16 December 2012
Accepted 19 December 2012
Available online 7 January 2013
Keywords:
Upgrading
Crude algal oil
Treated oil
Pt/c-Al2O3
Supercritical water

a b s t r a c t
We report herein on the catalytic upgrading of crude oil, produced from the hydrothermal liquefaction of
Chlorella pyrenoidosa over platinum on gamma alumina (Pt/c-Al2O3) in supercritical water (SCW) at
400 C for 1 h. We determined the inuence of catalyst loading (varied from 0 to 40 wt.%), water density
(varied from 0 to 0.1 g/cm3), and formic acid (HCOOH) loading (varied from 2 to 37 mmol) on the product
yields and properties of the treated oil. The product yields and properties of the treated oil were largely
insensitive to the catalyst loading and sensitive to water density and HCOOH loading. Increasing the catalyst loading or decreasing the water density and formic acid loading produced a lower yield but higher
quality treated oil. Moreover, including the Pt/c-Al2O3 in the reactor led to a product oil that was a freely
owing liquid, as opposed to being the viscous, sticky, and tar-like crude oil material. Compared to
SCW + H2, the presence of SCW + HCOOH effectively controls the coke formation. The catalyst experienced a reduction in surface area and micropore volume when used for hydrothermal upgrading. These
changes did not inuence the catalyst activity, however. Unreacted H2 was the main gaseous product,
together with lower yields of CO2 and C1AC5 hydrocarbon.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Currently, microalgae are among the biomass feedstocks that
are identied to be one of the best energy carriers for biofuel production because of their high photosynthetic efciency, fast
growth rate, and high area-specic yield relative to terrestrial bio Corresponding author. Address: College of Physics and Chemistry, Department
of Applied Chemistry, No. 2001, Century Avenue, Jiaozuo, Henan 454003, PR China.
Tel.: +86 0391 3986820; fax: +86 0391 3987811.
E-mail address: pgduan@hpu.edu.cn (P. Duan).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.12.074

mass [14]. Hydrothermal liquefaction is a promising method for

converting wet algal biomass into liquid biofuels because it obviates the need (capital, energy and time) for feedstock dewatering
and drying as did for other conversion methods such as gasication
and pyrolysis. Furthermore, the product oil from the hydrothermal
liquefaction of microalgae has lower oxygen content and higherenergy density than the oils produced from fast pyrolysis [46].
However, it still contains signicant quantities of oxygen, nitrogen
and sulfur. Therefore, additional upgrading including deoxygenation, denitrogenation, and desulfurization is needed to produce
a fungible transportation fuel. Since the liqueed oil will be formed

226

P. Duan et al. / Fuel 109 (2013) 225233

in an aqueous environment, it may be advantageous from a process

engineering perspective to do the oil upgrading in that same environment (water). The critical temperature of water (374 C) is
within the range of temperatures encountered in many oil renery
operations. Furthermore, supercritical water (SCW) possesses good
heat transfer and solubility of potential coke precursors, and gaslike transport properties, which militates against transport processes limiting catalytic reaction rates [7]. Therefore, bio-oil
upgrading in SCW may be a path toward oxygen, nitrogen and sulfur removal from the crude algal oil produced from the hydrothermal liquefaction.
Previous study [7] suggested that SCW reaction medium alone
(no catalyst) seemingly provided complete desulfurization of the
crude algal oil. Subsequent optimization study [8] indicated that
the lowest temperature examined (430 C), regardless of other variables, appeared to be the best for producing an upgraded oil with
higher-energy density. However, the properties of this upgraded
oil are extremely close to that of obtained at 400 C [7]. Therefore,
400 C might be the most suitable temperature for the upgrading
of crude algal oil in SCW. Interestingly, in situ generation of hydrogenating species, by the addition of formic acid (HCOOH) rather than
H2, was even more powerful than added H2 itself. Noble metal catalysts were commonly used in the crude algal oil upgrading to catalyze the deoxygenation, denitrogenation and desulfurization
reactions. Among the noble metals, platinum (Pt) is one of the most
active catalysts, which usually supports either on activated carbon
or gamma alumina (c-Al2O3) to maximize the surface area. However,
regeneration of the deactivated, carbon-supported catalyst was difcult because the catalyst alone cannot be separated from the solid
residue, and thus limits its further recycling use. In contrast, c-Al2O3
supported catalyst can be easily regenerated by calcination after
deactivation. Furthermore, c-Al2O3 having acid sites can be used
both as a potential catalyst and catalyst support for acid catalyzed
reactions. Therefore, one would expect that the combination of Pt,
for catalyzing hydrogenation reaction, and c-Al2O3, for promoting
acid-catalyzed reaction looked promising for crude algal oil upgrading, and this catalyst/support combination had not been explored
previously. It is not yet known whether Pt/c-Al2O3 will also be effective and maintain its activity if used for crude algal oil upgrading
(hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO)) in
a hydrothermal medium. Ni is known a typical catalyst for promoting the hydrogenation reactions and is also cheaper than Pt catalyst.
However, the nickel metal will react with the acidic components
such as fatty acid in the crude algal oil and is not active as Pt under
hydrothermal conditions [9]. Thus, Pt is selected rather than Ni as
the upgrading catalyst in the present study.
The purpose of this study is to evaluate the activity and reusability of Pt/c-Al2O3 upon the upgrading (HDN and HDO) of crude
algal oil in SCW. We selected crude algal oil produced from the
hydrothermal liquefaction of Chlorella pyrenoidosa (Chlorella p.) as
the model oil. We determined the effect of catalyst loading (0
40 wt.%), water density (0.00.10 g/cm3), and HCOOH loading (2
37 mmol) on the product yields, bulk properties (e.g., elemental
composition, and higher heating value (HHV)) and physico-chemical characteristics (e.g., molecular constituents, functional group
allocation, and carbon speciation) of the treated oil. Activity maintenance and characterization of catalyst were also examined. All
upgrading experiments were conducted at 400 C for 1 h.

