See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/230782615

Pyrolysis characteristics and kinetics of the

alga Saccharina japonica

Article in Bioresource Technology August 2012

DOI: 10.1016/j.biortech.2012.07.097 Source: PubMed

CITATIONS READS

37 96

5 authors, including:

Hoang Vu Ly Jinsoo Kim

Kangwon National University Kyung Hee University
20 PUBLICATIONS 169 CITATIONS 143 PUBLICATIONS 2,496 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Hoang Vu Ly on 22 July 2015.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
 Bioresource Technology 123 (2012) 445451

Contents lists available at SciVerse ScienceDirect

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

Pyrolysis characteristics and kinetics of the alga Saccharina japonica

Seung-Soo Kim a,, Hoang Vu Ly b, Gyeong-Ho Choi a, Jinsoo Kim b,, Hee Chul Woo c
a
Department of Chemical Engineering, Kangwon National University, 1 Joongang-ro, Samcheok, Gangwon-do 363-883, Republic of Korea
b
Department of Chemical Engineering, Kyung Hee University, 1 Seocheon-dong, Yongin, Gyeonggi-do 446-701, Republic of Korea
c
Division of Applied Chemical Engineering, Pukyong National University, 365 Sinseon-ro, Nam-gu, Busan 608-739, Republic of Korea

h i g h l i g h t s

" Pyrolysis for Saccharina japonica.

" Determination of global kinetic parameters including activation energy from TG analysis.
" Inuence of pyrolysis temperature and residence time on product yields and compositions.
" Calculation of kinetic parameters from a lumped kinetic model.

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

Article history: Saccharina japonica can be converted to bio-oil, gas, and char through pyrolysis. In this study, the pyro-
Received 19 January 2012 lysis characteristics of S. japonica were investigated using a thermogravimetric analyzer. Most of the
Received in revised form 20 June 2012 materials decomposed between 200 C and 350 C at heating rates of 1020 C/min. The apparent activa-
Accepted 25 July 2012
tion energy increased from 102.5 kJ mol1 to 269.7 kJ mol1 with increasing pyrolysis conversion. The
Available online 3 August 2012
kinetic parameters of S. japonica pyrolysis were determined using nonlinear least-squares regression of
the experimental data assuming rst-order kinetics. The kinetic rate constants indicated that the pre-
Keywords:
dominant reaction pathway was B (bio-oil) to C (gas; C1C4), rather than A (S. japonica) to B (bio-oil)
Biomass
Macroalgae
and/or to C (gas; C1C4). The proposed lumped kinetics of S. japonica pyrolysis offers a guide for the
Saccharina japonica scale-up of the process at the research and industrial level.
Lumped kinetic model 2012 Elsevier Ltd. All rights reserved.
Thermogravimetric analysis

1. Introduction In the present study, characteristics and kinetics of Saccharina

Macroalgae are a potential source of renewable energy (Um and
Kim, 2009; Demirbas, 2010; Lee et al., 2010; Adams et al., 2011), as
well as of polysaccharides such as laminarans, alginic acids, and
fucoidans (Vishchuk et al., 2011). Marine biomass such as macroal-
gae, which are primarily composed of polysaccharides, can be con-
verted to fuel such as bio-alcohol (Adams et al., 2009; Borines et al.,
2011) or bio-oil (Ross et al., 2008, 2009; Bae et al., 2011) by fer-
mentation and pyrolysis, respectively.
To understand the pyrolysis characteristics of macroalgae, ther-
mogravimetric analysis (TGA) has been performed (Ross et al.,
2009; Li et al., 2010, 2011), and Maddi et al. (2011) performed a
comparative study of the pyrolysis of algal biomass from natural
lake blooms and lignocellulosic biomass.
Corresponding authors. Tel.: +82 33 570 6544; fax: +82 33 570 6535 (S.-S. Kim),
tel.: +82 31 201 2492 fax: +82 31 202 1946 (J. Kim).
E-mail addresses: sskim2008@kangwon.ac.kr (S.-S. Kim), jkim21@khu.ac.kr (J.
Kim).
japonica pyrolysis were investigated to obtain information regard-
ing the types of fuel (gas, bio-oil, or bio-char) that can be gener-
ated. Global kinetic parameters including activation energy were
determined during pyrolysis in TGA. The kinetic parameters from
a lumped kinetic model were also calculated. Kinetic research is
useful in helping to understand the thermal degradation process
and provide information for designing a pyrolysis process using
macroalgae.
2. Experimental
2.1. Thermogravimetric analysis
S. japonica was obtained from the Cleaner Production Institute
of Pukyong National University and used after drying. The alga
material was ground with a knife mill and sieved to obtain frag-
ments 150 lm and 355 lm in length.
The moisture and ash contents were determined using ASTM E
1756 and ASTM E 1755, respectively (Annual Book of ASTM

