Article

pubs.acs.org/EF

Selection of Temperature for Bio-oil Production from Pyrolysis

of Algae from Lake Blooms
Rui Li, Zhaoping Zhong,* Baosheng Jin, and Aijun Zheng
Key Laboratory of Energy Thermal Conversion and Control, Ministry of Education, School of Energy and Environment,
Southeast University, Nanjing, 210096, China

ABSTRACT: A large abundance of biomass waste is generated from harmful algal blooms (HABs) which dramatically damages
the environment. Algae from lake blooms was pyrolyzed in a fixed-bed reactor at 300−700 °C in order to evaluate the effect of
temperature on the product distribution and bio-oil quality. Yields and compositions of bio-oil, char, and gases were analyzed.
The results demonstrated that the maximum yield (59%) of algal bio-oil was obtained at 500 °C. The bio-oil from algal blooms
was characterized with higher heating value (about 21 MJ/kg) and nitrogen content (2.68%) when compared with pine sawdust.
Elevated temperatures improved the bio-oil quality by increasing its heating value and hydrocarbon content. However, excessively
higher temperatures also lead to the formation of undesired products such as nitrogenous compounds and polycyclic aromatic
hydrocarbons (PAHs).

1. INTRODUCTION inherent properties of the feedstocks. Thus, pine sawdust was

Pyrolysis is a promising technology for utilizing the biomass,
because it not only proposes a new way for the disposal of solid
wastes but also produces liquid bio-oil which is beneficial for
fuel storage, transportation, and industrial application. A variety
of forest and agricultural residues, including sawdust, bark,
shavings, hulls, and straws, can be pyrolyzed to produce the bio-
oil.1 Besides the lignocellulosic biomass, algae also present
remarkable potential to produce substituted fuel by pyrolysis. In
recent years, both microalgae2−5 and marine macroalgae6−8
were pyrolyzed in laboratory-scale devices to produce bio-oil or
obtain their pyrolytic mechanism. With the biotechnological
method to manipulate the metabolic pathways, the pyrolysis of
microalgae was reported to produce high-quality bio-oil in high
yields.3 The quality gap between algal bio-oil and fossil fuels
could be bridged through further treatment, such as hydro-
genation in supercritical water.9
Biomass wastes are also generated from harmful algal blooms
(HABs) frequently occurring in aquatic systems and posing
serious risks for human and animal health. For example, Taihu
Lake, in China, in 2007 experienced a severe HAB, resulting in
a drinking water crisis in Wuxi city.10 With the application of
the pyrolysis technology, the cost for HABs treatment is pos-
sibly reduced by producing the valuable bio-oil. Recently,
Maddi et al.11 pyrolyzed the algae from lake blooms in a fixed
bed reactor and compared the yields and composition of
products, suggesting the probability to convert this wild algal
biomass into liquid fuel.
Reaction temperature has shown its ability to affect the
pyrolysis of lignocellulosic biomass significantly on the product
distribution and quality.12−17 In this paper, the pyrolysis of the
algae from lake blooms was carried out in a fixed-bed reactor
with temperature from 300 to 700 °C. The product yields and
quality, especially for bio-oil, were analyzed to determine the
optimal operation temperature. Furthermore, the characteristics
of the pyrolytic products from algae were anticipated to be
different than that from the lignocellulosic biomass due to the
also pyrolyzed for comparison.
2. EXPERIMENTAL SECTION
2.1. Feedstock. The algal sample, dominant genus of which was
Microcystis sp., was collected from the blooms in Meiliang Bay of Taihu
Lake, China. The collected sample was cleaned by distilled water, dried
at 60 °C for 24 h, and then milled to a particle size less than 0.18 mm.
Pine sawdust, collected from a timber mill in Nanjing, China, was also
dried, milled, and screened to have the same particle size as algae. The
proximate and ultimate analyses of these two samples were shown in
Table 1.
2.2. Experimental Setup and Procedure. The schematic
diagram of the experimental setup is shown in Figure 1. The pyrolysis
experiments were performed in a horizontal stainless steel tubular
reactor (80 mm i.d. and 340 mm length), externally heated by an
electric tube furnace. Nitrogen was used as the carrier gas at a flow rate
of 300 mL/min. The sample holder, consisting of a quartz boat and a
stainless steel stick, was applied to transport the sample or the solid
product to and from the heated zone in recycle. Approximately 7 g of
feedstock was placed in the boat of the sample holder, which initially
rested in an unheated section of the tube. Once the set temperature
was achieved, the sample was pushed to a predetermined location in
the furnace and pyrolyzed for 40 min. At the end of each experiment,
the boat was pulled back to the unheated part of the tube, and the
solid residue was cooled to room temperature. The bio-oil was
collected in two coil condensers cooled by the mixture of water and
ice. The gaseous products as well as carrier gas passed through a quartz
wool filter and a silica gel drier successively and were finally collected
by a gas bag.
2.3. Product Analysis. The char yield was determined by the
weight difference of the quartz boat with and without solid residue,
while the yield of liquid was estimated by the weight difference of the
condensers before and after the experiments. The yield of pyrolytic gas
was calculated from its density and volume. With the help of the gas
chromatography (GC), gas composition was analyzed to determine its
density. The volume was obtained by the reading difference between
Received: January 18, 2012
Revised: April 15, 2012
Published: April 16, 2012