2. Experimental section
2.1. Materials
Chlorella p. powder with cracked cell wall was purchased from
Shandong Binzhou Tianjian Biotechnology Co., Ltd. (North China).

Table 1 lists its proximate and ultimate analysis along with other
properties. Quantication methods of evaluating the moisture,
ash, crude protein, and crude lipid in the alga powder were described as previously [10]. The Pt/c-Al2O3 (5 wt.% Pt, surface
area = 99 m2/g, micropore volume = 0.241cm3/g, average particle
size = 25 lm) was purchased from SigmaAldrich and used as received. Freshly deionized water, prepared in the lab, was used
throughout the experiments. All other chemicals were purchased
from SigmaAldrich and used as received.
Stainless-steel reactors assembled from a nominal 1-in. Swagelok port connector and caps were used to produce the crude algal
oil. They were equipped with a temperature and magnetic mixer
controller. The batch reactor provides an internal volume of
25 mL. We used a custom-made high-pressure and corrosion-resistant mini autoclave to carry out the upgrading experiments, which
allowed for the recovery and analysis of both the liquid and gasphase products in a single run. It is rated up to a working pressure
of 40 MPa and working temperature of 450 C. The total internal
volume of this reactor is 17.2 mL. Prior to their use in experiments,
the reactors were loaded with water and seasoned at 400 C for 4 h
to remove any residual organic material from the reactors and to
expose fresh metal walls to supercritical water. After this condition, potential catalytic wall effects might be eliminated or reduced; however, they might also play a role in producing the
observed result.
2.2. Procedure
2.2.1. Algae liquefaction
We generated about 39 g of crude algal oil, which resulted in a
yield of 41 wt.% on the dry basis of alga by liquefying 96 g of alga
powder. Two batch reactors were used to perform the liquefaction
experiments. 6.0 g of dry alga powder and 13.7 mL of freshly
deionized water were loaded into each reactor. We initiated the
reaction by placing the reactors in a preheated molten salts (consists of potassium nitrate and sodium nitrate at a mass ratio of
5:4) tank at a temperature of 350 C. The temperature was controlled by an Omega temperature controller with precision of
2 C. Heating up time was about 5 min, and the total batch holding time was 60 min. The two reactors were removed from the
molten salts tank and immersed in a cold-water bath for about
10 min to quench the reaction.
After the reactors had cooled, they were depressurized and
opened. We added dichloromethane to extract the oil fraction
and separate it from the reaction mixture. The extract was next ltered, and then the dichloromethane in the extract was vaporized
by using a rotary evaporator. The remaining material was the crude
algal oil. Liquefaction experiments were repeated for eight runs
Table 1
Proximate and ultimate analysis of Chlorella p.
Property

Value

Moisture content (wt.%)

Ash content (wt.%)
Heating value estimate

11.0%
9.1%
22.7 MJ/kg

Chemical composition (wt.%, per supplier)

Crude protein
Carbohydrates
Crude Lipids

30%
36%
34%

Elemental composition (wt.%)

C
H
Oa
N
S

46.8%
6.9%
17.2%
8.4%
0.6%

a
Calculated by difference as 100  (ash + water + C + H +
N + S).

P. Duan et al. / Fuel 109 (2013) 225233

with those two batch reactors under the identical conditions. The
crude algal oil yield was calculated as the total mass of crude oil
divided by the total mass of alga powder loaded into the reactor.
2.2.2. Upgrading experiments
Upgrading experiments were carried out in a mini stainlesssteel autoclave reactor. In a typical run, 1.0 g of crude algal oil, desired amount of catalyst, 0.43 mL of freshly deionized water and
desired amount of HCOOH (88 wt.%, when needed) were loaded
into the reactor in sequence. The air inside the reactor was displaced by purging the reactor headspace with hydrogen for about
15 min. The reactor was next further charged with hydrogen to
6 MPa (room temperature) to provide a reducing environment.
This hydrogen loading is a large excess over the hydrogen demand
for complete heteroatoms removal from the crude algal oil. The
hydrogen was not further charged for those reactions performed
with HCOOH. We conducted two additional experiments with Pt/
c-Al2O3 that was either in pre-reduced or pre-sulde form to estimate their effect on the product yields and properties of the treated oils.
Bio-oil upgrading reactions were carried out by placing the
reactor vertically on the top center of a preheated molten salts
tank. The rotation speed was set at 120 r/min. After about 5 min,
the reactor reached 400 C and was isothermally controlled to
within 5 C by an Omega temperature controller (5 C), with a
thermocouple inserted into a thermal well in the reactor. When
1 h reaction duration had been reached, the reactor was removed
from the molten salts tank and immersed in an icewater bath
for about 15 min to stop the reaction. The reactor was weighted before and after ventilating the gas to determine the gas formation.
For those reactions conducted at different water density, the gas
was collected by using a metalized-lm gas sampling bag for analysis. We opened the reactor and added 10 mL of dichloromethane
to recover the treated oil fraction. The reactor was washed twice
more with additional 10 mL aliquots of dichloromethane. All the
dichloromethane extracts were ltered before they were transferred to a separatory funnel. After ltration, the lter paper together with the solid residue were dried in an oven at 110 C for
12 h, and then weighted. Non-catalyst solid residue was dened
as coke whose amount was evaluated by subtracting the weight
of catalyst from the solid residue. The dichloromethane in the separated ltrate was evaporated. The remaining material was the
treated oil, and its amount was determined gravimetrically. The
yield of each product was calculated by using the following
equations:


