J. Anal. Appl.

Pyrolysis 71 (2004) 855863

Fast pyrolysis of microalgae to produce

renewable fuels
Xiaoling Miao a,b , Qingyu Wu a, , Changyan Yang c
a

Department of Biological Sciences and Biotechnology, Tsinghua University, Beijing 100084, PR China
b Department of Biological Sciences, Ningde Teachers Colloge, Fujian, Ningde 352100, PR China
c Institute of Process Engineering, Chinese Academy of Science, Beijing 100080, PR China
Accepted 26 November 2003

Abstract
In the present study, fast pyrolysis tests of microalgae were performed in the fluid bed reactor. The experiments were completed at temperature of 500 C with a heating rate of 600 C s1
and a sweep gas (N2 ) flow rate of 0.4 m3 h1 and a vapour residence time of 23 s. In comparison with the previous studies on slow pyrolysis from microalgae in an autoclave, a greater amount
of high quality bio-oil can be directly produced from continuously processing microalgae feeds
at a rate of 4 g min1 in the present work, which has a potential for commercial application of
large-scale production of liquid fuels. The liquid product yields of 18 and 24% from fast pyrolysis of Chllorella protothecoides and Microcystis aeruginosa were obtained. The saturated and polar
fractions account for 1.14 and 31.17% of the bio-oils of microalgae on average, which are higher
than those of bio-oil from wood. The H/C and O/C molar ratios of microalgae bio-oil are 1.7 and
0.3, respectively. The gas chromatograph analyses showed that the distribution of straight-chain alkanes of the saturated fractions from microalgae bio-oils were similar to diesel fuel. Bio-oil product from fast pyrolysis microalgae is characterized by low oxygen content with a higher heating
value of 29 MJ/kg, a density of 1.16 kg l1 and a viscosity of 0.10 Pa s. These properties of bio-oil
of microalgae make it more suitable for fuel oil use than fast pyrolysis oils from lignocellulosic
materials.
2003 Elsevier B.V. All rights reserved.
Keywords: Microalgae; Fast pyrolysis; Bio-oil; Renewable energy sources

Corresponding author. Tel.: +86-10-62781825; fax: +86-10-62781825.

E-mail address: qingyu@tsinghua.edu.cn (Q. Wu).

0165-2370/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2003.11.004

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1. Introduction
Biomass resources include wood and wood wastes, energy crops, aquatic plants, agricultural crops and their waste by-products, municipal wastes and animal wastes [1,2]. Among
these, microalgae have been suggested as very good candidates for fuel production because
of their advantages of higher photosynthetic efficiency, higher biomass production and faster
growth compared to those lignocellulosic materials [35].
Almost every year, microalgal blooms cover extensive areas of many Chinese lakes,
such as Chaohu Lake, Taihu Lake and Dianchi Lake due to serious eutrophication. This
results in deterioration of water, death of fish and disaster to residents around the lakes.
Elimination of the microalgal blooms becomes an urgent project. Enormous microalgae
biomass consisting of Chllorella, Microcystis and other genera could be harvested from
these eutrophic lakes for fuel production. Meanwhile, utilization of planktonic microalgae
for pyrolysis may decrease the eutrophication of lakes. Therefore, pyrolysis of microalgae
is beneficial to both production of renewable fuels and improvement of the ecological
environment of lakes.
Pyrolysis produces energy fuels with high fuel-to-feed ratio, making it the most efficient
process for biomass conversion and the method most capable of competing and eventually
replacing nonrenewable fossil fuel resources [6]. The process can be adjusted to favor char,
liquid or gas production. As the liquid called bio-oil can be readily stored or transported
and has lower nitrogen and sulfur contents, much of the present interest in pyrolysis centers on liquid production. In recent years fast pyrolysis process for biomass has attracted
a great deal of attention for maximizing liquid yields, and many researches have been carried out. However, these researches have mainly concentrated on the fast pyrolysis of the
lignocellulosic materials.
Previous studies at our laboratory on the pyrolysis of Emiliana huxleyi, Gephyrocapsa
oceanica, Chlorella protothecoides and Spirulina platensis have shown the competitive
potential of fuel production from microalgae biomass [713]. The above studies were all
completed with traditional slow pyrolysis processes, they are performed at a low heating
rate and a long residence time. The longer residence times can cause secondary cracking of
the primary products, reducing yield and adversely affecting bio-oil properties. In addition,
a low heating rate and a long residence time may increase energy input. All of these are
not attractive for commercial application of liquid fuel production. There is no information available regarding the production of liquid fuel from fast pyrolysis of microalgae.
Therefore, in the present study, two kinds of microalgae C. protothecoides and Microcystis
aeruginosa were chosen as renewable energy source. The characteristics of the fast pyrolysis
of microalgae and the properties of the pyrolytic oils were investigated.

