Accepted Manuscript

Characteristics and kinetics study of simultaneous pyrolysis of microalgae

chlorella vulgaris, wood and polypropylene through TGA

Kolsoom Azizi, Mostafa Keshavarz Moraveji, Hamed Abedini Najafabadi

PII: S0960-8524(17)31059-3
DOI: http://dx.doi.org/10.1016/j.biortech.2017.06.155
Reference: BITE 18392

To appear in: Bioresource Technology

Received Date: 13 May 2017

Revised Date: 27 June 2017
Accepted Date: 28 June 2017

Please cite this article as: Azizi, K., Moraveji, M.K., Najafabadi, H.A., Characteristics and kinetics study of
simultaneous pyrolysis of microalgae chlorella vulgaris, wood and polypropylene through TGA, Bioresource
Technology (2017), doi: http://dx.doi.org/10.1016/j.biortech.2017.06.155

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 Characteristics and kinetics study of simultaneous pyrolysis of microalgae chlorella

vulgaris, wood and polypropylene through TGA

Kolsoom Azizia, Mostafa Keshavarz Moravejia*, Hamed Abedini Najafabadib

a
Department of Chemical Engineering, Amirkabir University of Technology (Tehran

Polytechnic), 424 Hafez Avenue, Tehran 1591634311, Iran

b
Mechanical Engineering Department, KU Leuven, 3001 Leuven, Belgium

*Corresponding author email: moraveji@aut.ac.ir

Abstract

Thermal decomposition behavior and kinetics of microalgae chlorella vulgaris, wood and

polypropylene were investigated using thermogravimetric analysis (TGA). Experiments were

carried out at heating rates of 10, 20 and 40 ℃/min from ambient temperature to 600 ℃. The

results show that pyrolysis process of C. vulgaris and wood can be divided into three stages

while pyrolysis of polypropylene occurs almost totally in one step. It is shown that wood can

delay the pyrolysis of microalgae while microalgae can accelerate the pyrolysis of wood. The

existence of polymer during the pyrolysis of microalgae or wood will lead to two divided groups

of peaks in DTG curve of mixtures. The results showed that interaction is inhibitive rather than

synergistic during the decomposition process of materials. Kinetics of process is studied by the

Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The average E values

obtained from FWO and KAS methods were 131.228 and 142.678 kJ/mol, respectively.

Keywords: Co-pyrolysis; Thermal behavior; Kinetics; TGA; Microalgae; Polymer.

1. Introduction

In recent decades, increasingly vast research efforts are devoted for developing renewable energy

resources due to the depletion of fossil fuels and their environmental issues such as air and water

pollution, acid rains and global warming. Of all the alternative renewable resources, biomass has

been recognized as a promising candidate to meet the global demand (Chen et al., 2014; Isahak

et al., 2012; Wu et al., 2015). Solid, liquid and gaseous bio-fuels can be obtained from different

biomasses which could be categorized into 1st, 2nd and 3rd generations according to their origin

(Chen et al., 2014).

First generation bio-fuels are produced from food crops. Feedstock for these fuels can be

categorized into starch and sugar crops, and oil seeds (Ho et al., 2014). Rice, wheat, maize,

sugarcane, oil palm, soybean and barley are some of such feedstocks (Guo et al., 2015; Patel and

Kumar, 2016; Vassilev and Vassileva, 2016). This kind of bio-fuel has destructive effect on the

environment and ecosystem because of their land-based feedstocks which cause issues related to

water and land-use changes (Guo et al., 2015; Ho et al., 2014; Patel and Kumar, 2016; Vassilev

and Vassileva, 2016). Moreover, this kind of bio-fuel cannot meet the world energy demand due

to competition with animal feed and human food for the source materials. Second generation are

produced from waste and ligno-cellulosic feedstocks such as wood, forest residues, straw,

demolition wood, municipal solid waste, refuse-derived fuel, grass and sewage sludge. Second

generation bio-fuels do not compete with food/feed supplies (Montingelli et al., 2015; Vassilev

and Vassileva, 2016). Besides, they offer higher bio-fuel production yield while they require

lower land for growing (Vassilev and Vassileva, 2016). Despite of these advantages over the first

generation of bio-fuels, they have some serious drawback of not being economically viable at
large scales (Naik et al., 2010; Nigam and Singh, 2011). Bio-fuels obtained from microalgae and

macroalgae has been considered as the third generation.

