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The direct pyrolysis and catalytic

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Fast microwave-assist ed pyrolysis of microalgae using microwave absorbent and HZSM-5 c…

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Microwave-assist ed pyrolysis of microalgae for biofuel product ion

Roger Ruan
 Bioresource Technology 101 (2010) 4593–4599

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

The direct pyrolysis and catalytic pyrolysis of Nannochloropsis sp. residue

for renewable bio-oils
Pan Pan a, Changwei Hu a,*, Wenyan Yang a, Yuesong Li a, Linlin Dong a, Liangfang Zhu a, Dongmei Tong a,
Renwei Qing b, Yong Fan b
a
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China
b
School of Life Science, Sichuan University, Chengdu, Sichuan 610064, China

a r t i c l e i n f o a b s t r a c t

Article history: Nannochloropsis sp. (a kind of green microalga) residue was pyrolyzed without catalyst or with different
Received 14 September 2009 amount of HZSM-5 catalyst in a fixed bed reactor in nitrogen flow. The effects of pyrolysis parameters
Received in revised form 17 January 2010 such as temperature and catalyst-to-material ratio on product yields were studied. The bio-oils obtained
Accepted 19 January 2010
were analyzed by elemental, GC–MS and FTIR analysis. The results indicated that the bio-oils from cat-
Available online 12 February 2010
alytic pyrolysis of Nannochloropsis sp. residue (BOCP) had lower oxygen content (19.5 wt.%) and higher
heating-value (32.7 MJ kg1) than those obtained from direct pyrolysis (BODP) which had an oxygen con-
Keywords:
tent of 30.1 wt.% and heating-value of 24.6 MJ kg1. The BODP mainly consisted of long carbon chain
Pyrolysis
Bio-oils
compounds with various terminal groups (LCTG), while the BOCP mainly consisted of aromatic hydrocar-
Microalgae bons. These properties of bio-oils demonstrated that the Nannochloropsis sp. residue can be used as a
Nannochloropsis sp. renewable energy resource and chemical feedstock.
HZSM-5 catalyst Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction directly as fuel due to their high oxygen content, high viscosity,
high corrosiveness and relative instability, and need to be up-
Presently, the widely used energy sources are still limited to the graded by complicated process (Czernik and Bridgwater, 2004;
conventional fossils such as coal, petroleum and natural gas, which Zhang et al., 2007). The poor quality of bio-oils is mainly attributed
are depleting, and their usage causes serious environmental prob- to the chemical components of lignocellulosic biomass (cellulose,
lems. The exploitation of renewable and environmentally friendly hemicellulose and lignin), thus exploiting more appropriate bio-
energy resources is urgent and significant. Biomass, mainly includ- mass is necessary and valuable.
ing crops, forestry products and marine products, is widespread on Microalga is a widely distributed low-grade water plant. Com-
the earth. With the exacerbation of energy crisis and environmen- pared with lignocellulosic biomass, microalgae as energy resource
tal deterioration, biomass as an environmentally friendly and have the following advantages: (1) microalgae have higher photo-
renewable energy resource has attracted more and more interests synthetic efficiency and higher biomass production (Peng et al.,
(Cercel, 2002; Goyal et al., 2008). 2001; Schenk et al., 2008); (2) microalgae can be cultivated in an
Biomass can be converted into fuel products by biological aquatic medium, and do not occupy arable land (Rodolfi et al.,
(fermentation and anaerobic digestion) or thermochemical (gasifi- 2009); (3) the chemical composition of microalgae can be modu-
cation, liquefaction) route. Among these conversion processes, lated easily by varying cultivation conditions, and high lipid con-
pyrolysis is considered to be an effective technology, by which bio- tent can be obtained (Rodolfi et al., 2009); (4) microalgae can
mass can be converted to valuable bio-oils, char and gaseous prod- utilize the salt and organic matter derived from waste water as fer-
ucts (Mohan et al., 2006). Especially, pyrolysis bio-oils are very tilizers (Schenk et al., 2008). In addition, microalgae can effectively
attractive because of their high energy density and convenience reduce greenhouse gas concentration in the atmosphere by their
in usage, storage and transport (Islam et al., 2004). Though numer- high capability in fixing carbon dioxide (Chiu et al., 2009;
ous progresses on producing pyrolysis bio-oils have been reported Kishimoto et al., 1994). So the exploitation and utilization of mic-
with lignocellulosic biomass as raw materials (Karaosmanoglu roalgae for fuel production can gain both economic and environ-
et al., 1999; Mohan et al., 2006; Muller-Hagedorn and Bockhorn, mental benefits. However, for the large-scale usage of
2007; Putun et al., 2004), the bio-oils obtained can not be used microalgae, there are still some fundamental challenges to be dealt
with, such as the high cost of microalgae cultivation and its collec-
* Corresponding author. Tel.: +86 28 88835525; fax: +86 28 85411105. tion, as well as the efficiency in microalgae utilization (Li et al.,
E-mail addresses: [email protected], [email protected] (C. Hu). 2007; Liliana et al., 2009).