0960-8524/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.07.097
446 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451

Nomenclature

A pre-exponential factor (s1) W weight of sample at time t (g)

E activation energy (kJ mol1) W0 initial weight of sample (g)
k pyrolysis rate constant (min1) Wt nal weight of sample (g)
n reaction order X conversion of samples
R gas constant (8.314 J g mol1 K1) k1, k2, k3 reaction rate constants (min1)
t pyrolysis time (min) CA, CB, CC yields of reactant and product (wt.%)
T absolute temperature (K)

eutectic salt of KNO3 (59 wt.%) and Ca(NO3)2 (41 wt.%) (Kim and
Kim, 2000; Park et al., 2009; Kim et al., 2010). The temperatures
of the molten salt bath were kept constant at 360 C, 370 C, and
380 C 1 C. Based on data from the differential thermogravimet-
ric (DTG) curves, pyrolysis temperatures of 360 C, 370 C, and
380 C were selected along with the heating rates of 10, 15, and
20 C/min. The tubing reactor, containing the S. japonica sample,
was placed into the molten salt bath. The reaction times ranged
from 1 to 5 min at each reaction temperature. After reaction, the
reactor was removed from the molten salt and cooled to room tem-
perature. The reaction products were analyzed by weighing gas, oil,
and char products. The gas yield, dened as (gas weight)  100/
(feed weight), was obtained by weighing the tubing reactor before
and after gas release. The other pyrolyzed products were separated
into oil (acetone soluble) and char (acetone insoluble) using a sol-
vent extraction technique (Ding et al., 1997). The solid yield was
dened as (weight of acetone insoluble)  100/(weight of feed),
while the oil yield was dened as (100  gas yield  char yield).

3. Results and discussion

1. Microscale tubing reactor 4. Mechanical stirrer 3.1. Material characterizations

2. Salt bath 5. Thermocouple
3. Heater 6. PID temperature controller
Fig. 1. Schematic diagram of experimental apparatus.
Standards, 1997). Thermogravimetric analysis of the S. japonica
samples (25.0 1.0 mg) was carried out using TGA (TA Instrument
Q50). Nitrogen was used as the carrier gas at a ow rate of 25 mL/
min. The heating rates were controlled at 10, 15, and 20 C/min
from 30 C to 800 C.
2.2. Tubing reactor
A tubing reactor was used to pyrolyze the samples. The exper-
imental apparatus consisted of a salt bath, temperature controller,
mechanical stirrer, and a micro tubing reactor (Fig. 1). The reactor
was used to test the effect of residence time on the pyrolysis of S.
japonica at a constant temperature. A sample mass of 3 g was used
in each experimental run. The molten salt bath was composed of a
The characteristics of the S. japonica samples are presented in
Table 1. The ash contents were similar to that of raw algae (Bird
et al., 2011). Bird et al. (2011) produced algal biochar from macro-
algae (seaweed) by pyrolysis of eight species of green tide algae.
Ash content of raw algae was 19.4 1.7 wt.%, which was similar
to our analysis result. The ash contents of Argassum kushimonte
and Sargassum cristaefolium were 26.67 wt.% and 24.90 wt.%,
respectively (Borines et al., 2011).
The carbon (C) content of S. japonica was higher than that of
other green tide algae such as Cladophorpha linum and Cladophora
coelothrix that had C contents from 20.5 to 32.1 wt.% (Bird et al.,
2011). The oxygen content of S. japonica was higher than that of
most woody biomass (Park et al., 2009; Kim et al., 2010). The high-
er heating value (HHV) of S. japonica as calculated according to
Channiwala and Parikh (2002) was 12.11 MJ/kg, and the H/C molar
ratio was 2.25.
The concentrations of calcium (Ca), magnesium (Mg), phospho-
rous (P), lithium (Li), potassium (K), and sodium (Na) are shown in
Table 2. S. japonica contained much more inorganic matter than