© 2012 American Chemical Society 2996 dx.doi.org/10.1021/ef300180r | Energy Fuels 2012, 26, 2996−3002
Energy & Fuels
Table 1. Proximate and Ultimate Analyses of Studied Raw Materials
proximate analysisa (wt %)
samples moisture volatile fixed carbon b
algae from lake blooms 7.52 68.52 19.61
pine sawdust 7.80 75.38 15.72
a
As received basis. bBy difference. cDry and ash free basis.
Figure 1. Schematic diagram of the pyrolysis experimental setup.
the two integral flowmeters before and after the tube reactor. The
experimental results were considered to be acceptable since the error
of the mass-balance is less than 5%. Otherwise the experiment should
be performed in duplicate.
Proximate analysis of the raw materials and char was performed
according to ASTM E870-82. Gaseous products in the gas bags were
analyzed using an Agilent 6890N gas chromatography (GC) equipped
with a thermal conductivity detector (TCD) and a flame ionization
detector (FID) and using high-purity argon (99.999%) as the carrier
gas. The functional groups of the bio-oil samples were identified by a
Bruker Vector 22 Fourier transform infrared spectrometer (FTIR).
The frequency range of the spectrometer was 4000−400 cm−1. The
resolution of the collected spectra was set to be 1 cm−1. The
elemental compositions of the biomass and bio-oil were performed in
a Vario EL-III elementar made by ELEMENTAR Analysensysteme
GmbH in Germany. The high heating values (HHV) of the feed-
stocks and liquid products were determined by a calorimeter,
SDACM3000.
The chemical composition of bio-oil was analyzed using gas
chromatography/mass spectrometry (GC/MS, Agilent 7890A/
5975C). A Varian Cp-sil 8cb capillary column (30 m × 0.25 mm
i.d., 0.25 μm film thickness) was applied to the analysis. Helium
(99.999%) was used as the carrier gas at a constant flow rate of
3 mL/min. The oven temperature was programmed from 40 to 180 °C
at the heating rate of 5 °C/min followed by temperature increasing to
280 °C at the heating rate of 20 °C/min. MS was conducted in the
following operational conditions: transfer line 230 °C, ion source
230 °C, and electron energy 70 eV.
Energy recovery (ER) was calculated to evaluate the energy yield in
bio-oil using eq 1
ER = HHVbio ‐ oil × Yieldbio ‐ oil /HHVbiomass
where Yieldbio‑oil is the weight yield of bio-oil and HHVbio‑oil and
HHVbiomass are the higher heating values of bio-oil and biomass,
respectively.
Article
ultimate analysisc (wt %)
−1
ash HHV (MJ·kg ) C H N Ob
4.35 19.95 50.78 7.30 3.45 38.48
1.10 20.17 55.02 6.08 0.09 38.81
3. RESULTS AND DISCUSSION
3.1. Product Yield. The yields of bio-oil, char, and gases
obtained from the pyrolysis of algae between 300 and 700 °C
are presented in Figure 2. For comparison, the product yields
Figure 2. Product yield as a function of temperature for the pyrolysis
of algal biomass from lake blooms.
from pine sawdust at 500 °C are also shown in Figure 2. With
increasing temperature, the gases yield increased steadily and
the char yield kept declining. Figure 2 demonstrated that the
maximum yield of bio-oil appeared at 500 °C. The influence of
temperature on the distribution of pyrolytic products from algal
blooms was similar to previous observations with lignocellulosic
biomass17,18 and other algae.3,6,19 The maximum yield of bio-
oil (59.1%) at 500 °C was close to that of microalgae oil in
references, which were 57.9% at 450 °C3 and 55.3% at 400 °C.6
Pyrolysis of algal biomass at 500 °C resulted in a lower yield of
bio-oil (59.1%) and gases (15.3%) but a higher yield of chars
(25.6%), compared to 61.3% oil yield, 18.5% gaseous yield, and
20.2% solids yield for the pyrolysis of pine sawdust at the same
temperature. It was possible that the higher ash content and
lower volatile content in algal biomass led to greater char
formation but less oil production.
3.2. Characterization of Char and Gas. Figure 3 illustrates
the proximate analysis of the char obtained at 300−700 °C,
represented in weight per mass of feedstock. It was observed that
the increase of pyrolysis temperature enhanced the volatiles release
and reduced the fixed carbon content slightly, but it had no
influences on the ash content. Moreover, the volatile matter con-
tent decreased rapidly above 300 °C and then dropped slowly after
(1) 500 °C. The results indicated that the temperature of 500 °C in
this paper was high enough for the release of the volatiles.
Figure 4 shows the accumulated amounts of each major gas
released at 300−700 °C, represented in mole per mass of
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Energy & Fuels Article