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.01.070
4594 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599

Generally, microalgae contain varying amounts of lipids, sugars, Lipid in cells of Nannochloropsis sp. was extracted by the mixed
proteins and pigments etc. Presently, the attentions about the con- solvent of ethylether and petroleum ether (1/2, v/v), and then used
version of microalgae to fuel products mostly focus on the lipid for the production of bio-diesel by esterification and transesterifi-
which can be used to produce high-quality bio-diesel by the con- cation. After residual solvent in algal residue was removed by vac-
ventional esterification and transesterification (Chisti, 2007; Li uum distillation, the algal residue which occupied approximately
et al., 2007; Miao and Wu, 2006). However, after lipid is extracted 70 wt.% in cells dry weight was used as pyrolysis material. The
from microalgae cells (Li et al., 2007), numerous residues of micro- proximate and ultimate analysis of Nannochloropsis sp. residue
algae which mainly contain almost all soluble polysaccharide, pro- was shown in Table 1. Since metal salts contained in biomass ex-
tein and some residual lipid are thrown away or sometimes used as erted a significant impact on the pyrolysis process (Ross et al.,
animal feed. (Liliana et al., 2009) With the development of technol- 2008; Williams and Horne, 1994a), the contents of metals in the
ogy in producing low-cost fuel products derived from microalgae, sample were determined by Inductively Coupled Plasma Spec-
the utilization of algal residues will become significant. trometry (ICP). The result was also listed in Table 1.
Nannochloropsis sp. has a high lipid content (about 46%, deter- The HZSM-5 used in the catalytic pyrolysis of Nannochloropsis
mined with Bligh–Dyer method, using methyl alcohol–chloroform sp. residue was purchased from Nankai University. It had elliptical
mixture (2/1, v/v) as the extraction solvent), and is considered to pore of 0.56 nm diameter, with a silica–alumina ratio of about 25
be a promising green microalgae for fuel products (Gouveia and and pore volume of 0.19 cm3 g1. The surface area was
Oliveira, 2009; Rebolloso-Fuentes et al., 2001). In the present work, 347.9 m2 g1. Before use, HZSM-5 was activated in a muffle furnace
the direct pyrolysis of Nannochloropsis sp. residue was studied. at 400 °C under air atmosphere for 4 h, with a heating rate of
In addition, based on numerous researches on catalytic pyroly- 10 °C min1.
sis of lignocellulosic biomass, catalytic pyrolysis by using molecu-
lar sieves as catalysts can not only effectively upgrade the quality
of bio-oils but also adjust the components of bio-oils to meet dif- 2.2. Experimental apparatus
ferent demands (Adjaye and Bakhshi, 1995; Demiral and S ß ensöz,
2008; Vitolo et al., 1999; Williams and Horne, 1995a; Williams A fixed bed reactor designed by ourselves was used as experi-
and Nugranad, 2000). Molecular sieves are well-known heteroge- mental apparatus. The schematic diagram of the reactor was
neous catalysts used in petroleum industry, and have been suc- shown in Fig. 1. The outer tube was 35 mm diameter  600 mm
cessfully applied in the interconversion of hydrocarbons, such as height. Nannochloropsis sp. residue (1 g) and catalyst (different
alkylation, isomerization, aromatization and thermal cracking amount) were mixed and packed in the inner vessel (25 mm diam-
reactions. Among various molecular sieve catalysts, HZSM-5 has eter  120 mm height), and were heated by an electric furnace.
gained great favors. ZSM-5 is an aluminosilicate zeolite with a high Temperature was controlled by a temperature controller (SKW-
silica-to-alumina ratio and strong acidity. Its structure is based on 100). Nitrogen as a carrier gas was ventilated to the reactor from
channels with insecting tunnels. The substitution of H+ for Na+ the inlet located in the top of the reactor and its flow rate was con-
made the acidity of zeolite stronger, which facilitates the conver- trolled by a flow meter. A condenser (ice trap) connected at the exit
sion of hydrocarbons, such as thermal cracking (Pujadóa et al., of the reactor was used to collect the liquid products.
1992). At present, most studies are aiming at the pyrolysis or cat-
alyzed pyrolysis of lignocellulosic biomass to obtained bio-oil (De-
miral and Sßensöz, 2008). And there is no literature available 2.3. Experimental procedure
concerning the direct pyrolysis or catalyzed pyrolysis of algal res-
idue to produce bio-oils. This paper will give some primary results. The direct pyrolysis of Nannochloropsis sp. residue was per-
formed in the fixed bed reactor mentioned above. The material
was heated by an electric furnace with a heating rate of
2. Experimental 10 °C min1 from room temperature to the final temperature, and
then kept for 2 h at the final temperature. The volatiles produced
2.1. Material and catalyst in the pyrolysis process were swept out by carrier gas with a flow
rate of 30 ml min1. The condensable components in volatiles
Nannochloropsis sp. was cultivated in laboratory. The culture formed liquid products which were collected in the condenser,
medium was artificial seawater concocted by ourselves (using f/2 and the incondensable components in volatiles formed gaseous
medium) (Guillard, 1975). Irradiance provided by fluorescent products which were collected in a gas bag.
lamps was constant at 70 lmol m2 s1 and the ambiance temper- In the catalytic pyrolysis experiment of Nannochloropsis sp. res-
ature was maintained at 23 ± 0.2 °C. Cells of Nannochloropsis sp. idue, the same fixed bed reactor was used. Catalyst and material
were collected by centrifugation and washed with distilled water, were mixed directly at the ratio from 0.2/1 to 1/1, and then placed
and then dried in a vacuum desiccator at 65 °C for 24 h. The consti- in the inner vessel. Other experiment parameters were the same as
tution of dry Nannochloropsis sp. was listed in Table 1. those in the direct pyrolysis experiment.