weight of treated oil
weight of crude oil loaded

Yield of treated oil wt:%

 100%

Yield of coke wt:%

Yield of gas wt:%


weight of coke
 100%
weight of crude oil loaded



weight of gas  initial weight of H2
weight of crude oil loaded
 100%

At least duplicate independent runs were conducted under

identical conditions to determine the uncertainties in the experimental results. Results reported herein represent the mean values
for the two independent trials.
2.2.3. Analytical chemistry
Shanghai Precision & Scientic Technology model GC-102AT gas
chromatograph equipped with a thermal conductivity detector
(TCD) was used to analyze the gas products as reported previously

227

[10]. A PerkinElmerClarus 600 GC equipped with a mass-spectrometric (MS) detector was used to analyze the bio-oils. An Agilent J&W HP-5MS non-polar capillary column (30 m length,
0.25 mm I.D., 0.10 lm lm thickness) separated the constituents.
A volume of 2 ll was injected for each sample, and the inlet temperature and split ratio were 300 C and 3:1, respectively. Two
minutes solvent delay was set to protect the lament. The column
was initially held at 40 C for 4 min. The temperature was ramped
to 300 C at 4 C/min and held isothermally for 4 min, giving a total
runtime of about 73 min. Helium owing at 3 mL/min served as
the carrier gas. A Wiley mass spectral library was used for compound identication.
Elemental analyses, fourier transform infrared spectrometry
(FT-IR) and 13C nuclear magnetic resonance (NMR) were performed
as described previously [10]. The Dulong formula was used to estimate the HHV of the bio-oils based on their elemental
compositions.
The total BET surface area, pore volume, and pore size distribution of the Pt/c-Al2O3 catalyst were measured by the Micromeritics
ASAP2020 accelerated surface area and porosimetry analyzer. The
catalyst sample was placed inside a tube and degassed at a vacuum
of 500 mmHg and temperature of 350 C for 240 min. After that,
the sample was transferred to the analysis section to analyze the
BET surface area using N2. The surface area was calculated according to the BrunauerEmmettTeller (BET) equation. The pore size
distribution was obtained from the HorvathKawazoe Differential
Pore Volume Plot.

3. Results and discussion

3.1. Effect of operating conditions on the product yields
Fig. 1a shows the effect of Pt/c-Al2O3 loading on the product
(treated oil, coke and gas) yields from the catalytic upgrading of
crude algal oil in SCW at 400 C for 1 h. The initial H2 pressure
and water density are 6 MPa and 0.025 g/cm3, respectively. Mass
balance closure varies between 93% and 99% depending on the catalyst loading. Good mass balance is always achieved at higher catalyst loading. The most likely reason for the comparatively lower
mass balance at lower catalyst loading, especially in the absence
of catalyst was the loss of treated oil due to its tendency to stick
to the reactor wall and tubing.
More specically, increasing the catalyst loading on crude algal
oil decreases the treated oil yield and increases the coke and gas
yield, respectively. At the highest catalyst loading of 40 wt.%, the
treated oil yield is only 58.6 wt.%, which is lowered by about 16%
comparing with that of without catalyst. Coke yield decreases
when going from 0 to 5 wt.% of catalyst loading. The lowest coke
yield (16.6 wt.%) is obtained at a catalyst loading of 5 wt.%. Further
increase in catalyst loading moderately increases the coke yield.
Therefore, from a coke control perspective, a 5 wt.% catalyst loading on crude algal oil seems to be the preferred loading. Similar
coke yield as a function of catalyst loading was reported by Panariti
et al. [11], in which a solvent free upgrading strategy was used to
upgrade a petroleum residue. Gas yield increases with increasing
the catalyst loading, and then it hits a peak at 15 wt.%. Further increase in catalyst loading leads to almost constant gas yield. One
possible reason for this result might be that the gas yield at a catalyst loading of 15 wt.% already approached the upper bound of
what is possible given.
We did no pre-reduction of the Pt/c-Al2O3 because it would be
exposed to the oxidizing hydrothermal environment when in use.
To nd out whether the pre-reduction is responsible for the yields
difference; we carried out an experiment with pre-reduced Pt/cAl2O3. Experiment with pre-sulde Pt/c-Al2O3 was also conducted

228

P. Duan et al. / Fuel 109 (2013) 225233

(a)

Gas

Coke

Coke

Treated oil

90

100
90

80

80

70

Yield (wt.%)

Yield (wt.%)

Gas

(b) 100

Treated oil

70
60
50
40

60
50
40
30

30

20

20
10

10

0
0

0.013

0.025

0.05

0.075

0.1

Water density (g/cm3)

Catalyst loading (wt.%)

(c) 180

Gas

Coke

Treated oil

160

Yield (wt.%)

140
120
100
80
60
40
20
0
2.3

4.7

9.3

18.7

28

37.3

Formic acid loading (mmol)

Fig. 1. (a) Effect of catalyst loading on product yields (400 C, 1 h, qwater = 0.025 g/cm3, 6 MPa H2); (b) effect of water density on product yields (400 C, 1 h, 5 wt.% Pt/c-Al2O3,
6 MPa H2); (c) effect of formic acid loading on product yields (400 C, 1 h, 5 wt.% Pt/c-Al2O3).