with previous observations from the lignocellulosic bio-

mass.15,20−22 Unlike CO2, CO, and CH4, H2 was almost absent
in the gaseous products at the temperature below 600 °C.
However, in a temperature range of 600−700 °C, the amount
of H2 increased sharply and reached 1.89 mmol/g-biomass. The
hydrogen in pyrolytic gas might be formed from the reactions,
as shown below.
C + H 2O ↔ CO + H 2

Figure 3. Effect of pyrolysis temperature on the proximate analysis of chars.
CH4 + H 2O ↔ CO + 3H 2
3.3. Properties of Bio-oil. Table 2 illustrates the elemental
analysis and HHV of bio-oil from the pyrolysis of algal blooms
at 300−700 °C and pine sawdust at 500 °C. Table 2 also lists
the properties of fossil fuel and the bio-oil samples from
microalgae in the references for comparison. The oxygen
content of the oil from algal blooms was found to decrease
from 32.20% at 300 °C to 26.36% at 700 °C with increasing
temperature. As mentioned in Section 3.2, elevated temper-
atures favored the formation of CO2 and CO, which was related
to the cracking reactions of oxygen functional groups and led to
the removal of oxygen. The decrease of the oxygen content
with increasing temperature contributed to an increase in HHV.
The ER of the bio-oil from algal blooms achieved its maximum
(62.99%) at 500 °C, the same temperature at which the
maximum oil yield appeared. The liquid yield of algal blooms at

Figure 4. Accumulated amounts of gases released from the pyrolysis of

algal biomass from lake blooms.

biomass. The gas product consisted of CO, CO2, CH4, and H2,
suggesting the presence of deoxygenation, demethylation, and
dehydrogenation during the pyrolysis process. All of these gases
showed increasing trends in quantity at elevated temperatures.
The results indicated that the secondary cracking reactions
were enhanced at higher temperatures, which was consistent Figure 5. Infrared spectra of bio-oil from algal bloooms.