Table 1
The proximate, ultimate and metal analysis of Nannochloropsis sp. residuea.

Proximate analysis (wt.%) Ultimate analysis (wt.%) Metal analysis (ppm)

Moisture 7.0 C 44.10 Ca 5503
Volatile 63.5 H 7.09 K 1660
Fixed C 19.6 N 5.51 Na 893
Ash 9.9 Ob 33.40 Mg 7915
Heating-valuec 20.7 MJ kg1

HHV (MJ kg1) = (3.55 C2  232 C  2230 H + 51.2 C  H + 131 N + 20600)  103.
a
Analyzed as received, after lipid in cells of Nannochloropsis sp. was extracted according to the depiction in the text.
b
By difference, O (%) = 100-C–H–N-Ash sed as received.
c
Heating-value was calculated by the following formula (Friedl et al., 2005).
 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599 4595

thermocouple nitrogen 40 °C for 2 min then to 90 °C with the heating rate of 25 °C min1,
and kept for 15 min at 90 °C; inlet temperature: 70 °C; detector
temperature: 140 °C). An Elementar Vario El IV analyzer was used
to determine the elemental composition of bio-oils. The infrared
spectra analysis of bio-oils was conducted using a NEXUS 670-FTIR
infrared spectrometric analyzer. The compounds in bio-oils were
determined by a gas chromatography–mass spectrometry (Agilent
inner vessel 5973 GC–MS: column: DB-5; inlet temperature: 250 °C; detector
temperature: 230 °C; helium flow: 16 ml min1; mode: split).