to determine whether the sulde form catalyst is inuential or not

on the product yields. Fig. 1a shows the experimental results
(400 C, 1 h, 5 wt.% catalyst and 6 MPa H2). The gas yields with
pre-reduced and pre-sulde Pt/c-Al2O3 decrease respectively to
13 wt.% and 11 wt.%, compared to 16 wt.% for the Pt/c-Al2O3 as received. Slight decrease in treated oil yield is also observed. However, the coke yields for these two reactions are close, which is
slightly higher than that of using Pt/c-Al2O3. It seems that the
pre-reduced or pre-sulde form of Pt/c-Al2O3 would suppress the
gas formation and favor the coke formation, although the reasons
are not clear.
Previous studies [1215] suggested that change of water density affected the reaction route, rate, and equilibrium, as well as
the yield and quality of the treated oil in the upgrading of heavy
oil. Thus, water density was varied while keeping other process
variables xed to explore its effect on the product yields from
the crude algal oil upgrading. Fig. 1b shows the experimental results (400 C, 1 h, 5 wt.% Pt/c-Al2O3 and 6 MPa H2), which indicates
signicant effect of water density on the product yields. In the absence of water, both the coke and gas yields are the highest
whereas the treated oil yield is the lowest observed in any of our
experiments. The coke yield decreases steadily as the water density increases from 0 to 0.1 g/cm3, suggesting coke formation is
very well controlled in SCW, especially at higher water density.
One possible explanation for the coke control in SCW might attribute to the good solubility of potential coke precursors of SCW
so that to extract and transport them from the catalyst pores,
and thus retarded the coke formation. Similar results were observed in previous studies on the upgrading of crude algal oil
[7,8,16], vacuum residue and heavy oil [13,14] in SCW. The gas

yield decreases with increasing water density, which is consistent

with the results observed in the partial oxidation of bitumen in
SCW [15]. The treated oil yield increases from 53.9 wt.% in the absence of water to 64.8 wt.% at a water density of 0.025 g/cm3 and
then levels off. The reason for higher treated oil yield at higher
water density is related to the reaction of water with the crude algal oil that is unavailable in its absence in the upgrading. The overall mass balance can also be evaluated from Fig. 1b. Increasing
water density leads to reduced mass balance. Only 87 wt.% mass
balance is obtained at the highest water density of 0.1 g/cm3, suggesting some water soluble formed in the upgrading remained in
the aqueous phase.
Effect of HCOOH loading on the product yields from crude algal
oil upgrading was studied by varying the loading from 2.3 to
37.3 mmol. Fig. 1c shows the experimental results (400 C, 1 h,
5 wt.% Pt/c-Al2O3), which indicates signicant effect of HCOOH
on the product yields. The highest HCOOH loading (37.3 mmol)
contains the same amount of hydrogen as charged 6 MPa external
gas hydrogen. Clearly, HCOOH loading strongly affects the product
yields and mass balance. Compared to SCW + H2 or SCW, the presence of SCW + HCOOH effectively controls the coke formation. The
coke yield decreases from 19.9 to 11 wt.% as the formic acid loading increases from 2.3 to 37.3 mmol. Possibly, the active hydrogen
formed from the in situ decomposition of HCOOH is responsible for
the suppression of coke formation. Increasing the HCOOH loading
favors the treated oil yield which increases from 43.7 to
79.8 wt.% with increasing HCOOH loading from 2.3 to 37.3 mmol,
suggesting HCOOH was reacted and incorporated into the treated
oil. Increasing the HCOOH loading also increases the gas yield because of the decomposition of HCOOH. The major gaseous products

229

P. Duan et al. / Fuel 109 (2013) 225233

are always CO2 and H2 because decarboxylation is the preferred

reaction path for HCOOH decomposition under hydrothermal conditions [17]. The gas phase fraction makes up around 76 wt.% of the
total mass at the highest HCOOH loading of 37.3 mmol. The mass
balance also increases because of the incorporation of HCOOH into
the reaction products. The mass balance is even higher than the
upper bound of the reaction at HCOOH loading beyond 9.3 mmol.
3.2. Effect of operating conditions on treated oil composition
Table 2 compares the elemental compositions and HHVs of the
Chlorella p. powder, crude algal oil and treated oils produced under
different reaction conditions. In addition, the molar H/C, O/C and
N/C ratios are also shown. As shown in Table 2, the carbon and
hydrogen content of the crude algal oil is always much higher than
that of the Chlorella p. powder, whereas the oxygen content is reduced to 7.8 wt. % (vs. 17.2 wt.% in the Chlorella p.). Of course,
the increased C and H levels and reduced O content leads to the
crude algal oil having a much higher-energy density than the
raw material. Nevertheless, this crude oil still contains heteroatoms (O, N, S) which are much higher than that of typical hydrocarbon fuels, and thus further chemical or physical upgrading is
needed if the material is to be used as a transportation fuel or feedstock for the existing renery equipment.
In Table 2, with added H2, hydrothermal upgrading alone (no
added catalyst) produces treated oil with lower carbon, hydrogen
and nitrogen content and higher oxygen content compared to the
crude algal oil. The treated oil also has a lower-energy density than
the crude algal oil. With added H2 and Pt/c-Al2O3, regardless of the
catalyst loading, the carbon content in treated oil is always higher
than that of crude algal oil. The hydrogen content in the treated oil
almost keeps constant with increasing catalyst loading. Although
the hydrogen was consumed in the upgrading, it was removed in
the form of NH3 and/or H2O and thus resulted in nearly constant