Third generation bio-fuels are known as the most promising alternative resource that avoid the

disadvantages of first and second generation bio-fuels (Saber et al., 2016). These new potential

alternative feedstocks can be used for large scale generation of bio-fuels without disrupting the

environment (Sirajunnisa and Surendhiran, 2016; Vassilev and Vassileva, 2016). They can grow

much faster than the other plants; therefore their bio-fuel production rate is much higher (Saber

et al., 2016). Moreover, they are able to grow in non-arable lands, and have no overlap with food

supply (Saber et al., 2016). They can use carbon from flue gases and atmospheric carbon

dioxide, so carbon capture is achieved while they are growing (Chiaramonti et al., 2016). Lipid

content of algae is high in comparison with the other traditional crops (Rajanren et al., 2015;

Suganya et al., 2016). Microalgae can produce 15-300 times more lipid for biodiesel production

(Suganya et al., 2016).

Microalgal biomass can be converted into bio-fuels in different forms of solid, liquid and gas

products via thermochemical processes. Of all thermochemical processes, pyrolysis is a

promising method which plays a crucial role in biomass conversion. This process is a series of

complex reactions which is influenced by several parameters such as temperature, heating rate,

residence time and feedstock composition (Li et al., 2013)(Duan et al., 2015)(Bhola et al.,

2011)(Muradov et al., 2010)(Cho et al., 2015). Pyrolysis characteristics of pure microalgae in

neutral atmosphere have been studied by many researchers. For example, Ceylan and Kazan

(Ceylan and Kazan, 2015) studied the pyrolysis behavior of Nannochloropsis oculata (NO) and

Tetraselmes sp (TS) by themogravimetric analysis. Their results showed three devolatilization

stages. First, physically adsorbed water and low molecular weight hydrocarbons are removed.
Second stage included a strong peak and attributed to the main pyrolysis stage. Finally, the solid

residue decomposed during the third stage (above 600℃). They also showed that heating rate had

slight effect on the decomposition trend. Besides, they stated that when heating rate increases the

residence time of sample inside the reactor is shorten. As a result, the corresponding initial and

final decomposition temperatures shifted towards higher temperatures.

In the other work, Chang et al. (Chang et al., 2015) reported the influence of reaction

temperature (200-410℃) on the yield of bio-oil obtained from catalytic hydropyrolysis of

Chlorella pyrenoidosa and bio-oil composition. They showed that temperature enhancement

increases the yield of bio-oil production. The highest bio-oil yield obtained at 310℃. Further

increase in temperature enhanced the thermal decomposition of oil and produced more light ends

and thereby gradually decreased the bio-oil yield. They illustrated that higher temperature will

produce bio-oil with higher C and H content and lower N and O content.

However, microalgae are hydrogen deficient which has adverse effects on hydrocarbon

production from the pyrolysis process (Borges et al., 2014). Co-pyrolysis of biomass with an

additional feedstock with higher hydrogen content is a method to increase the hydrocarbon yield

of bio-oil obtained from pyrolysis (Borges et al., 2014).

The main aim of co-pyrolysis is to improve the quality of bio-fuels. Co-pyrolysis feedstocks

contain biomass, coal, sewage sludge, polymer and municipal solid waste (Wang et al., 2016).

Co-pyrolysis of microalgae and coal through TGA showed that main pyrolysis temperature of

microalgae and coal blends is lower than coal and close to pure microalgae (Chen et al., 2012).

They determined activation energy of process by KAS and FWO method and showed that there

is no obvious difference between calculated activation energy by two mentioned methods. They

also showed that interaction between materials inhibits the thermal decomposition. Besides, co-
pyrolysis of biomass and coal can decrease emission of carbon dioxide during the downstream

utilization of pyrolysis products in comparison with coal pyrolysis (Wang et al., 2016). Xie et al.

(Xie et al., 2015) studied co-pyrolysis of microalgae and scum. They showed that the ratio of

microalgae and scum should be optimized to enhance bio-oil and aromatic production. They also

calculated the actual value and theoretical value of bio-oil yield and showed that the positive

effect (actual value of bio-oil > theoretical value of bio-oil) of co-feeding during the pyrolysis

will be significant when the hydrogen index of feedstock is larger than 0.7. Wu et al. (Wu et al.,

2015) investigated co-pyrolysis behavior of polypropylene and microalgae and showed that

polypropylene interacts with carbon dioxide produced by microalgae or carbonyl groups in the

microalgae and consequently carbon dioxide emission decreases. They also showed that

activation energy of co-pyrolysis process calculated by FWO method is lower than pure

materials pyrolysis. Co-pyrolysis of microalgae and sewage sludge showed that co-pyrolysis

with microalgae is superior to pyrolysis individual with sewage sludge because microalgae have

higher heating value and can improve operation of sewage sludge pyrolysis system (Wang et al.,

2016). Peng et al. (Peng et al., 2015) studied kinetics behavior of C. vulgaris and textile dyeing

sludge mixture through TG-FTIR by FWO and KAS method and showed that the lowest

activation energy obtained when blending ratio of microalgae was 80%. The kinetics analysis of

Isochrysis and Chlorella by Lorentzian fitting method showed that activation energy and initial

temperature of co-pyrolysis process decreased (Zhao et al., 2015). Co-pyrolysis of agricultural

and plastic wastes showed that the required activation energy needed to achieve thermal

degradation for mixtures is lower than that of the plastic wastes and the mixtures have different

pyrolysis reactivities at different temperatures ranges (Çepelioǧullar and Pütün, 2013).