electric furnace
3. Results and discussion

3.1. The effect of temperature on the direct pyrolysis of

outer tube Nannochloropsis sp. residue
gas bag
The yields of various products obtained from the direct pyroly-
sis of Nannochloropsis sp. residue as a function of final pyrolysis
condenser
temperature were presented in Fig. 2. As can be seen, the yield of
liquid product was low at 300 °C, and then markedly increased
Fig. 1. The schematic diagram of the fixed bed reactor. with increasing temperature, while the highest yield of 47.6 wt.%
was obtained at 400 °C. Above 400 °C, the yield of liquid product
gradually decreased. The liquid product obtained in our experi-
The total yield of liquid products was calculated by the weight
ments was a mixture of an oily phase (upper phase) and an aque-
difference of the condenser before and after reaction. Oily phase
ous phase (lower phase), which separated automatically. The
(defined as bio-oils) and aqueous phase of liquid product were sep-
change of the bio-oil yield in upper phase had a similar trend to
arated and weighted respectively. Mass of char was determined by
that of liquid product with increasing temperature. And the maxi-
weight, and the weight of catalyst needed to be subtracted for the
mum bio-oil yield of 31.1 wt.% was obtained at 400 °C. The yield of
catalytic process. Coke on the catalyst was reckoned to the char be-
char markedly decreased from 45.3 to 24.2 wt.%, while the yields of
cause of the difficulty of separating coked catalyst powder from
aqueous and gaseous product gradually rose from 13.8 to 20.0 wt.%
reaction residue in this study. And the gas yield was calculated
and from 18.9 to 33.5 wt.%, respectively, as the pyrolysis tempera-
by overall mass balance. The yields of various products were calcu-
ture rose from 300 to 500 °C. Table 2 showed the yields of various
lated as follow:
gaseous products. It could be seen that the gaseous product con-
Y L ¼ ðW L =W M Þ  100ð%Þ; Y A ¼ ðW A =W M Þ  100ð%Þ; sisted large amount of CO2. Among various gaseous hydrocarbons,
Y o ¼ ðW o =W M Þ  100ð%Þ ¼ Y L  Y A ; the content of CH4 was the highest. The total yield of gaseous
hydrocarbons markedly increased from 0.12 to 5.12 wt.% as the
Y C ¼ ðW C =W M Þ  100ð%Þ; Y G ¼ 1  ðY L þ Y C Þ
pyrolysis temperature increased from 300 to 500 °C.
where YL denoted the yield of liquid product; WL, the weight of li- At lower temperature, the yield of oil/gas was low. This might
quid product; WM, the weight of material; YA, the yield of aqueous be caused by the low conversion of raw material on the one hand,
product; WA, the weight of aqueous product; Yo, the yield of bio-oil; and additionally, various components in algal residue could not be
Wo, the weight of bio-oil; YC, the yield of char; YG, the yield of gas- vaporized and pyrolyzed adequately. Thus the yield of ‘‘char” was
eous product. relatively higher. With increasing temperature, the volatiles de-
In the present work, experiments were divided into three series. rived from the pyrolysis of materials gradually increased. These
The first series of experiments was performed to investigate the ef-
fect of temperature on product yields in the direct pyrolysis pro-
cess. The final pyrolysis temperature was maintained at 300, 350, liquid products (YL)
400, 450 and 500 °C, respectively. The second series of experiments bio-oils (YO)
was performed to investigate the effect of catalyst-to-material ra- 60 aqueous products (YA)
tio (0/1, 0.2/1, 0.4/1, 0.6/1, 0.8/1 and 1/1, wt/wt) on product yields. char (YC)
In this series of experiments, the final temperature of 400 °C was 50 gaseous products (YG)
chosen. The third series of experiments was carried out to deter-
mine the effect of temperature (from 300 to 500 °C) on product 40
yields in the catalytic pyrolysis process. The catalyst-to-material
Yield(wt%)

ratio was kept at 1/1 in all experiments in the third series.

30

2.4. Characterization
20
Gaseous product collected in the gas bag was analyzed by two
different gas chromatography analyzers. CO, CO2 and H2 were 10
determined by GC7890T using a 5A molecular sieve column with
a thermal conductivity detector (TCD) and nitrogen as the carrier
0
gas (column temperature: 80 °C; inlet temperature: 90 °C; detector
300 350 400 450 500
temperature: 120 °C). Gaseous hydrocarbons were analyzed by SP- o
Temperature( C)
6800A in temperature programming using a column packed with
porapak Q with a thermal conductivity detector (TCD) and nitrogen Fig. 2. The effect of temperature on the product yields in the direct pyrolysis
as the carrier gas (column temperature: column was heated to process.
4596 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599

Table 2
liquid products (YL)
The yields (wt.%) of various gaseous products at different temperature in the direct
pyrolysis process. bio-oils (YO)
a
60 aqueous products (YA)
Temperature H2 CO2 CO CH4 C2H4 C2H6 Cn
char (YC)
300 °C 0.05 14.49 4.28 0.12 ndb nd 0.12
350 °C 0.15 18.56 3.80 0.93 nd trc 0.93 50 gaseous products (YG)
400 °C 0.23 18.73 3.68 0.97 tr 0.83 1.80
450 °C 0.45 21.40 3.66 2.75 tr 1.79 4.54
500 °C 0.52 25.01 2.86 3.44 0.84 0.84 5.12 40
a

Yield(wt%)
The total yields of gaseous hydrocarbons.
b
Not detected. 30
c
Trace amount.