hydrogen in treated oil over the catalyst loading range. Reduced

N content in treated oil is observed with increasing the catalyst
loading. The oxygen content shows no clear trend with catalyst
loading, but the oxygen content of the treated oil is smaller than
that of the crude algal oil. No sulfur was detected in the treated
oil because supercritical water upgrading alone would provide
complete desulfurization of the crude algal oil [7]. The H/C ratio
of treated oil is smaller than of the crude algal oil and almost keeps
constant with increasing catalyst loading. Increasing the catalyst
loading increases the O/C ratio and decreases the N/C ratio of treated oil. These differences are small, however. The HHV of the treated oil is insensitive to the catalyst loading. The elemental
composition and HHVs of oils treated with pre-reduced or pre-sulde catalyst are almost the same as Pt/c-Al2O3 used, suggesting
pretreatment of the catalyst is unnecessary for crude algal oil
upgrading under hydrothermal conditions. We, therefore, conclude
that Pt/c-Al2O3 played multiple roles such as hydrogenation (hydrodenitrogenation, hydrodeoxygenation or hydrodesulfurization)
and deoxygenation (decarboxylation or decarbonylation) in the
upgrading of crude algal oil under hydrothermal conditions.
Table 2 shows that the presence of water signicantly affects
the elemental composition and HHV of the treated oils. In the absence of water, the treated oil has the highest carbon and hydrogen
content and lowest oxygen and nitrogen content than the oils produced with water. This treated oil also has the highest H/C ratio
and lowest O/C and N/C ratios. However, this high quality treated
oil was accompanied by the lowest treated oil yield and highest
coke yield at the same time. Water density is more inuential on
the carbon and oxygen content in the treated oil than of hydrogen
and nitrogen. The carbon content in the treated oil decreases from
80.6 wt.% to 76.2 wt.% whereas the oxygen content increases from
4.7 wt.% to 9.6 wt.% as the water density increases from 0 to 0.1 g/
cm3. However, the lowest carbon content in the treated oil produced at the highest water density of 0.1 g/cm3 is still higher than

Table 2
Elemental composition (wt.%) and heating value of crude and treated oils (400 C, 1 h).

Experimental conditions

H/C

O/C

N/C

HHV (MJ/kg)

Chlorella p.
Crude algal oil

46.8
75.1

6.8
9.9

8.4
7.3

17.2
7.8

1.76
1.58

0.275
0.078

0.154
0.083

22.6
38.1

Catalyst/crude oil (wt.%) (6 MPa H2, 0.025 g/cm3)

0%,
73.6
1%
78.5
5%,
79.0
10%,
77.2
15%
78.6
20%
77.9
30%
78.2
40% 1st usea
79.8
40% 2nd use
78.8
40% 3rd use
78.9
5% reduced
78.5
5% Sulde
78.2

9.0
9.7
9.9
9.8
9.7
9.6
9.6
9.8
9.8
10.1
9.8
9.8

5.1
5.2
4.8
4.7
4.6
4.7
4.6
4.7
2.9
2.4
4.78
4.7

12.3
6.6
6.3
8.3
7.1
7.8
7.6
5.6
8.5
8.7
7.0
7.3

1.47
1.48
1.51
1.52
1.49
1.48
1.48
1.48
1.49
1.53
1.49
1.50

0.125
0.063
0.060
0.080
0.067
0.075
0.073
0.053
0.081
0.083
0.067
0.070

0.059
0.057
0.052
0.051
0.046
0.052
0.051
0.051
0.031
0.026
0.052
0.051

35.6
39.2
39.7
38.6
39.2
38.7
38.8
40.0
39.1
39.5
39.2
39.1

Water density (g/cm3) (5% wt. catalyst, 6 MPa H2)

0
80.6
0.013
79.5
0.025
79.0
0.050
77.8
0.075
77.6
0.100
76.2

10.3
10.0
9.9
9.8
9.8
9.6

4.4
4.6
4.8
4.5
4.7
4.6

4.7
5.9
6.3
7.9
8.0
9.6

1.54
1.51
1.51
1.51
1.51
1.52

0.044
0.056
0.060
0.076
0.077
0.095

0.047
0.050
0.052
0.049
0.052
0.052

41.1
40.1
39.7
38.9
38.7
37.8

Formic acid loading (mmol) (5 wt.% catalyst)

2.3
77.3
4.7
77.2
9.3
73.2
18.7
71.0
28.0
71.7
37.3
68.3

10.0
10.2
9.7
9.2
9.0
9.2

5.8
5.1
5.0
5.0
4.4
4.7

6.9
7.5
12.1
14.8
14.9
17.9

1.55
1.58
1.59
1.55
1.51
1.61

0.067
0.073
0.124
0.157
0.156
0.197

0.064
0.056
0.058
0.053
0.053
0.058

39.2
39.3
36.5
34.5
34.4
33.0

1st with fresh catalyst used; 2nd with solid residue from the rst run; 3rd with solid residue from the second run.