2. Experimental
2.1. Microalgae and sample preparation
The strain of C. protothecoides was provided by the Culture Collection of Algae at the
University of Texas (Austin, USA). The culture medium and method were described as

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857

before [7,8]. The alga was grown autotrophically and axenically in batch culture under
25 C (1) with continuous illumination at intensities of 40 mol m2 s1 . Aeration was
provided by bubbling air at regular pressure. Cells were harvested by centrifugation and
washed one time with distilled water and then dried by freeze dryer. The sample was prepared
by pulverization in a mortar and stored in a desiccator. The strain of M. aeruginosa was
collected from Chaohu Lake in China. The powder of M. aeruginosa was obtained as same
as C. protothecoides mentioned above.
2.2. Quantification of the main chemical components
The main chemical components of C. protothecoides and M. aeruginosa were measured.
The crude protein was determined by dye binding method [14]. Extraction of crude lipids
from biomass powder was performed according to the procedure of Zhu et al. [15]. Solvent
phase was recovered by centrifugation, and evaporated on circulation baths at 70 C and
dried under infrared light at 30 C. The content of carbohydrate was determined by the
method of 3,5-dinitrosalicylic acid colorimetry [16]. 0.5 g powder was acidified with HCl
to a final concentration of 2.5N and hydrolyzed at 100 C for 30 min. After neutralization,
the volume was adjusted to 100 ml and then filtered. The resulting solution was used for
assay of carbohydrate. The moisture content was determined from the weight loss on heating
at 105 C for 24 h, and the ash content was determined as the residue after ignition at 600 C
for 3 h.
2.3. Fast pyrolysis
The algal cell samples were screened to pass through a screen of 0.18 mm aperture to
give small particles to ensure rapid heat transfer rates in the reactor. Two hundred grams of
sample was subjected to pyrolysis in the fluid bed reactor (Fig. 1). The combustor was used
for the further pyrolysis of some biomass that was not completed pyrolyzed in the reactor.
The biomass-feeding rate was 4 g min1 . The experiments were carried out at temperature
of 500 C with a heating rate of 600 C s1 and a sweep gas (N2 ) flow rate of 0.4 m3 h1 and
a vapour residence time of 23 s. The total liquid products were comprised of an aqueous

Fig. 1. Fluid bed fast pyrolysis system.

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and an oil phase, which were separated and weighed. After pyrolysis, the solid char was
removed and weighed, and then the gas yield was determined by the difference. All the
yields were expressed on the basis of the dry weight of samples.
2.4. Analysis of the bio-oil
The chemical class compositions of oils were determined by thin layer chromatography (IATROSCAN MK-5). Oils were fractioned using column liquid chromatography. Oils
were separated into n-hexane soluble and n-hexane insoluble compounds (asphaltenes)
using 30 ml n-hexane. The n-hexane soluble fraction samples were added by adsorption
onto an inert silica-gel support. The column was then eluted successively with n-hexane,
dichloromethane/n-hexane (2:1) and ethanol to produce saturated, aromatic and polar chemical class fractions respectively. The saturated fraction was subjected to gas chromatograph
analysis. The gas chromatograph analysis with flame ionization detection (FID) was performed using a HP 5890 gas chromatography with hydrogen carrier gas and an OV1 capillary column (25 m 0.22 mm i.d.). The temperature program was 100 C followed by a
6 C min1 heating rate to 320 C.
The elemental compositions of oils were determined by CE-440 elemental analyzer. The
heating value, density and viscosity of oils were determined.