Table 1
Characteristics of the S. japonica biomass.

Sample V.M.a Fixed carbona Moisture (%)b Ash (%)c Element (%) HHV (MJ/kg)
C H N Od
S. japonica 68.79 4.1 6.90 20.21 32.89 6.17 0.93 60.01 12.11
a
Determined by thermogravimetric analysis.
b
ASTM E1756, standard test method for the determination of the total solids of biomass.
c
ASTM E1755, standard test method for determination of ash content of biomass.
d
By difference.
 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451 447

Table 2 the reason why the ash content of S. japonica was higher than that
Calcium, magnesium, phosphorous, lithium, potassium, and sodium contents of of S. of woody biomass in Table 2.
japonica biomass.

Sample Element [ppm] 3.2. Thermogravimetric analysis and kinetic parameters of the
Ca Mg P Li K Na pyrolysis of S. japonica
S. japonica 7001.54 4781.17 1401.56 1.11 64786.73 30836.43
The results of thermogravimetric experiments are expressed as
a function of the conversion X, which is dened as

W0  W
1; 10 oC/min X 1
2; 15 oC/min
W0  W1
1.0

DTG, dX/dt x 10 [wt%/min]

o
3; 20 C/min 400
where W0 is the initial mass of the sample, W is the mass of the
0.8 pyrolyzed S. japonica sample, and W1 is the nal residual mass.
Conversion, X

300 The degrees of conversion versus temperature at heating rates

5
3
of 10, 15, and 20 C/min for S. japonica obtained via TGA are shown
0.6 2
1
in Fig. 2. At temperatures lower than 190 C, the small change in
3
200 conversion of the samples is attributed to vaporization of the mois-
0.4 2 ture attached to the surfaces of the samples. The S. japonica sam-
1 ples started to decompose at 200 C. The TGA graphs at different
100
0.2 heating rates of 10, 15, and 20 C/min showed similar results.
The TGA curves shifted toward the right with increasing heating
0.0 0 rate. As the heating rates increased, the higher instantaneous ther-
0 100 200 300 400 500 600 700 800 mal energy was released into the reaction system and resulted in a
o
Temperature [ C ] higher rate of conversion. The TGA curves of the S. japonica samples
showed two weight loss steps, with major decomposition occur-
Fig. 2. TG (thermogravimetric) and DTG (differential thermogravimetric) curves for
ring between 200 and 350 C. Similar thermal degradation patterns
S. japonica at heating rates of 10, 15, and 20 C/min.
were noted for three red macroalgae samples (Pophyra yezoensis,
Polcarnium telfairiae Harv, and Corallina pilulifera) by Li et al.
(2011).
-5.5 The differential rate of conversion, dX/dt, was obtained from dif-
5%
-6.0 10% ferential thermogravimetric analysis (DTG) at heating rates of 10,
20%
30%
15, and 20 C/min (Fig. 2). The DTG curve at each heating rate
-6.5
40% has three extensive peaks between 20 and 350 C. The rst step,
-7.0 50%
60%
at temperatures lower than 190 C, corresponds to dehydration,
-7.5 70% and the next steps, between 200 and 350 C, correspond to decom-
ln(dX/dt)