230

P. Duan et al. / Fuel 109 (2013) 225233

that of crude algal oil. The oxygen content in the treated oil is larger than that of crude algal oil as the water density is beyond
0.025 g/cm3, and contrary result is observed for the hydrogen content. Therefore, from an oil quality perspective, a 0.025 g/cm3
water density seems to be preferred to both higher water densities
and to the absence of water. Water density has very little effect on
the nitrogen content in the treated oil, which is consistent with the
result identied by the HDN of pyridine in SCW [18]. The H/C and
N/C ratios are insensitive to the water density and maintain almost
at 1.51 and 0.052, respectively. The O/C ratio in treated oil increases with increasing water density and will exceed the crude algal oil with increasing water density to 0.1 g/cm3. The HHV of
treated oils decreases with increasing water density because of
the incorporation of water in the treated oils.
Table 2 also shows the change in properties of the treated oil
caused by varying the loading of HCOOH from 2.3 to 37.3 mmol.
Like the water density of marked effect on treated oil properties,
the presence of HCOOH also strongly affects the elemental composition and HHV of the treated oils. The carbon, hydrogen and nitrogen contents decrease and the oxygen content increases with
increasing HCOOH loading. At HCOOH loading 64.7 mmol, the
treated oil has higher carbon and hydrogen content and lower oxygen content compared to the crude algal oil. At HCOOH loading
>4.7 mmol, the hydrogen and carbon contents in the treated oil
are smaller than that of crude algal oil and decrease with increasing the HCOOH loading, The carbon content in treated oil is only
68.3 wt.% (much lower than the crude feed) at the highest HCOOH
loading of 37.3 mmol. The oxygen content in the treated oil significantly increases with increasing HCOOH loading, which reaches as
high as 17.9 wt.% at the highest HCOOH loading. This value is also
higher than that of microalgae feedstock. Therefore, we consider
that HCOOH not only acted as a hydrogen precursor, but also a
reactant in the upgrading of crude algal oil. The lower carbon
and hydrogen content and higher oxygen content are thus accompanied by a reduced energy density of the treated oil at higher
HCOOH loading. The HHV of treated oil decreases from 39.2 to
33.0 MJ/kg as the HCOOH loading increases from 2.3 to 37.3 mmol.
With increasing the HCOOH loading, the H/C and O/C ratios increase whereas the N/C ratio decreases. Therefore, from an energy
density perspective, a 4.7 mmol HCOOH loading seems to be preferred to the higher HCOOH loadings. Although the presence of
HCOOH can control the coke formation and improve the pour
behavior of treated oil, severe corrosion of the reactor would occur,
and thus certain amounts of metal oxides such as NiO and Fe2O3
would be formed. Possibly, they would deposit on the catalyst surface, and thus deactivate the catalyst. We, therefore, conclude that
the amount of HCOOH must be well controlled in the upgrading of
crude algal oil in SCW if one expects to produce a high quality treated oil.
In conclusion, from the treated oil yield and elemental composition point of view, the optimal conditions for the upgrading of
crude algal oil over Pt/c-Al2O3 under hydrothermal conditions
are: 5 wt.% Pt/c-Al2O3, qH2O = 0.025 g/cm3 and HCOOH loading of
4.7 mmol.
3.3. Molecular characterization of bio-oil
3.3.1. GCMS analysis
The crude algal oil was dark-brown, viscous, tar-like, and it possessed a smoky odor. In contrast, however, most of the treated oils
were freely owing liquid products. We used GCMS to separate
and identify several of the molecular components in the crude
and treated oils. Both the crude and treated oils were dissolved
in dichloromethane. The inlet temperature of the GC was 300 C,
at this temperature about 50% of the crude oil sample was volatilized as the rest had a higher boiling point. This was estimated by

performing a simulated distillation of the oils using vaporization

test in a helium atmosphere.
Fig. 1S compares the total ion chromatograms of crude algal oil
and treated oils produced from different reaction conditions. The
differences in the molecular compositions of the crude and treated
oils are clearly evident. The conditions used in the upgrading
experiment eliminated some of the fatty amides in the crude oil
and also reduced the relative amount of others. The chromatogram
(a) for the crude oil shows very little material eluting prior to
40 min, and it shows a large, broad signal around 46 min that corresponds to fatty amide. In contrast, the treated oils show some
large peaks at retention times shorter than 40 min and many regularly spaced peaks, which correspond to a series of n-alkanes
starting at C11. We did not detect appreciable amounts of alkanes
smaller than C15 in the crude algal oil, so these lighter molecules in
the treated oils may have formed from cracking of the longer chain
alkanes during the supercritical upgrading. Since this GC column
separates largely on the basis of boiling point or volatility, it is clear
that the hydrothermal upgrading has produced treated oils with
more low-boiling species. This physical change is also very apparent in the treated oil being a freely owing liquid whereas the
crude starting material has more of a tarry consistency.
Specically, the peak regions at retention time of 45.6 min and
28.0 min represent fatty amide (palmitic amide) and alkane
(pentadecane), respectively. The fatty amide can be hydrolyzed
to fatty acid under supercritical water conditions [19]. Under
high-pressure H2, adding the Pt catalyst, which has good activity
for the deoxygenation of fatty acids under hydrothermal conditions [20], leads to treated oil with very tiny peak height in the
fatty amide region. Converting fatty amide to alkane improved
the storage stability of fuel and also increased its energy density.
The net effects for the catalytic upgrading process on the molecular composition of the treated oils are that the amount of alkanes
and aromatics increased, oxygenated- and nitrogen-containing
compounds decreased, and sulfur compounds were removed.
These effects are all desirable, and they indicate that the Pt/cAl2O3/SCW combination was effective for the crude algal oil
upgrading. The reaction conditions used in this study are not sufcient, however, because the treated oil still contained some oxygenated compounds and nitrogen-containing compounds.
Therefore, additional upgrading and process optimization is
needed to reduce further the oxygen and nitrogen content in the
treated product oil.
3.3.2. FT-IR analysis
Fig. 2 shows the FT-IR spectra for crude and treated oil (400 C,
1 h, 40 wt.% 40 wt.% Pt/c-Al2O3 and 6 MPa H2). We show just one of
the treated oils because they all have similar FT-IR spectra, which
suggest that the same types of functional groups exist in each. A
comparatively lower free hydroxyl stretching vibration (near
3520 cm1) can be observed in the treated oil. Both the crude
and treated oils display strong absorbance between 2850 and
3000 cm1, indicating a high content of methyl and methylene
groups. This result is consistent with the presence of a collection
of fatty amides and alkanes in the total ion chromatogram. Absorbance peaks between 1650 and 1760 cm1 represent the C@O
group stretching vibration in amides. The treated oil shows a proportionately lower absorbance in this wave number range, which is
consistent with their reduced fatty amides content. Strong intensity of alkyl CAH stretch bands occur between 1450 and
1360 cm1 indicates a large proportion of alkyl substituted compounds in the crude oil.
3.3.3. NMR analysis
Fig. 3 displays the 13C NMR spectra for crude and treated oil
(400 C, 1 h, 40 wt.% 40 wt.% Pt/c-Al2O3and 6 MPa H2). There are