Table 2. Properties of Bio-oil Obtained from the Pyrolysis of Algal Biomass from Lake Blooms and Pine Sawdust
algal biomass from lake blooms microalgae
pine heterotrophic
properties sawdust Chlorella protothecoides6 C. protothecoides3 fossil oil3
pyrolysis temperature, °C 300 400 500 600 700 500 400 450
yield, % 48.29 54.92 59.14 56.37 45.34 61.30 55.3 57.9
C, % 59.31 60.26 61.66 61.68 61.87 58.73 n.d.a 76.22 83.0−87.0
H, % 6.64 7.55 7.93 8.04 8.07 5.76 n.d. 11.61 10.0−14.0
N, % 1.85 1.87 2.68 3.37 3.7 0.1 n.d. 0.93 0.01−0.7
S, % n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.05−5.0
O, % 32.2 30.31 27.73 26.91 26.36 35.42 n.d. 11.24 0.05−1.5
O/C ratio 0.41 0.38 0.34 0.33 0.32 0.45 n.d. 0.11
HHV, MJ/kg 19.19 20.26 21.25 21.42 21.57 18.1 39.7 41 42
ER, % 46.46 55.78 62.99 60.53 49.02 55.02 93 87.9

a
Not determined.

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Energy & Fuels Article

Table 3. GC/MS Analysis of the Bio-oil from Algal Biomass and Pine Sawdust (Relative Area, %)
algal biomass from lake blooms
group compound 300 °C 400 °C 500 °C 600 °C 700 °C pine sawdust
hydrocarbons 1-hexene, 5-methyl- - - 0.80 0.60 0.83 -
1-heptene, 2-methyl- 0.71 0.88 0.91 1.16 1.31 -
1-decene 1.40 1.26 1.05 0.40 0.54 -
1-tridecene - - - 1.42 1.64 -
1-tetradecene 0.50 0.49 0.67 1.36 1.39 -
heptadecane 1.32 1.79 3.78 3.01 3.10 -
octadecane 0.48 0.51 0.72 0.51 0.56 -
9-octadecyne 0.96 1.11 2.71 1.30 1.07 -
sum 5.38 6.03 10.65 9.76 10.44 -

acids acetic acid 3.30 3.82 3.72 6.57 7.63 8.52

propanoic acid - - - - - 0.25
pentadecanoic acid 1.47 - 1.21 0.34 0.29 -
hexadecenoic acid, Z-11- 2.99 2.59 2.36 1.36 1.42 -
n-hexadecanoic acid 13.55 14.75 7.82 5.66 3.74 -
9,12-octadecadienoic acid (Z,Z)- 1.32 1.29 1.41 - - -
oleic acid 2.67 2.13 1.90 0.44 0.21 -
octadecanoic acid 1.00 1.47 0.62 0.41 0.46 -
sum 26.31 26.05 19.05 14.80 13.74 8.77

nitrogenous compounds 1,3-diazine 0.66 0.27 0.33 0.78 0.75 -

pyridine - 0.52 1.06 0.53 0.64 -
pyrrole - 0.30 0.85 0.71 1.07 -
pyridine, 2-methyl- 1.26 0.23 0.97 1.12 1.34 -
pyrazine, methyl- 0.37 0.39 0.35 0.55 0.94 -
1H-pyrrole, 3-methyl- 0.97 1.08 1.51 1.62 2.10 -
pentanenitrile, 4-methyl- - 0.29 - 0.57 0.97 -
propanenitrile, 2-hydroxy- 3.26 2.95 0.45 - - -
pyridine, 3,5-dimethyl- - - 0.45 0.84 1.09 -
benzenamine, 4-methoxy- 1.54 0.70 1.53 - - -
4-pyridinol 0.51 2.30 0.89 - - -
3-pyridinol 0.56 0.38 - - - -
benzonitrile, 2-methyl- - - 0.62 1.89 1.73 -
3-pyridinol, 6-methyl- 1.17 1.37 - - - -
benzenepropanenitrile 0.89 0.53 1.19 1.27 1.89 -
i Indole 0.94 1.01 4.60 5.85 6.20 -
1H-indole, 3-methyl- 2.60 1.11 1.28 2.46 4.67 -
hexadecanenitrile 0.22 0.20 1.32 1.26 1.16 -
octadecanamide 1.40 0.70 3.48 1.74 1.22 -
sum 16.34 14.34 20.88 21.20 25.75 -