80%
-8.0 90% position of the different bio-polymer fractions. The second peak
95% between 200 and 270 C is attributed to the decomposition of car-
-8.5
bohydrates, and the third peak below 350 C denotes decomposi-
-9.0 tion of proteins (Ross et al., 2008; Bae et al., 2011).
-9.5 Decomposition of S. japonica at 350 C or higher likely progressed
more slowly because of the remaining protein and char (Ross
-10.0
et al., 2008; Bae et al., 2011; Sanchez-Silva et al., 2012; Kim and
-10.5 Agblevor, 2007; Yang et al., 2007). The maximum rate of dX/dt in
0.0010 0.0012 0.0014 0.0016 0.0018 0.0020 0.0022 0.0024 0.0026 0.0028
-1
the DTG curves increased with increasing heating rate (Fig. 1).
1/T [ K ] The maximum rate of decomposition tended to increase at higher
Fig. 3. Application for the calculation of activation energy of Eq. (5) with heating
heating rates because there was more thermal energy to facilitate
rates of 10, 15, and 20 C/min at conversion values ranging from 595%. better heat transfer between the surroundings and the insides of
the samples (Caballero et al., 1997). The maximum point rates of
decomposition observed in the DTG curves occurred at 273, 289,
and 304 C at heating rates of 10, 15, and 20 C/min, respectively.
woody biomass, such as Pinus rigida and Quercus variabilis, (Seo The TGA graph was analyzed to determine the kinetic parame-
et al., in press). Specically, the contents of magnesium, potassium, ters of S. japonica pyrolysis, including the activation energy and the
and sodium of S. japonica were much higher. These differences are Arrhenius frequency. The differential method was used to

Table 3
Calculated kinetic parameters for the pyrolysis of S. japonica.

Conversion (%)
5 10 20 30 40 50 60 70 80 90 95
Ea (kJ/mol) 35.25 102.52 118.21 121.83 123.99 157.12 186.06 284.03 208.40 244.78 269.68
n 0th 1.17  10 5.11  107 2.26  109 7.42  108 8.42  108 7.35  1011 1.66  1014 2.38  1022 1.83  1013 2.38  1013 3.07  1011
1st 1.23  10 5.65  107 2.76  109 1.00  109 1.25  109 1.21  1012 3.03  1014 4.79  1022 4.07  1013 5.86  1013 7.94  1011
2nd 1.30  10 6.24  107 3.38  109 1.35  109 1.87  109 1.99  1012 5.53  1014 9.65  1022 9.07  1013 1.44  1014 2.05  1012
448 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451

Table 4
Compounds identied by GCMS in S. japonica bio-oil produced by pyrolysis at 380 C for 5 min.

RT (min) Compositions Area % Structure

7.479 4-Hydroxy-4-methyl-2-Pentanone 3.67

9.012 1-(2-Furanyl)-ethanone 15.06

9.142 Dihydro-2(3H)-Furanone 2.21

10.53 Phenol 1.19

11.55 2-Hydroyxy-3-methyl-2-cyclopentene 2.51

11.76 2,3-Dimethyl-2-cyclopenten-1-one 1.55

12.06 3,5-Dimethyl cyclopentenolone 2.61

12.97 3-Hydroxy pyridine 3.13

14.57 Dianhydromannitol 38.21

15.64 Isosorbide 8.01

determine the pyrolysis kinetic parameters from the thermogravi- dX

kf X 2
metric data (Kim and Agblevor, 2007; Maiti et al., 2007; Kim et al., dt
2010). The rate of conversion, dX/dt, in thermal decomposition is The reaction rate constant k is expressed by the Arrhenius
expressed as, equation
 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451 449

 
E mannitol. Dianhydro-mannitol was the highest (27.28%) at 300 C
k A exp  3
RT
The temperature independent conversion function, f(X), is ex-
pressed as,
f X X n 4 aromatic compounds such as ethanone, furanone, phenol, cyclo-
Substituting Eqs. (3) and (4) into Eq. (2) and taking a natural
logarithm, the above equation yields
 