P. Duan et al. / Fuel 109 (2013) 225233

Crude oil

1.02

Treated oil

Transimittance

0.96

0.9

0.84

0.78
3600

2800

2000

1200

400

Wave number (cm-1)

Fig. 2. FT-IR spectra for crude oil and treated oil (400 C, 1 h, 40 wt.% Pt/c-Al2O3,
6 MPa H2).

231

are consistent with the presence of alkenyl and aromatic carbon

being present in the bio-oils. Integrating these peaks leads to an
estimate of the overall alkenyl or aromatic carbon content as 14%
and 26% of the crude and treated oil, respectively. Finally, the peak
at about 170180 ppm in the spectrum of the crude oil is located in
the region where one would expect to nd carbon atoms in carboxylic acid and amide groups. Of course, this peak is consistent with
the presence of fatty acids and amides in the bio-oil. These peaks
were not detected in the treated oils. Like the FT-IR results, these
NMR results are consistent with the trends discussed earlier in detail when reviewing the GCMS characterization results. The treated oil shows a resonance at about 208 ppm, which are in the
region where the carbonyl carbon in ketones and aldehydes appears. This peak also presents in the crude algal oil, and we saw
evidence for derivatives of pyrrolidinone in the total ion
chromatogram.
3.4. Effect of water density on gas composition

numerous peaks in the 1055 ppm region, where aliphatic methyl

and methylene carbon atoms appear for the crude and treated oil,
respectively. One can also observe an increase in treated oil in the
peak areas at about 110 and 160 ppm. Resonances in this region

We only studied the effect of water density on the gas composition because it signicantly affected the product yields and properties of the treated oils. Fig. 4 shows the experimental results

Crude oil

Treated oil

Fig. 3.

13

C NMR spectra for crude (top) and treated bio-oil (bottom) (400 C, 1 h, 40 wt.% Pt/c-Al2O3,6 MPa H2).

232

P. Duan et al. / Fuel 109 (2013) 225233

C2-C5

CO2

CO

CH4

H2

100

80

creased and oxygen content decreased in the treated oil with

increasing the water density, respectively. The CO2 (if formed from
the oxygenation) would be expected to dissolve in the water or react with the ammonia derived from the denitrogenation, and thus
would be not detected in the presence of water.

Percentage

3.6. Catalyst activity maintenance and characterization

60

40

20

0.013

0.025

0.05

0.075

0.1

Water density (g/cm3)

Fig. 4. Effect of water density on gas composition (400 C, 1 h, 5 wt.% Pt/c-Al2O3,
6 MPa H2).

(400 C, 1 h, 5 wt.% Pt/c-Al2O3, 6 MPa H2). For all experiments

tested, the most abundant components are unreacted H2, CO2,
CH4 and C2AC5. The un-reacted H2 presented in the nal reaction
gas components indicates that the upgrading reactions were not
performed under hydrogen starvation conditions. Clearly, water
density also affects the gas composition. The H2 content in the
gas mixture increases from 68 to 94 mol% as the water density increases from 0 to 0.1 g/cm3. The methane content decreases with
increasing the water density. The CO and CO2 are only detected
in the absence of water. Increasing the water density would promote the watergas shift reaction and the dissolution of CO2 in
water. Another likely pathway for the formation of CO2 is decarboxylation of fatty acids. Lighter molecules such as C2AC5 in the
gas phase may have formed from cracking of the longer chain alkanes during the supercritical upgrading. No molecular nitrogen
was detected in any of the experiments. Nitrogen atoms removed
from the crude oil during the supercritical upgrading probably exist in the form of ammonia. Undoubtedly, ammonia peak appeared
in the gas chromatogram when using Porapak Q column to separate the gas components. The pH of aqueous phase after the
upgrading process revealed that the aqueous phase was indeed basic, and ammonia was found from the GCMS analysis of the aqueous phase.
3.5. Reactions progressed in the upgrading
Under high-pressure H2, different types of reactions happened
simultaneously in the upgrading of crude algal oil in SCW. Beside
the hydrogenation reaction, hydration and/or oxygenation reaction
also occurred, where water molecules took part in the upgrading
reaction, H and O atoms were incorporated into the treated oil. If
the hydration reaction occurred only, the hydrogen in the treated
oil would be expected to increase as its content in water is higher
than that of crude algal oil. In fact, the hydrogen in the treated oil
decreased with increasing water density. Thus, oxygenation reaction cannot be ruled out in the upgrading. We, therefore, conclude
that hydrogenation, hydration and oxygenation reactions progressed simultaneously in the crude algal oil upgrading. The hydration and oxygenation reactions were predominant at higher water
density, and thus resulted in higher treated oil yield. The partial
pressure of H2 decreased with increasing the water density, and
lower partial pressure of H2 was unfavorable for the hydrogenation
reaction. The nal outcomes were that the hydrogen content in-