According to previous studies, simultaneous pyrolysis of microalgae, polymer and woody

biomass has not been investigated yet. The objective of this paper is to study the interaction

between microalgae, wood and polypropylene. Lower activation energy and higher weight loss

for simultaneous pyrolysis of materials are expected in comparison with pure material pyrolysis.

Interaction between co-pyrolysis feedstock materials is an important research aspect.

Thermogravimetric analysis is one of the most common techniques which has been used to

characterize the thermal process, to describe the decomposition profiles and to determine kinetics

parameters.

Chlorella vulgaris has been used widely to produce biodiesel and bio-fuel because of its rapid

growth and suitable lipid content. Besides, the use of wastes derived from forest industries as

pyrolysis feedstock is essential for development of this technology at large scale. Moreover, co-

pyrolysis can handle waste plastic efficiently, which is the arch-criminal of white pollution. TGA

is chosen to estimate pyrolysis behavior and kinetics parameters. Apparent activation energy (E),

pre-exponential factor (A) and reaction order (n) obtained by Flynn-Wall-Ozawa (FWO) and

Kissinger-Akahira-Sunose (KAS) method.

2. Methods

2.1. Sample collection and preparation

The feedstock used in this study consisted of powder of Chlorella vulgaris, wood and

polypropylene. C. vulgaris is widespread in fresh water. Mentioned species was at first cultured

in 250 ml Erlenmeyer flask containing 100 ml sterilized BG11 medium. Culture medium

contained Sodium nitrate (1500mg/l), Calcium chloride (36mg/l), Magnesium sulphate (75mg/l), Ferric

chloride (4.05mg/l), EDTA (5.6mg/l), Boric acid (2.86mg/l), Zinc sulphate (0.22mg/l), Manganese

chloride (1.81mg/l), Ammonium heptamolybdate (0.391mg/l), Cupric sulphate (0.08mg/l), Cobaltous

nitrate (0.05mg/l) and di-potassium hydrogen orthophosphate (40mg/l) . Cells were transferred to a 4
liter tubular photobioreactor maintained at room temperature and was illuminated internally by

red light emitting diodes (LEDs). Light intensity was 500 lux. Algal cell concentration was

determined by measuring the optical density at 680 nm. When they reached constant phase they

were harvested and dried at 105 ℃ for 24 h in oven, and then held in desiccators.

The residual of red carpentry wood which is one of the major wastes derived from forest

industries in Iran, was used as woody biomass. One of the major waste plastics produced in Iran

is polypropylene. It was provided by Petrochemical Research & Technology Co. (Arak center).

The particle size of woody biomass and polypropylene was about 1 mm.

2.2. Sample characterization

Ultimate analysis was performed to determine the elemental composition of microalgae, wood

and polymer. It was carried out by elemental analyzer (Eager 300 for EA1112) which determines

carbon, hydrogen, nitrogen and sulfur percentage. The oxygen content of samples was obtained

by difference. The elemental analysis of materials is presented in Table 1.

Table 1.Elemental analysis of Chlorella vulgaris

Species C% H% N% O%a S%

Chlorella vulgaris 54.49 7.74 5.13 32 0.64

Wood 47.08 6.32 1.24 45.36 0.00

Polypropylene 84.31 15.30 0.31 0.00 0.08

a calculated by difference

2.3. Thermogravimetric analysis

The high temperature thermal decomposition of the biomass samples were evaluated using TGA

(Q50 V6.3 Build 189). The experiments were carried out to study the pyrolysis behavior of

biomass samples. In each experiment, the materials were weighted and mixed together manually.

Then, they were put under pressure to obtain a pellet. After that, the pellet which was about 9 mg
was placed on the sample holder. It should be noted that the ratio of materials in binary and

tertiary mixtures was equal in all experiments. Subsequently, the sample was heated from room

temperature to 600℃ at heating rates of 10, 20, 40 ℃/ under a high purity argon flow of 40

ml/min to ensure an inert atmosphere. The experimental errors are lower than 5% by three runs

repeatedly at the same time.