dX E1
ln lnAX n  5
dt RT
The activation energy, E, based on Eq. (5), can be determined
from a plot of ln(dX/dt) vs. 1/T. Fig. 3 shows the plots of ln(dX/dt)
vs. 1/T at various conversions ranging from 5% to 95%, resulting
in a family of parallel straight lines with a slope of E/R. When
the conversion of the S. japonica was 20%, for example, the corre-
sponding temperatures were 225.3 C, 232.0 C, and 237.3 C for
heating rates of 10, 15, and 20 C/min, respectively. At these tem-
peratures, the values of ln(dX/dt) were 7.67, 7.0, and 6.62
for heating rates of 10, 15, and 20 C/min, respectively. From the
slope of ln(dX/dt) vs. 1/T for the 20% conversion, the activation en-
ergy was calculated to be 118.21 kJ/mol. The intercept lnA  X n
was obtained from Fig. 3 for each conversion. From Eq. (5), when
the apparent order of reaction (n) is assumed to be 0, 1, or 2, the
pre-exponential factor (A) can be obtained from Eq. (6).
lnA  X n ln A n lnX 6 reaction time at pyrolysis temperatures of 360 C, 370 C, and
The moisture attached to the surfaces of the S. japonica was
vaporized at temperatures less than 190 C. Thus, the activation
energy at the 5% conversion level was not the pyrolysis of S. japon-
ica but the vaporization of moisture. The activation energy for the
pyrolysis of S. japonica ranged from 102.52 to 269.68 kJ/mol,
depending on the conversion. Up to a conversion of 40%, the acti-
vation energies maintained similar values and correspond to car-
bohydrate decomposition. The activation energies increased
slowly with increasing conversion from 50% to 95%, and those val-
ues are mainly attributed to protein degradation. These results are
in good agreement with those reported by Kim and Agblevor
(2007).
Table 3 shows the apparent activation energies and pre-expo-
nential factors calculated using Eqs. (5) and (6) based on Fig. 3,
assuming a zero-, rst-, or second-order reaction. The pre-expo-
nential factors were between 107 and 1022 s1, when the conver-
sion was between 10% and 95%.
3.3. Bio-oil composition
and decreased to 2.17% at 600 C.
In the current study, dianhydro-mannitol showed the highest
selectivity among the produced compounds, and the remaining
bio-oil products produced by pyrolysis of S. japonica were mostly
pentene, cyclopentenolone, pyridine, and isosorbide. Pyrolysis
products derived from S. japonica are a potential source of trans-
port fuels; specically, dianhydro-mannitol can be directly used
as a substitute and/or additive to gasoline.
3.4. Pyrolysis mechanism
The yields of oil, gas, and char as a function of the pyrolysis con-
ditions are shown in Table 5. The results show the effects of the
pyrolysis temperature and residence time on product yields. The
yields of oil and gas were in the range of 8.2128.78 wt.% and
2.0112.09 wt.%, respectively, at pyrolysis temperatures of
360 C, 370 C, and 380 C with a reaction time of 15 min. The
char yield was greater than 59 wt.% under the same conditions.
As shown in Table 2, S. japonica showed a large amount of inor-
ganic compounds, which resulted in a high char yield.
To simplify the kinetic model of the experimental data, the frac-
tions of gas, oil, and char were considered, and the pyrolysis kinetic
model was assumed for two groups of series and parallel reactions.
Fig. 4(a)(c) shows the yields of oil, gas, and char as a function of
380 C, respectively. The initial fraction of S. japonica was consid-
ered to be 100 wt.% and decreased with increasing reaction time
at a given temperature. The fractions of gas and oil increased with
increasing reaction time at temperatures of 360 C, 370 C, and
380 C. The yields of gas and oil remained essentially constant de-
spite an increase in reaction time to over 4 min between 360 C
and 380 C.
The pyrolysis mechanisms assumed for the kinetic model devel-
oped previously (Park et al., 2009; Kim et al., 2010) was:
C (Gas; C1-C4)
k1
A (Saccharina japonica) k3 7
k2
B (Bio-oil)