To test the suitability of Pt/c-Al2O3 as an upgrading catalyst in

hydrothermal media, we conducted experiments to probe the
activity and property changes of the catalyst after being used.
Since the catalyst alone cannot be separated from the solid residue,
activity maintenance was determined by employing the overall solid residue (catalyst and coke) recovered from the reactor at the
end of a previous run as the catalyst in a subsequent run. We have
done nothing to the recovered solid residue prior to use. The rst
upgrading run was done at 400 C for 1 h with added 6 MPa H2.
1 g of crude algal oil and 0.4 g of fresh Pt/c-Al2O3 were loaded into
the reactor. The new run was in a different batch reactor with a
fresh loading of crude algal oil and water, but the overall recovered
solid residue from the previous run was used as the catalyst. We
assessed the activity by measuring the product yields and, elemental composition of treated oils from fresh catalyst (1st run), from
solid residue recovered in the rst run (2nd run), and from solid
residue recovered in the second run (3rd run).
Fig. 1a shows the product yields from the upgrading of crude algal oil for the 1st run, 2nd run, and 3rd run. The treated oil yields
for these three runs are 58.6 wt.%, 61.2 wt.%, and 66.3 wt.%, respectively. Coke yield is insensitive to the catalyst recycling. The gas
yield shows some modest decrease after the catalyst was reused
for the second and third time. Table 2 shows the elemental compositions of treated oils from these three runs. The Pt/c-Al2O3 catalyst
shows some modest activity loss at its second and third use for
HDO, and thus results in higher treated oil yield when using the
recycled catalyst. The treated oil also has low HHV when using
the recycled catalyst. Interestingly, however, the nitrogen content in the treated oil decreases when using the recycled catalyst
for the second and third run. Catalyst activity will be affected if the
reaction conditions cause a loss of surface area. Therefore, we measured the surface area, pore volumes, and pore size distribution of
the fresh catalyst and of the reused catalyst to identify any value
changes. Table 3 shows the characterization results. The surface
area of the catalysts decreases signicantly (about 60% reduction)
after the catalyst was reused for three times. Even so, this reduction in surface area did not have an obvious impact on the treated
oil properties. In comparison, the surface area of the catalyst treated with pure water under identical conditions decreases only
about 30%. We suspect the coke deposition on the catalyst caused
the surface area loss and the cover of active sites, and thus decreased the catalyst activity. The micropore volume of the catalyst
is reduced about half of its original value in the rst run, and keeps
almost the same for the second and third run. Interestingly, the
micropore volume shows a slight increase when the catalyst was
Table 3
Catalyst characterization.
Catalyst

Surface area/
m2 g1

Micropore volume/
cm3 g1

Pore size
distribution (%)
0

<2
A

2
0

>50 A

50 A

Pt
Pt
Pt
Pt
Pt
a

fresh
H2Oa
1st use
2nd use
3rd use

99
71
47
42
38

Treated with pure water.

0.241
0.252
0.124
0.124
0.124

0.8
0.8
0.4
0.2
0.2

90.9
80.0
12.1
11.8
11.1

8.3
19.2
87.5
88.0
88.7

P. Duan et al. / Fuel 109 (2013) 225233

treated with pure water, although the reasons are not clear. Significant changes in the pore size distribution of the catalyst are observed in the second run, and almost the same pore size
distribution is kept for the third run. More specically, the proportion of mesopores decreases whereas the proportion of macropores
increases after the catalyst is reused, and thus leads to a reduction
of the surface area. This catalyst characterization work shows that
the materials experienced a signicant reduction in surface area
and micropore volume, however, the catalyst still remained very
active even these changes. That is, the denitrogenation and deoxygenation activities of the catalyst are independent to the surface
area and micropore volume. A similar phenomenon for the deoxygenation of fatty acid over Pt/C was observed under hydrothermal
conditions [20].
4. Conclusion
Pt/c-Al2O3 shows good activity toward the upgrading of crude
algal oil in SCW. Increasing the catalyst loading produced a lower
yield but higher quality treated oil. The presence of water and
HCOOH signicantly affected the product yields and appeared to
contribute to the treated oil yield. Coke formation was well controlled at higher water density and HCOOH loading. However,
the HHV of the treated oils decreased with increasing the water
density and HCOOH loading. 0.025 g/cm3 water density and
4.7 mmol HCOOH loading seem to be preferred to the higher water
densities and HCOOH loading. Hydrogenation, hydration, and oxygenation reactions progressed simultaneously in the upgrading
process under hydrothermal conditions. The catalyst experienced
a reduction in micropore volume and surface area when used for
hydrothermal upgrading. These changes did not seem to inuence
its activity, however. Thus, this work shows that the crude algal oil
from hydrothermal liquefaction of Chlorella p. can be effectively
upgraded in supercritical water in the presence of Pt/c-Al2O3 catalyst and high-pressure H2.
Acknowledgements
We gratefully acknowledge numerous helpful suggestions from
Phillip E. Savage from University of Michigan and the nancial support from the Henan Polytechnic University (B2011-008) and from
the National Science Foundation of China (21106034 and
20903036).

233

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2012.12.074.
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