2.4. Kinetic model

An overall kinetic model which has been developed to describe the rate of degradation or

conversion can be expressed in the following form:


= () ( ) (1)


where t is time and α is conversion degree which is defined as:

 − 
= (2)
 − 

where  is the initial mass of the sample,  is the mass of sample at time t and  is the final

mass of sample in the reaction (Agrawal and Chakraborty, 2013).

As it can be seen from the equation (1), the rate of degradation is a linear function of a

temperature-dependent rate constant, k, and a temperature-independent function, ( ). Reaction

rate constant has been usually described by the Arrhenius expression (López-González et al.,

2014; Sharara et al., 2014; Shuping et al., 2010).

$
 =  !" #− & (3)
%

where A is the pre-exponential factor, E is the activation energy, R is the gas constant and T is

the absolute temperature. The combination of Equation (1) and (3) gives:

 $
=  !" #− & . ( ) (4)
 %
Define the heating rate ( as


(= (5)


By substituting this into equation (4), it is transformed to:

  $
= !" #− & . ( ) (6)
 ( %

The integrated form of the above equation is generally expressed as:


+
 , $
) ( ) = * = * !" #− &  (7)
  ( ) ( ,- %

where )( ) is the integrated form of  ( ).

Different methods can be applied to estimate the activation energy. It is known that the iso-

conversional methods can give an estimation of activation energy. In such methods, there is no

need to know the mechanism of reaction. In this article, two iso-conversional methods, Flynn-

Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) are applied. A great number of the

other kinetic methods for non-isothermal solid state reactions have been proposed and used.

However, in this article, the mentioned two methods will be considered because of their relative

higher reliability (Zhao et al., 2015).

The Kissinger-Akahira-Sunose (KAS) method is based on the following equation (Ceylan et al.,

2014):

( % $0
. # & = . # & − − ln ()( )) (8)
/ $0 %

3
For a given conversion , the plot of . 2, 45 verses 1/T yields straight line with slope given by

67
. While Flynn-Wall-Ozawa (FWO) method is proposed by the following equation (Agrawal
8

and Chakraborty, 2013):

 0.0048$0 1.5016$0
.(( ) = . # &− (9)
%)( ) %

The activation energy can be determined from the linear correlation of .(( ) verses 1/T as well.

Master-plots method is a useful method that can be used for mechanism function determination

in decomposition reactions. The lower limit of the integral on the right hand side of equation (7)

can be neglected due to very slow decomposition rate at sub-ambient temperatures (Shuping et

al., 2010). So, the integrated form can be expressed by the following equation:

$
) ( ) = ;(<) (10)
(%
?
where the temperature integral, ;(<) = = −( >? ⁄ / )
< < (< = $/%) has no analytical

solution and can be approximated. The rational approximation of Doyle gives accurate results:

;(<) = 0.00484. !"(−1.051<) (11)

For a single-step process with an invariant)( ), an analysis using the master plots presents

precise choice of the appropriate kinetic model. Taking account into a single-step process, A and

E are constant. Using a reference at point a = 0.5 and according to equation (10), one gets:

$
)(0.5) = ;(<.A ) (12)
(%

where <.A = $/%.A . The following equation is obtained by dividing equation (10) by equation

(12).

B(+) C(?)
= C(? (13)
B(.A) -.D )

B(+)
Plotting against  corresponds to theoretical master plots of various )()functions (Chen
B(.A)

C(?)
et al., 2012). To draw the experimental master plots of against  from experimental data
C(?-.D )

obtained under any heating rates, the experimental master plot is independent of the heating
 C(?)
schedule. Equation (13) shows that, for a given, the experimental value of and
C(?-.D )

B(+)
theoretically calculated values of B(.A) are equivalent when an appropriate kinetic model is used

(Shuping et al., 2010).

3. Results and discussion

3.1. Pyrolysis behavior of Chlorella vulgaris, Wood and polypropylene
Pyrolysis behavior of the three used materials are similar to the previous literatures (Chen et al.,

2012; Tranvan et al., 2014; Wu et al., 2015), (Aboulkas et al., 2008). Pyrolysis behavior of C.

vulgaris, wood and polypropylene at ( = 20℃/ are described in this section with

thermogravimetry (TG) and differential thermogravimetry (DTG) curves.