20
volatiles could undergo various reactions like dehydration and
thermal cracking at higher temperature, and generated polar and 10
nonpolar organic compounds with low molecule weight such as
water (Mohan et al., 2006; Putun et al., 2004). Consequently, the
0
yields of aqueous product, gaseous product and bio-oil gradually
0/1 0.2/1 0.4/1 0.6/1 0.8/1 1/1
increased as the temperature increased from 300 to 400 °C. How-
catalyst-to-material ratio(wt/wt)
ever, once the pyrolysis temperature exceeded 400 °C, a part of vol-
atiles which should form bio-oils at lower pyrolysis temperature Fig. 3. The effect of the catalyst-to-material ratio on the product yields.
could be cracked further into more incondensable gaseous prod-
ucts, and then caused the decrease of bio-oils yield.
These results indicated that the optimal temperature range un- increasing catalyst-to-material ratio. At 400 °C, the total yield of
der the present conditions for the direct pyrolysis of Nannochlorop- gaseous hydrocarbons, which was 1.80 wt.% in the direct pyrolysis
sis sp. residue was 350–450 °C, which was much lower than that process, increased to 3.08 wt.% when catalysts-to-material ratio
for the direct pyrolysis of lignocellulosic biomass (commonly was 0.2/1, and further increased to 5.78 wt.% when catalyst-
450–650 °C) (Karaosmanoglu et al., 1999; Qi et al., 2006). It could to-material ratio was 1/1. We gathered that the increase of
be mainly attributed to the following three factors. Firstly, Nanno- catalyst-to-material ratio enhanced the direct contact between
chloropsis sp. residue mainly contains lipid, soluble polysaccharide heterogenous catalyst and solid materials, and promoted the ther-
and protein, which can be pyrolyzed more easily than lignocellu- mal cracking and secondarily reactions of reactants to produce
losic feedstocks (Mohan et al., 2006). Secondly, the cell structure more gas and aqueous products.
of Nannochloropsis sp. is relatively incompact compared to ligno-
cellulosic biomass, and may be destroyed further in the extraction
process. Thirdly, Nannochloropsis sp. residue contains more inor- 3.3. The effect of temperature on the catalytic pyrolysis of
ganic ions than some typical lignocellulosic biomass such as wood, Nannochloropsis sp. residue
as demonstrated by the ICP analysis results shown in Table 1. The
higher metal salt content can also lower the pyrolysis temperature The catalyst-to-material ratio was chosen to be ratio 1/1 in all
because of its notable catalytic effect (Ross et al., 2008; Williams experiments of this series. The product yields obtained at different
and Horne, 1994a). temperature were shown in Fig. 4. It can be seen that the yield of
liquid product sharply increased with increasing temperature
when pyrolysis temperature was below 400 °C. Above 400 °C, the
3.2. The effect of the catalyst-to-material ratio on the catalytic yield of liquid product had only a slight decrease. The yield of
pyrolysis of Nannochloropsis sp. residue bio-oil rose from 11.2 to 19.7 wt.% as the temperature rose from
300 to 400 °C, and then decreased to 16.9 wt.% at 500 °C. The yield
Based on the results of the first series of experiments, 400 °C of aqueous product continuously rose with increasing tempera-
was chosen as pyrolysis temperature in this series of experiments. ture. Compared with the first series of experiments, the yield of
The yields of various products at different catalyst-to-material ra- bio-oil was lower, whereas the yield of aqueous product was high-
tio were given in Fig. 3. As can be seen, the yield of liquid product er in the presence of HZSM-5 catalyst at all pyrolysis temperatures.
had a notable decrease with a simultaneous increase of char from The yield of char markedly decreased as the pyrolysis tempera-
28.01% to 34.56%, as catalyst HZSM-5 was added into reaction ture increased. Compared with the yield of char obtained in the di-
material. It can be explained as the coking trend over molecular rect pyrolysis process, the yield of char obtained in the catalytic
sieves (Vitolo et al., 1999). When the volatile intermediates formed pyrolysis process was higher when temperature was below
in the primary pyrolysis process passed over the catalyst surface or 400 °C, but was lower when temperature was above 400 °C. This
went deep into its micropores, the high acidity of catalyst might phenomenon was not only resulted from more decomposition of
enhance various secondarily reactions of the intermediates such char at higher temperature but also related to the decrease of coke
as repolymerization and aromatization. As a result, bio-oil reduced. over catalyst surface. It can be speculated that coke on catalyst sur-
Cokes were remained on the catalyst surface and in its micropores, face could be easily formed at relatively low temperature, and
with more gas and aqueous products produced. partly decomposed at higher temperature over 400 °C when Nan-
When the catalyst-to-material ratio increased from 0.2/1 to 1/1, nochloropsis sp. residue is used as pyrolysis material. This tendency
the yield of liquid product had a slight change. The yield of bio-oil was similar to the results reported by Williams et al. that is, the
gradually decreased from 25.1 to 20.7 wt.%, while the yields of coke formation on catalyst ZSM-5 decreased with temperature
aqueous product and gaseous product gradually increased from increasing from 400 to 600 °C when rice husks was used for pyro-
15.8 to 24.9 wt.% and from 24.5 to 29.8 wt.%, respectively. The lysis (Williams and Nugranad, 2000).
yields of gaseous products were given in Table 3. It was worth not- The yield of gaseous product sharply increased with increasing
ing that the total yield of gaseous hydrocarbons increased with temperature. The detailed components and their yields in gaseous
 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599 4597