The bio-oil obtained from pyrolysis at 380 C for 5 min was used
for GCMS (Agilent 7890A) analysis to obtain an example of the Table 5
composition of such bio-oils generated by pyrolysis in a tubing Oil, gas, and char yields (wt.%) from pyrolysis S. japonica biomass pyrolyzed under
reactor (Table 4). A total of 78.15% of the compounds in the liquids different conditions in a micro-tubing reactor.
product were identied with this method. Reaction time (min)
Ross et al. (2008) studied classication of macroalgae as fuel
1 2 3 4 5
and its thermochemical behavior. In their research, pyrolysis-GC
MS was used for the pyrolysis of Macrocystis pyrifera at 500 C. Pyrolysis at 360 C
Gas (wt.%) 2.01 7.33 8.81 9.64 10.81
The degradation products were classied as carbohydrate, protein Oil (wt.%) 9.01 13.17 18.42 22.87 23.68
or polyphenolics. Unlike woody biomass, macroalgae did not con- Char (wt.%) 88.98 79.50 72.77 67.49 65.51
tain as many phenolic compounds because there were no lignin Pyrolysis at 370 C
type materials. Maddi et al. (2011) performed a comparative pyro- Gas (wt.%) 2.13 5.84 9.23 10.50 11.60
lysis study of algal biomass from natural lake blooms and lignocel- Oil (wt.%) 8.21 17.79 18.27 21.00 24.55
lulosic biomass. Algal bio-oils were compositionally different and Char (wt.%) 89.66 79.37 72.50 68.50 63.85
contained several N-compounds, attributed to protein degradation. Pyrolysis at 380 C
Bae et al. (2011) carried out pyrolysis of three marine macroalgae Gas (wt.%) 2.83 7.62 9.91 11.24 12.09
Oil (wt.%) 10.54 17.60 21.25 27.97 28.78
in a pecked tube reactor between 300 C and 600 C. Bio-oils of
Char (wt.%) 86.63 74.78 68.84 60.79 59.13
laminaria showed higher selectivity for ethanone and dianhydro-
450 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451

Table 6
(a) 360 oC S. Japonica
Reaction rate constants (min1) for the pyrolysis of S. japonica.
Oil
100 Gas
S. Japonica, Model Temperature (C) Rate constant (min1)
Oil, Model
Gas, Model k1 k2 k3
80
Yield [ wt% ]

360 0.0051 0.0917 0.1624

370 0.0058 0.0921 0.1659
60 380 0.0069 0.1135 0.1468

40
X
N
minimize S Y calculated;i  Y experimental;i 2 11
20 i1

where Ycalculated,i and Yexperimental,i refer to the value calculated by

0 Eqs. (8)(10) and the experimental values at a given temperature
0 1 2 3 4 5 6
Time [ min ] and time of reaction, respectively.
The reaction rate constants were estimated by applying Eq. (11)
to the results shown in Figs. 4(a)(c). The calculated reaction rate
(b) 370 oC S. Japonica
constants for the pyrolysis of S. japonica are shown in Table 6.
Oil
100 Gas The reaction rate constants k1, k2, and k3 increased with increasing
S. Japonica, Model
Oil, Model pyrolysis temperatures from 360 C to 380 C, except at 380 C for
Gas, Model
80 k3. Since the reaction pathway from bio-oil to gas is part of a series
Yield [ wt% ]

of reactions in a closed batch reactor, k3 might be affected by the

60 reactor conditions such as increased pressure at 380 C. The reac-
tion rate constants were higher for k3 (bio-oil ? gas) than for k1
40 (S. japonica ? gas) and k2 (bio-oil ? gas) at each temperature.
These results indicate that the predominant pyrolysis reaction
pathway of S. japonica was from B to C rather than from A to B
20
and/or to C. The kinetic parameters for S. japonica were slightly dif-
ferent compared to woody biomass. In the case of pine trees, k1
0
0 1 2 3 4 5 6 was higher than k2 and k3. (Kim et al., 2010). The results of S. japon-
Time [ min ] ica were slightly different from the results obtained from the pyro-
lysis of woody biomass such as oak trees, where k2 was higher than
k3 (Park et al., 2009). First-order lumped kinetics provide an excel-
(c) 380 oC S. Japonica
Oil lent t for the products obtained from S. japonica at 360 C, 370 C,
100 Gas and 380 C. The lumped reaction scheme proposed previously
S. Japonica, Model
Oil, Model (Park et al., 2009; Kim et al., 2010) is supported by the pyrolysis
Gas, Model
80 mechanism of S. japonica in Eqs. (8)(10). This mechanism is gen-
Yield [ wt% ]

erally in agreement with the experimental results and accounts for

60 the formation of the bio-oil; however, some discrepancy between
experiment and model for the formation of gas does exit, due to
40 gas formation from two different reaction pathways.