3. Results and discussion

3.1. Product yields
Fast pyrolysis is a high temperature process in which biomass is rapidly heated in the
absence of oxygen. The essential features of a fast pyrolysis process are very high heating and
heat transfer rates, carefully controlled pyrolysis reaction temperature of around 500 C,
short vapour residence times of less than 2 s and rapid cooling of the pyrolysis vapour
[17,18]. Therefore, the typical temperature of 500 C was used in the study in order to
investigate the fast pyrolytic characteristics of microalgae.
Fig. 2 shows the product yields of fast pyrolysis from micoalgae at temperature of 500 C
with a heating rate of 600 C s1 and the sweep gas (N2 ) flow rate of 0.4 m3 h1 and a vapour
residence time of 23 s. The bio-oil yields from C. protothecoides and M. aeruginosa were
17.5 and 23.7%, respectively (Fig. 2). Much of the microalgae powder adhered to the
wall of the reactor probably because of electrostatic forces. Therefore, they could not react
completely and resulted in the high yields of the char. At the same time, the pyrolysis vapour
was not effectively condensed. All of these caused the decrease in the bio-oil yields. The
bio-oil production yields could be expected to be higher by improving the apparatus of fast
pyrolysis system.
The above preliminary work indicates that it is a feasible and promising way to produce
liquid fuels from microalgae by fast pyrolysis. The present study has advantages over the
previous studies on slow pyrolysis of microalgae [713] in the following aspects. First,
almost no flowing bio-oil products were directly produced from slow pyrolytic process in
the previous works. The viscous materials regarded as oils in the previous studies were

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859

Fig. 2. The product yields of fast pyrolysis from miroalgae C. protothecoides and M. aeruginosa at temperature
of 500 C.

organic extracts separated from reaction mixtures by washing with dichloromethane and
filtering. The organic extracts were rubber-like after the dichloromethane was evaporated
and not suitable for liquid fuels. However, the higher yield (about 21% and could be expected
to be higher) of flowing bio-oil products were directly produced from microalgae while in
the fast pyrolytic process. Second, the quantity of algal cells used in the previous studies on
slow pyrolysis was very small and the entire process was discontinuous, whereas a greater
amount of high quality bio-oil can be continuously produced from continuously processing
microalgae feeds at a rate of 4 g min1 in the present work. In addition, the fast pyrolytic
process is time saving and lower energy input compared to the slow pyrolytic process of
the previous studies. All these advantages suggest that there is a commercial potential for
large-scale production of liquid fuels from microalgae by fast pyrolysis.
3.2. Chemical composition and characterization of bio-oils from microalgae
The results of thin layer chromatography of the oils shows that the bio-oils from C.
protothecoides and M. aeruginosa are similar in their chemical class compositions (Table 1).
They have rather high contents of asphaltenes, while the organic contents of the bio-oils
of C. protothecoides and M. aeruginosa are 35.9 and 29.99%, respectively (Table 1). The
saturated and polar fractions account for 1.14 and 31.17% of the bio-oils from microalgae
on average, while the saturated fraction accounts for less than 1% of the bio-oil from wood
and the polar fraction are 12% [19]. The differences in chemical class compositions between
the bio-oil from fast pyrolysis of microalgae and that of wood are probably because of the
Table 1
The chemical class compositions (wt.%) of bio-oils from fast pyrolysis of C. protothecoides and M. aeruginosa
Bio-oils