Table 3
The yields (wt.%) of various gaseous products at different catalyst-to-material ratios (wt/wt) at 400 °C.

Catalyst-to-material ratio H2 CO2 CO CH4 C2H4 C2H6 C3H6 Cna

b c
0/1 0.23 18.73 3.68 0.97 tr 0.83 nd 1.80
0.2/1 0.26 18.25 2.94 2.16 tr 0.92 nd 3.08
0.4/1 0.18 18.88 2.38 2.02 0.57 0.75 tr 3.34
0.6/1 0.14 19.97 1.39 1.95 1.05 1.05 0.23 4.28
0.8/1 0.16 20.76 1.17 1.85 0.92 1.10 0.51 4.65
1/1 0.14 20.40 0.72 2.38 1.42 1.23 0.75 5.78
a
The total yields of gaseous hydrocarbons.
b
Not detected.
c
Trace amount.

liquid products (YL) much higher than those in original materials (44.10% and 7.09%,
bio-oils (YO) respectively). After HZSM-5 catalyst was introduced to pyrolysis
60 aqueous products (YA) process, the contents of carbon and hydrogen in the BOCP in-
char (YC) creased to 65.21% and 9.83%, respectively. Meanwhile, the oxygen
50 gaseous products (YG) concentration decreased from 33.4% in original materials, to
30.09% in the BODP, and further to 19.53% in the BOCP. The results
demonstrated that the catalytic pyrolysis using HZSM-5 as catalyst
40
could efficiently decrease the oxygen content of bio-oils, and in-
crease the heating-value of bio-oils, though the yield of BOCP
Yield(wt%)

30 was lower than that of BODP at the same reaction conditions.

