The Direct Pyrolysis and Catalytic Pyrolysis of Nannochloropsis Sp. Residue For Renewable Bio-Oils
The Direct Pyrolysis and Catalytic Pyrolysis of Nannochloropsis Sp. Residue For Renewable Bio-Oils
The Direct Pyrolysis and Catalytic Pyrolysis of Nannochloropsis Sp. Residue For Renewable Bio-Oils
Bioresource Technology
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
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.
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
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.
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%)
Table 5
The characteristics of BODP and BOCP.
Table 6
The molecular formula and relative content of typical compounds in the bio-oils.
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Acknowledgements Rodolfi, L., Zittelli, G.C., Bassi, N., Padovani, G., Biondi, N., Bonini, G., Tredici, M.R.,
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This work is financially supported by the National Basic Re- 102, 100–112.
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.,
the Special Research Fund for the Doctoral Program of Higher Edu- Kruse, O., Hankamer, B., 2008. Second generation biofuels: high-efficiency
microalgae for biodiesel production. Bioenergy Res. 1, 20–43.
cation of China (No. 20050610013). The characterization of the cat- Vitolo, S., Seggiani, M., Frediani, P., Ambrosini, G., Politi, L., 1999. Catalytic upgrading
alyst and bio-oils from Analytical and Testing Center of Sichuan of pyrolytic oils to fuel over different zeolites. Fuel 78, 1147–1159.
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–
236.
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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