Saturated (%)

Aromatics (%)

Polar (%)

Asphaltenes (%)

C. protothecoides
M. aeruginosa

1.31
0.96

0.75
0.53

33.84
28.50

64.10
70.01

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X. Miao et al. / J. Anal. Appl. Pyrolysis 71 (2004) 855863

Table 2
Contents of the main chemical components in cells of C. protothecoides and M. aeruginosa
Strains

Protein (%)

Lipid (%)

Carbohydrate (%)

Ash (%)

Moisture (%)

Others (%)

C. protothecoides
M. aeruginosa

52.64
30.80

14.57
12.50

10.62
11.60

6.36
13.26

5.39
4.40

10.42
27.44

differences in the main chemical components of microalgae and wood. Table 2 shows the
main chemical components of C. protothecoides and M. aeruginosa. The main components
of microalgae are protein, lipid and carbonhydrate, and they constitute 6080% (Table 2),
while the main components of higher plants such as wood are hemicelluloses, cellulose
and lignin, they make up more than 95% [6,20,21]. The amount of hydrocarbons that
can be obtained from any component of biomass is limited by its percentage of carbon and
hydrogen [3], and thus lipids, proteins and carbonhydrates appear to be preferable to convert
into hydrocarbons than hemicelluloses, cellulose and lignin through pyrolytic reaction.
The gas chromatograph analyses of saturated fractions of n-hexane solubles of bio-oils
are given in Fig. 3. The analysis of saturated fraction from C. protothecoides bio-oil shows
that the straight-chain alkanes range from C10 to C30 (Fig. 3a), while the straight-chain
alkanes of saturated fraction of bio-oil from M. aeruginosa range from C10 to C28 (Fig. 3b),
however both of them exhibit a maximum in the range of C17 C19 (Fig. 3a and b). When
these results are compared to the diesel chromatogram, the distribution of straight-chain
alkanes are found to be similar to diesel fuel [22].
The elemental compositions and heating values of fast pyrolysis oils from C. protothecoides and M. aeruginosa are listed in Table 3. The differences in the main chemical components of microalgae and wood result in not only the different chemical class compositions of
their bio-oils, but also the different elemental compositions of oils. The high-quality bio-oils
are obtained from fast pyrolysis of microalgae. The contents of carbon and hydrogen of
bio-oils from microalgae are higher than those of oil from wood [17,19,23] (Tables 3 and 4),
whereas the oxygen content is lower than that of wood oil. The H/C and O/C molar ratios
are 1.72 and 0.26 on average (Table 3), while the H/C and O/C molar ratios of bio-oil from
wood are 1.38 and 0.37, respectively [19]. The bio-oils of microalgae are characterized by
low oxygen contents with higher H/C ratios (Table 3) than the bio-oil from wood, sunflower
bagasse and cotton straw and stalk [6,22,24]. The decrease in the oxygen contents of bio-oils
from microalgae compared to the bio-oil from higher plants such as wood is important because the high oxygen content is not attractive for the production of transport fuels. Bio-oil
products from C. protothecoides and M. aeruginosa have higher heating values of 30 MJ/kg
and 29 MJ/kg because of their higher contents of carbon and hydrogen and lower contents of

Table 3
Elemental compositions (wt.%) of bio-oils from fast pyrolysis of C. protothecoides and M. aeruginosa
Bio-oils

H/C

O/C

Heating value (MJ kg1 )

C. protothecoides
M. aeruginosa

62.07
60.99

8.76
8.23

19.43
20.95

9.74
9.83

1.72
1.71

0.24
0.27

30
29

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861

Fig. 3. Gas chromatograms of saturated fractions of n-hexane solubles of bio-oils from C. protothecoides (a) and
M. aeruginosa (b).