20 4. Conclusions

0 Global kinetic parameters, including the apparent activation

0 1 2 3 4 5 6 energies determined by the differential method for S. japonica,
Time [ min ] were between 102.5 and 269.7 kJ/mol. S. japonica bio-oil showed
the highest selectivity for dianhydro-mannitol when pyrolysis
Fig. 4. Oil, gas and char production at (a) 360 C, (b) 370 C, (c) 380 C and reaction
times of 15 min. was carried out at 380 C for 5 min in the micro-tubing reactor.
The proposed lumped kinetic model represent the experimental
results well and kinetic rate constants suggest a predominant
Based on Eq. (7), the kinetic equations for the reaction in terms pyrolysis reaction pathway from bio-oil to gas (C1C4) rather than
of yields (CA, CB, and CC) are as follows. from biomass to bio-oil and/or to gas. The proposed lumped kinet-
ics of S. japonica pyrolysis offers a guide for scale-up to produce va-
C A C A0 expk1 k2 t 8
lue-added products.
 
expk1 k2 t expk3 t
C B C B0 k2 C A0  9 Acknowledgements
k3  k1 k2 k3  k1 k2
This work was nancially supported by the Ministry for Food,
C C C A0  C A  C B 10
Agriculture, Forestry and Fisheries (20111001212-00).
The reaction rate constants k1, k2, and k3 were obtained by
applying an optimization procedure (LevenbergMarquardt meth- References
od) to the values of each component product at the three different
reaction temperatures. The method of parameter measurement Annual Book of ASTM Standards, 1997.
Adams, J.M., Gallagher, J.A., Donnison, I.S., 2009. Fermentation study on Saccharina
can be formulated into the following constrained nonlinear optimi- latissima for bioethanol production considering variable pre-treatments. Journal
zation program: of Applied Phycology 21, 569574.
 S.-S. Kim et al. / Bioresource Technology 123 (2012) 445451
Adams, J.M.M., Ross, A.B., Anastasaki, K., Hodgson, E.M., Gallagher, J.A., Jones, J.M.,
Donnison, I.S., 2011. Seasonal variation in the chemical composition of the
bioenergy feedstock Laminaria digitata for thermochemical conversion.
Bioresource Tehcnology 102, 226234.
Bae, Y.J., Ryu, C., Jeon, J.-K., Park, J., Suh, D.J., Suh, Y.-W., Chang, D., Park, Y.-K., 2011.
The characteristics of bio-oil produced from the pyrolysis of three marine
macroalgae. Bioresource Technology 102, 35123520.
Bird, M.I., Wurster, C.M., Silva, P.H.P., Bass, A.M., Nys, R., 2011. Algal biochar
production and properties. Bioresource Technology 102, 18861891.
Borines, M.G., Leon, R.L., McHenry, M.P., 2011. Bioethanol production form farming
non-food macroalgae in Pacic island nations: chemical constituents,
bioethanol yields, and prospective species in the Philippines. Renewable and
Sustainable Energy Reviews 15, 44324435.
Caballero, J.A., Conesa, J.A., Font, R., Marcilla, A., 1997. Pyrolysis kinetics of almond
shells and olive stones considering their organic fractions. Journal of Analytical
and Applied Pyrolysis 42, 159175.
Channiwala, S.A., Parikh, P.P., 2002. A unied correlation for estimating HHV of
solid, liquid and gaseous fuels. Fuel 81, 10511063.
Demirbas, A., 2010. Use of algae as biofuel sources. Energy Convrsion and
Management 51, 27382749.