sugars 1,4:3,6-dianhydro-.alpha.-D-glucopyranose 4.25 5.36 3.19 2.46 2.53 3.25

.beta.-D-glucopyranose, 1,6-anhydro- 17.92 21.07 12.10 7.09 3.62 26.68
sum 22.17 26.43 15.28 9.54 6.14 29.94

phenols phenol 1.81 1.81 3.02 3.57 5.48 0.76

phenol, 2-methyl- - 0.33 0.74 1.65 1.83 0.96
phenol, 4-methyl- 1.49 1.80 2.55 2.63 2.34 1.32
phenol, 2,4-dimethyl- - - 1.34 1.47 1.69 0.67
phenol, 4-ethyl- - - 2.41 2.47 2.76 1.43
phenol, 2-methoxy-4-methyl- - - - - - 1.33
1,2-benzenediol - - - - - 9.20
1,2-benzenediol, 3-methoxy- - - - - - 3.34
1,2-benzenediol, 4-methyl- - - - - - 6.08
phenol, 2,6-dimethoxy- - - - - - 1.50
1,3-benzenediol, 4-ethyl- - - - - - 3.55
vanillin - - - - - 0.61
sum 3.30 3.95 10.07 11.78 14.09 30.75

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Energy & Fuels Article

Table 3. continued
algal biomass from lake blooms
group compound 300 °C 400 °C 500 °C 600 °C 700 °C pine sawdust
carbonyls and alcohols propanal - - - - - 1.58
2-butenal 4.17 3.63 0.71 0.60 - -
2-cyclopenten-1-one, 2-methyl- - 0.27 - - - -
1,2-cyclopentanedione - - - - - 2.95
1,2-cyclopentanedione, 3-methyl- 1.02 0.44 - - - 3.36
maltol 0.74 0.47 - - - 0.76
octanal - 5.08 2.25 2.06 1.56 -
cyclohexanol, 4-methyl-1-(1-methylethyl)- 0.22 0.71 2.02 2.07 1.94 -
sum 6.15 10.60 4.98 4.73 3.49 8.65

furans furfural - - - - - 3.20

2-furanmethanol 0.84 0.78 - - - 0.56
2-furancarboxaldehyde, 5-methyl- - - - - - 1.06
furan, 2,5-diethoxytetrahydro- - - - - - 1.05
benzofuran, 2,3-dihydro- - - 0.64 1.09 1.44 -
sum 0.84 0.78 0.64 1.09 1.44 5.87

PAHs naphthalene - - - 5.87 6.53 -

naphthalene, 2-methyl- - - - 2.29 3.46 -
naphthalene, 2-ethenyl- - - - 1.09 1.68 -
naphthalene, 2,6-dimethyl- - - - 1.01 1.64 -
sum - - - 10.26 13.30 -