oxygen (Tables 3 and 4). The high nitrogen contents of bio-oils from microalgae (Table 4)
are due to chlorophyll and proteins.
The fast pyrolysis of biomass is complicated since the decomposition represents a large
number of reactions in parallel and series. Different kinds of biomass possess different reactions in pyrolytic process, which caused the complexity and difference in the compositions
of their bio-oils. Although the bio-oils from different biomass have different compositions,
the key properties of bio-oils for use as diesel substitute are viscosity, heating value, density
and stability [25]. Comparison of typical properties of fossil oil and bio-oils from fast pyrolysis of wood and microalgae are shown in Table 4. The pyrolysis oils from biomass usually
contain higher proportion of oxygen than fossil oil (Table 4), and thus they are quite reactive

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Table 4
Comparison of typical properties of fossil oil and bio-oils from fast pyrolysis of wood and microalgae
Properties

Typical value
Bio-oils

Fossil oil

Wood

Microalgae

C
H
O
N
S
Density
Viscosity (Pa s)

56.4%
6.2%
37.3%
0.1%
n.d.a
1.2 kg l1
0.040.20 (at 40 C)

61.52%
8.50%
20.19%
9.79%
n.d.
1.16 kg l1
0.10 (at 40 C)

Heating value
Stability

21 MJ kg1
Not as stable as fossil
fuels

29 MJ kg1
Not as stable as fossil fuels, but more
stable than the bio-oil from wood

83.087.0%
10.014.0%
0.051.5%
0.010.7%
0.055.0%
0.751.0 kg l1
21000 (depends on
temperature, density
and its contents etc.)
42 MJ kg1

n.d.: Not determined.

and not as stable as fossil fuels and their characteristics change rapidly during condensation
and under storage conditions [22]. Their utilization as fuels or sources of chemical feedstock
requires some form of upgrading to improve storage stability and heating value. However,
the pyrolysis oil from microalgae has lower content of oxygen than the bio-oil from wood
(Table 4), which makes it more stable than the bio-oil from wood. Compared with the bio-oil
from wood, the bio-oil from microalgae has higher heating value, lower viscosity and lower
density (Table 4). The heating value of bio-oil from microalgae is 29 MJ/kg on average,
which is about 1.4 times of that of wood (Table 4). These physical properties of bio-oil of
microalgae make it more suitable for fuel oil use than pyrolysis oils from lignocellulosic
materials.

4. Conclusion
Microalgae have advantages of higher photosynthetic efficiency, larger biomass, faster
growth and higher content of components preferable for pyrolysis compared to those lignocellulosic materials and been suggested as very good candidates for fuel production.
Through fluid bed fast pyrolysis system, a greater amount of high quality bio-oil can be
directly produced from continuous processing of microalgae feeds at a rate of 4 g min1 .
The bio-oil from fast pyrolysis of mocroalgae has a higher heating values of 29 MJ/kg,
which is about 1.4 times of that of wood. The lower oxygen contents of microalgae bio-oil
will make them have better storage stability than that of wood. The liquid fuels from fast
pyrolysis of microalgae can be used in many applications as direct substitutes for conventional fuels or as a source of chemicals. There still exist some problems to be solved in the
process of producing fuels from microalgae by pyrolysis. For example, there are challenges
to harvest the microalgae biomass at a economically feasible cost, to find a way for efficiently separating and collecting the liquid product of fast pyrolysis, to design and set up

X. Miao et al. / J. Anal. Appl. Pyrolysis 71 (2004) 855863

863

large-scale commercial installations for fast pyrolysis of microalgae and to reduce the cost
of fuel production. However, as an optimal resource of renewable fuels, microalgae may
play an important role in providing energy in the future.

Acknowledgements
The authors are thankful to the Multiphase Reaction Laboratory Institute of Process
Engineering, Chinese Academy of Science for having provided the fast pyrolysis apparatus.
This research was supported by the 863 project 2001AA514070 and project 40272054 and
key project 40332022 supported by NSFC.

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