Ding, W., Liang, J., Anderson, L.L., 1997. Kinetics of thermal and catalytic coal
liquefaction with plastic-derived liquids as solvent. Industrial and Engineering
Chemistry Research 36 (5), 14441452.
Kim, S.-S., Kim, S.H., 2000. Pyrolysis kinetics of waste automobile lubricating oil.
Fuel 79, 19431949.
Kim, S.-S., Agblevor, F.A., 2007. Pyrolysis characteristics and kinetics of chicken
litter. Waste Management 27, 135140.
Kim, S.-S., Kim, J., Park, Y.-H., Park, Y.-W., 2010. Pyrolysis kinetics and
decomposition characteristics of pine trees. Bioresource Technology 101,
97979802.
Lee, J.-W., Lee, D.-G., Park, J.-I., Kim, J.-Y., 2010. Bio-hydrogen production from a
marine brown algae and its bacterial diversity. Korean Journal of Chemical
Engineering 27 (1), 187192.
Li, D., Chen, L., Zhao, J., Zhang, X., Wang, Q., Wang, H., Ye, N., 2010. Evaluation of the
pyrolytic and kinetic characteristics of Enteromorpha prolifera as a source of
View publication stats
451
renewable bio-fuel from the Yellow Sea of China. Chemical Engineering
Research and Design 88, 647652.
Li, D., Chen, L., Zhang, X., Ye, N., Xing, F., 2011. Pyrolytic characteristics and kinetic
studies of three kinds of red algae. Biomass & Bioenergy 35, 17651772.
Maddi, B., Viamajala, S., Varanasi, S., 2011. Comparative study of pyrolysis of algal
biomass from natural lake blooms with lignocellulosic biomass. Bioresource
Technology 102, 1101811026.
Maiti, S., Purakayastha, S., Ghosh, B., 2007. Thermal characterization of mustard
straw and stalk in nitrogen at different heating rates. Fuel 86, 15131518.
Park, Y.-H., Kim, J., Kim, S.-S., Park, Y.-W., 2009. Pyrolysis characteristics and kinetics
of oak trees using thermogravimetric analyzer and micro-tubing reactor.
Bioresource Technology 100, 400405.
Ross, A.B., Jones, J.M., Kubacki, M.L., Bridgeman, T., 2008. Classication of
macroalgae as fuel and its thermochemical behavior. Bioresource Technology
99, 64946504.
Ross, A.B., Anastasakis, K., Kubacki, M., Jones, J.M., 2009. Investigation of the
pyrolysis behavior of brown algae before and after pre-treatment using PY-GC/
MS and TGA. Journal of Analytical and Applied Pyrolysis 85, 310.
Sanchez-Silva, L., Lpez-Gonzlez, D., Villaseor, J., Snchez, P., Valverde, J.L., 2012.
Thermogravimetric-mass spectrometric analysis of lignocellulosic and marine
biomass pyrolysis. Bioresource Technology 109, 163172.
Seo, Y.H., Ly, H.V., Kim, J., Kim, S.-S., Cho, W., Baek, Y., in press. Gasication
characteristics of Pinus rigida (pitch pine) and Quercus variabilis (oriental oak)
with dolomite catalyst in a uidized bed reactor. Energy Sources, Part A:
Recovery, Utilization, and Environmental Effects.
Um, B.-H., Kim, Y.-S., 2009. Review: A change for Korea to advance algal-biodiesel
technology. Journal of Industrial and Engineering Chemistry 15, 17.
Vishchuk, O.S., Ermakova, S.P., Zvyagintseva, T.N., 2011. Sulfated polysaccharides
from brown seaweeds Saccharina japonica and Undaria pinnatida: isolation,
structural characteristics, and antitumor activity. Carbonydrate Research 346,
27692776.
Yang, H., Yan, R., Chen, H., Lee, D.H., Zheng, C., 2007. Characteristics of
hemicelluloses, cellulose and lignin pyrolysis. Fuel 86, 17811788.