400−500 °C was similar to the microalgae listed in Table 2.
The bio-oils from microalgae in the references were much
preferable to that from lignocellulosic materials in terms of the
HHV.23 The HHV of the bio-oil from algal blooms was only
equal to about half of that from microalgae and fossil fuel but is
still superior to that from pine sawdust. Since HHV was an
important parameter for the fuel combustion, the bio-oil from
algal blooms might be more prospective than that from pine
sawdust.
During the combustion, nitrogen in fuels can be oxidized to
NOx, which is a severe pollutant to the environment. Therefore,
the nitrogen percentage plays a remarkable role in determining
oil quality. It was found that the bio-oil from algal blooms had
26.8 times higher nitrogen content than that from pine sawdust
at the same pyrolysis temperature, which was obviously due to
the presence of protein and chlorophyll in the algal biomass.3 It
was worth noting that the content of nitrogen in the bio-oil of
algal biomass from lake blooms increased with temperature,
especially from 400 to 500 °C, during which the nitrogen
content rose abruptly from 1.87% to 2.68% and finally reached
3.70% at 700 °C. The results from the ultimate analysis of chars
indicated that more volatile matters were released from solid
phase as the temperature elevated, which contributed to the
transfer of the nitrogen element to liquid phase. Although the
nitrogen reduction in algal oil had been reported through
catalytic treatment in supercritical water,24 lower temperatures
were suggested to control the nitrogen content in crude oil.
3.4. Composition of Bio-oil. The structural groups in the
algal bio-oil can be identified with the application of FTIR
(Figure 5). The spectra in the wavenumbers of 3600−3100 cm−1
are assigned to N−H and O−H functional groups, which
represent nitrogenous compounds and hydroxy groups. The
spectrum peaks at 2926 and 1401 cm−1 characterize the
stretching and bending vibrations of C−H, respectively, both
of which represent alkyl groups. The stretching vibrations of
CO at 1655 cm−1 represent carbonyl compounds, carboxylic
3000
acids, or esters. The characteristic peak of CC stretching
vibrations appears at 1544 cm−1 indicating the existence of
aromatic compounds in the bio-oil. The stretching bands at
1244 and 1047 cm−1 correspond to C−O functional groups for
phenols, alcohols, carboxylic acids, or esters. The results above
indicate the algal bio-oil may contain nitrogenous compounds,
alcohols, acids, esters, phenols, hydrocarbons, carbonyl
compounds, and aromatic compounds.
Table 3 shows the GC/MS analysis of the bio-oils from the
pyrolysis of algal biomass and pine sawdust. The chemical
compounds identified by GC/MS were classified into several
groups as hydrocarbons, acids, nitrogenous compounds, sugars,
phenols, furans, polycyclic aromatic hydrocarbons (PAHs),
carbonyls, and alcohols, which match the results from the FTIR
analysis. Table 3 also presents the total relative areas of each
group. Hydrocarbons, naturally present in fossil oil, are
currently the world’s main energy source. Thus, the existence
of hydrocarbons is a remarkable advantage for the algal oil. As
shown in Table 3, higher relative content of hydrocarbons was
found in the bio-oil at elevated temperatures (500−700 °C)
than that at 300 and 400 °C. However, in the range of 500−
700 °C, the relative percentage of hydrocarbons did not
strongly depend on temperature. The hydrocarbons in the algal
oil were conventionally identified as the pyrolytic products
from lipid and chlorophyll.11 Besides that, it might be generated
from the decarboxylation reaction of fatty acids accompanied
with the release of carbon dioxide.25 For example, it was pos-
sible to produce heptadecane from octadecanoic acid. Addi-
tionally, at elevated temperatures, the medium- and long-chain
hydrocarbons probably cracked into short-chain ones which
existed in gas phase. Above all, these mechanisms could make
reasonable explanations for the relative content variation of
hydrocarbons in pyrolytic oil obtained at 500−700 °C.
The fatty acids in the bio-oil with algal biomass were mainly
produced from the pyrolysis of lipid,3 identified as short-chain
(acetic acid) and long-chain (C15−C18) compounds in this
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Energy & Fuels
Table 4. Compounds with Medium- and Long-Aliphatic Tails Identified in Bio-oil from Algal Biomass from Lake Blooms
(Relative Area, %)
paper, and furthermore, lower temperatures were more benefi-
cial for the generation of fatty acids, because they were possibly
cracked into other compounds like hydrocarbons did as
mentioned above.26 Nitrogenous compounds in algal oil are
originated from the pyrolysis of protein and chlorophyll, for