Nitrogen content of bio-oils could derive from the protein and
20
chlorophyll of algal residues, and was generally higher in those
bio-oils obtained from lignocellulosic biomass. In addition, the re-
sults implied that catalytic pyrolysis by using HZSM-5 as catalyst
10 could not reduce the nitrogen content under present condition.
According to the elemental analysis, bio-oils obtained from the
0 Nannochloropsis sp. residue contained more carbon, more hydro-
300 350 400 450 500 gen, less oxygen, and possessed higher heating value, compared
Temperature( C)
o to the bio-oils obtained from lignocellulosic biomass. And the for-
mer bio-oil would be more suitable to be used as engine fuels.
Fig. 4. The effect of temperature on the product yields in the catalytic pyrolysis The compounds identified in the bio-oils were divided into four
process. kinds – chain hydrocarbons, aromatic compounds, long carbon
chain compounds with various terminal functional groups (LCTG)
and others. Table 6 showed the total relative contents of the four
product were given in Table 4. As can be seen, the total yield of gas-
kinds of compounds. The chain hydrocarbons mainly contained
eous hydrocarbons obviously increased with increasing tempera-
dodecane and 3,7,11,15-tetremethyl-2-hexadecene. The aromatic
ture. Moreover, the yield of gaseous hydrocarbons obtained in
compounds mainly consisted of phenol, alkylated benzenes and
the catalytic pyrolysis process was higher than that obtained in
naphthalene such as toluene, p-xylene and 2-methyl-naphthalene.
the direct pyrolysis process at all pyrolysis temperatures.
The LCTG largely consisted of fatty acids and their methyl ester,
with long carbon chain amide and nitrile. Other products were
3.4. Analysis of the bio-oils
mainly the oxygenous and nitrogenous compounds such as dian-
hydro mannitol, indole and pyrrole.
The bio-oils obtained in the direct pyrolysis process at 400 °C
The results of GC–MS analysis showed that there were great dif-
(BODP) and in the catalytic pyrolysis process with the catalyst-
ferences between the BODP and the BOCP in chemical component.
to-material of 1/1 at 400 °C (BOCP) were analyzed comparatively
The relative content of the aromatic compounds in the BOCP
by elemental, FTIR and GC–MS analysis.
reached 48.60%, and was much higher than that in the BODP
Table 5 showed the characteristics of the BODP and BOCP in
(10.89%). A small quantity of aromatic compounds like phenol, 4-
comparison with wood pyrolysis bio-oils and heavy fuel oil. It
methyl-phenol and toluene, were detected with low concentra-
can be seen from Table 5 that the contents of carbon and hydrogen
tions in the BODP, whereas numerous aromatic hydrocarbons,
in the BODP were 56.13% and 7.13%, respectively, which were
which were various alkylated benzene and alkylated naphthalene,
were identified with high concentrations in the BOCP. Among the
Table 4 compounds in the BOCP, the relative content of p-xylene was the
The yields (wt.%) of various gaseous products at different temperature in the catalytic highest and reached 12.24%. However, the relative content of LCTG
pyrolysis process. in the BOCP markedly decreased compared to the BODP. Most of
Temperature H2 CO2 CO CH4 C2H4 C2H6 C3H6 Cna LCTG, which were present in the BODP with high relative concen-
trations, such as pentadecanenitrile and hexadecanenitrile, were
300 °C 0.05 9.55 2.58 0.13 trb tr tr 0.13
350 °C 0.08 14.78 4.37 0.82 0.20 0.21 tr 1.23 not detected in the BOCP.
400 °C 0.14 20.40 0.72 2.38 1.42 1.23 0.75 5.78 The FTIR analysis of the BODP and BOCP were also in consistent
450 °C 0.18 22.70 1.56 2.67 1.25 0.93 1.04 5.89 with the results mentioned above (see to the Supplementary mate-
500 °C 0.17 27.47 0.63 3.50 1.99 1.21 0.44 7.14 rial). It was proved that BOCP contained more alkyl functional
a
The total yields of gaseous hydrocarbons. groups (especially substituted aromatic compounds) and less oxy-
b
Trace amount. genated functional groups than BODP.
4598 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599

Table 5
The characteristics of BODP and BOCP.

BODP BOCP Wood pyrolysis bio-oilsb Heavy fuel oilb

Ultimate analysis (wt.%)
C 56.13 65.21 54–58 85
H 7.63 9.83 5.5–7.0 11
N 5.34 5.43 0–0.2 0.3
Oa 30.09 19.53 35–40 1.0
Elemental ratio
H/C 1.63 1.89 – –
O/C 0.40 0.22 – –
Empirical formula CH1.63O0.40N0.08 CH1.89O0.22N0.06 – –
Heating-value(MJ kg1) 24.4 c 32.2 c 16–19 40
a
By difference, O (%) = 100-C–H–N.
b
Derived from the reference Czernik and Bridgwater (2004).
c
Heating-value was calculated using the following formula (Friedl et al., 2005) HHV (MJ kg1) = (3.55 C2  232 C  2230 H + 51.2 C  H + 131 N + 20600)  103.

Table 6
The molecular formula and relative content of typical compounds in the bio-oils.

Categories Components Formula Relative content (%)a

BODP BOCP
Chain hydrocarbons 12.25 8.91
Dodecane C12H26 6.32 3.22
3,7,11,15-Tetremethyl-2-hexadecene C20H40 4.59 1.28
Aromatic compounds 10.89 48.6
Benzene C6H6 ndb 0.67
Toluene C7H8 0.53 3.24
p-Xylene C8H10 0.22 12.24
1-Ethyl-2-methyl-benzene C9H12 nd 3.41
1,2,3-Trimethyl-benzene C9H12 nd 2.54
2-Methyl-naphthalene C11H10 nd 6.54
1,4,6-Methyl-naphalene C13H14 nd 1.14
Phenol C6H6O 1.43 nd
4-Methyl-phenol C7H8O 1.84 nd
LCTG 62.24 24.85
Tetradecanoic acid C13H27COOH 3.62 1.96
Methyl palmitate C16H34O2 1.17 nd
(Z)-11-Hexadecenoic acid C15H29COOH 13.04 10.06
n-Hexadecanoic acid C15H31COOH 10.03 8.27
Oleic acid C17H33COOH 1.94 0.98
(Z)-9-Hexadecenoic-acid methyl ester C17H34O2 1.06 nd
Stearic acid C17H35COOH 4.40 nd
Tetradecanamide C13H27CONH2 1.45 nd
Hexadecanamide C15H31CONH2 4.06 2.14
Pentadecanenitrile C14H31CN 1.94 nd
Hexadecanenitrile C16H33CN 1.64 nd
Others 14.62 17.64
Dianhydro mannitol C6H10O4 8.53 4.25
Indole C8H6N 3.97 nd
a
The amount of the compounds was evaluated through the peek area; no response factors were introduced.
b
Not detected.