which nitrogen is an essential element. They were classified into
amides, nitrile, and N-heterocycles. Generally, the relative
percentage of the nitrogenous compounds was enhanced at
higher temperatures, which was in accordance with the result
from the nitrogen content of in algal bio-oil between 300 and
700 °C.
Besides the lipid and protein, polysaccharose is also a major
component in algae and characterized by its long carbohydrate
structure and sugars can be obtained from the rupture of
glycosidic bonds in this structure.22,27 Table 3 shows that the
relative percentage of the sugars reaches a maximum value at
400 °C. Similar trends had been reported for the pyrolysis of
the lignocellulosic biomass, suggesting that the formation of
sugars was favored at mild temperatures but was possibly
degraded at excessively high temperatures.22,28
As typical pollutants, PAHs not only exist in fossil fuels but
also can be produced from fuel combustion and pyrolysis.
Table 3 presented that PAHs were not detected in the bio-oil
from algal biomass at 300−500 °C. However, the percentage
increased sharply when the temperature exceeds 600 °C,
3001
Article
indicating the formation of PAHs were boosted at high tem-
peratures.29 The results were in accordance with the findings
about the pyrolysis of the polysaccharide and biomass in the
previous reports.30,31 PAHs were possibly generated through
Diels-Alder reaction and the deoxygenation of oxygenated aro-
matic compounds, because all of the reactants for these reactions
(hydrocarbons, phenols, and furans) could be obtained from
the pyrolysis of algal biomass.12,32,33 Additionally, PAHs might
be also produced from the pyrolysis of protein, which could be
enhanced in the presence of sugars.34,35 Therefore, it was
suggested to restrain the pyrolysis temperature below 600 °C
for bio-oil production avoiding emergence of PAHs.
Table 3 also shows the pronounced differences on the oil
composition between algal biomass and pine sawdust, due to
their individual components. The oil from algal biomass was
characterized by higher contents of acids, hydrocarbons, and
nitrogenous compounds but lower contents of phenols and
sugars than that with pine sawdust at the same pyrolysis
temperature.
Hydrocarbons are valuable organic compounds because of
the energy produced when burnt. Among the constituents of
bio-oil, the compounds with medium- and long-aliphatic tails
(shown in Table 4), including amides, nitriles, aldehydes, and
fatty acids, have the potential to produce straight-chain
hydrocarbons via the denitrification and deoxygenation
dx.doi.org/10.1021/ef300180r | Energy Fuels 2012, 26, 2996−3002
Energy & Fuels
reactions.25 The relative percentage of these compounds
achieved the maximum of 28.48% at 400 °C and was 22.38%
at 500 °C. As a result, the bio-oil from algal biomass was
possibly superior to that from pine sawdust when producing
substituted fuel with high content of hydrocarbons.
4. CONCLUSION
Algal biomass from lake blooms was pyrolyzed in a fixed-bed
reactor to evaluate the influence of temperature on the yields
and compositions of the pyrolytic products. The pyrolysis of
algal blooms at 500 °C produced the bio-oil with the maximum
yield of 59% and heating value about 21 MJ/kg, compared to
61% and 18 MJ/kg of the pine sawdust oil. The nitrogen
content in algal oil was 26.8 times higher than that from pine
sawdust, which needs to be improved in further research.
Pyrolysis at elevated temperatures resulted in upgrading the
bio-oil on the heating value and hydrocarbon content. How-
ever, excessively high temperatures increased the percentages of
nitrogen and PAHs in bio-oil. Therefore, a moderate tempera-
ture (500 °C in this paper) was suggested for producing the
algal oil with the optimal yield and quality. Additionally,
the high percentage (22.38% relative content at 500 °C) of the
compounds with medium- and long-aliphatic tails (amides,
nitriles, and fatty acids) indicated the feasibility to promote the
oil quality by converting these compounds into straight-chain
hydrocarbons.
■ AUTHOR INFORMATION
Corresponding Author
*Tel. 86-25-83794700. E-mail: liruiseu@hotmail.com (R.L.);
zzhong@seu.edu.cn (Z.Z.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was supported by grants from the National Basic
Research Program of China (973 Program, 2007CB210208,
and 2011CB201505), the National Natural Science Foundation
of China (NSFC, 50776019), and the China MOST for
Intergovernment S&T Optional Cooperation between China
and Europe (2010DFA61960).
■ NOMENCLATURE
HAB = harmful algal bloom
HHV = high heating value, MJ/kg
ER = energy recovery, %
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dx.doi.org/10.1021/ef300180r | Energy Fuels 2012, 26, 2996−3002