3.5. Discussions sult was attributed to the different composition of reaction

materials. The main components in lignocellulosic biomass were
The bio-oils obtained from the direct pyrolysis of lignocellulosic cellulose, lignin and hemi-cellulose, while microalgae contained
biomass were multicomponent mixtures consisted of hundreds of largely residual lipid (mainly long chain fatty acid ester and free
compounds such as acids, aldehydes, ketones, alcohols, phenols fatty acid), which could be converted into various hydrocarbons
and their derivatives and so on (Karaosmanoglu et al., 1999; Qi through decarboxylation and thermaldegradation processes.
et al., 2006). Almost all these compounds were with low heating- In previous researches, HZSM-5 catalyst was used to upgrade
value, high acidity and instability due to the oxygenous functional vapors derived from the pyrolysis of lignocellulosic biomass in or-
groups. The BODP from microalgae residue were absolutely differ- der to improve the quality of bio-oils, and the increase in the con-
ent from the bio-oil from lignocellulosic biomass pyrolysis in centration of aromatic compounds in the bio-oils was observed
chemical composition. The most attractive chain hydrocarbons, (Williams and Horne, 1995a; Williams and Nugranad, 2000). In
nearly absent in lignocellulosic biomass pyrolysis bio-oils, were our experiments, the same increase in the concentration of aro-
detected with high concentration (12.25%) in the BODP. And alde- matic compounds was found in the BOCP. Nevertheless, bio-oils
hydes, ketones and phenolic compounds which were present with obtained from the HZSM-5 catalyzed pyrolysis of lignocellulosic
high concentrations in lignocellulosic biomass pyrolysis bio-oils biomass contained various types of aromatic compounds such as
were hardly detected in the BODP. The main oxygenated com- benzene, naphthalene, phenanthrene, pyrene, phenol and their
pounds in the BODP were fatty acid and dehydrated sugars. This re- derivatives, while the BOCP contained only several alkylated ben-
 P. Pan et al. / Bioresource Technology 101 (2010) 4593–4599 4599

zene and alkylated naphthalene (Williams and Horne, 1995a; Wil- Cercel, H.F., 2002. Production and characterization of pyrolysis liquids from
sunflower-pressed bagasse. Bioresour. Technol. 85, 113–117.
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search Program of China (973 program, No. 2007CB210203) and Schenk, P.M., Thomas-Hall, S.R., Stephens, E., Marx, U.C., Mussgnug, J.H., Posten, C.,
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microalgae for biodiesel production. Bioenergy Res. 1, 20–43.
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University are greatly appreciated. The supervision of academician Williams, P.T., Horne, P.A., 1994a. The role of metal salts in the pyrolysis of biomass.
Renew. Energy 4, 1–13.
Qingshi Zhu is highly acknowledged. Williams, P.T., Horne, P.A., 1994b. Characterisation of oils from the fluidised bed
pyrolysis of biomass with zeolite catalyst upgrading. Biomass Bioenergy 7, 223–
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Appendix A. Supplementary data
Williams, P.T., Horne, P.A., 1995a. The influence of catalyst type on the composition
of upgraded biomass pyrolysis oils. J. Anal. Appl. Pyrol. 31, 39–61.
Supplementary data associated with this article can be found, in Williams, P.T., Horne, P.A., 1995b. The influence of catalyst regeneration on the
the online version, at doi:10.1016/j.biortech.2010.01.070. composition of zeolite upgraded biomass pyrolysis oils. Fuel 74, 1839–1851.
Williams, P.T., Nugranad, N., 2000. Comparison of products from the pyrolysis and
catalytic pyrolysis of rice husks. Energy 25, 493–513.
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