As shown in Figure 1 (a and b), the thermal decomposition process of C. vulgaris and wood can

be divided into three stages. For C. vulgaris, the first stage is from ambient temperature (25℃) to

around 150 ℃. In this stage, both water and light volatile compounds are lost. Stage 2, which is

the main decomposition stage, is from the end of first stage to around 480℃ . Most of the

organic species are decomposed in this stage. Multiple peaks observed in this stage (DTG curve

of C. vulgaris) are corresponded to degradation of protein, carbohydrate and lipid (Wu et al.,

2015). Finally, the third stage is from 480℃ to 600℃. Very slight weight loss is observed in TG

curve. Carbonaceous residues are decomposed at a very slow rate in this stage.

Pyrolysis behavior of wood is similar to C. vulgaris. However, second stage for wood starts at

higher temperature and terminates at lower temperature. The first stage is from room temperature

to 250℃. The main thermal decomposition stage of wood initializes at around 250℃ and

finalizes at around 400℃. The final stage is from 400℃ to 600℃. The result of analysis of the

thermal degradation of wood is the overlapping of decomposition of each individual.

Hemicelluloses decomposition peak is hidden with cellulose decomposition peak. So, it appears

as a shoulder rather than a clear peak. The main component of wood is cellulose and the peak
temperature is considered as the maximum temperature of cellulose degradation (Tranvan et al.,

2014). Lignin decomposes on a large temperature zone. This peak cannot be seen but it affects

the corresponding temperature range (Tranvan et al., 2014). It should be noted that

decomposition results can be influenced by external atmosphere. In mentioned article argon is

used to investigate degradation process.

The pyrolysis of polypropylene is different in comparison with the other two materials and it

occurs almost totally in one step. This conclusion is because of the presence of only one peak in

its DTG curve. The TG curve shows that thermal decomposition of polypropylene starts at

around 300℃ and finishes at around 500℃. The mass loss of polypropylene is around 99.75%

while the mass loss of C. vulgaris and wood are 77.94% and 74.42%, respectively. It can be

concluded that some components of C. vulgaris and wood form tar during the process, but

polypropylene almost does not produce tar (Wu et al., 2015). The characteristic of pyrolysis

process of materials used in this article is summarized in Table 2.

Table 2.Characteristic of TG analysis of pure materials at a heating rate of EF℃/GHI

a b c d
Tin T1 Dmax Tmax eTf
Materials Total weight loss (wt.%)
℃ ℃ J%. /℃ ℃ ℃
C. vulgaris 150 310.17 3.302 256.56 480 77.94

Polypropylene 300 464.98 4.961 428.56 500 99.75

Wood 250 351.07 3.141 270.07 400 74.42

a
initial decomposition temperature
b
temperature of the higher DTG peak
c
the maximum reaction rate
d
temperature of the maximum reaction rate
e
terminated temperature of the second stage

(a)
 120

C. vulgaris

100 Polypropylene
Wood

80
TG (wt.%)

60

40

20

0
50 100 150 200 250 300 350 400 450 500 550
Te mperature (C)

(b)

0.5

-0.5
DTG (wt.%/C)

-1

-1.5

C. vulgaris

-2
Polypropylene

Wood

-2.5
50 100 150 200 250 300 350 400 450 500 550
Temperature (C)

Figure 1. (a) TG profiles of C. vulgaris, polypropylene and wood at L = EF℃/GHI, (b) DTG profiles of

C. vulgaris, polypropylene and wood at L = EF℃/GHI

3.2. Interaction between materials

The thermogravimetric data and derivative curves of material blends are presented in Figure 2 at

a heating rate of20℃/min. The characteristics of degradation process of material mixtures are

also tabulated in Table 3.

As it can be seen from the Figure 2, the profiles of TG and DTG curves of C. vulgaris, wood and

polypropylene blends are similar to pure materials and they are laid between TG and DTG

curves of individual materials. TG curve of C. vulgaris and wood mixture could be divided into

three stages. The first stage extended from room temperature to around 200℃. The volatile

matters of small molecules are decomposed in this stage. Besides, water is evaporated in this

stage. The second stage starts at 200℃ and completes at around 450℃. With the addition of

wood to microalgae, the DTG peak of microalgae moves to higher temperature while the peak of

wood shifts to lower temperature. This phenomenon could be explained as follows. Wood main

components are cellulose, hemicelluloses and lignin. Because of their tough structure,

decomposition of cellulose and hemicelluloses occurs at higher temperature in comparison with

microalgae components.

The profile of TG and DTG of the other blends are also shown in Figure 2. According to DTG

curves, two divided groups of peaks can be obtained. Each peak represents the degradation of an

individual material. The first peak and the second peak in DTG curve of microalgae and

polypropylene correspond to microalgae and polymer, respectively. Corresponded temperatures

of these peaks are 304℃ and 472℃. It should be noted that the peak temperature of pure

polymer and microalgae are 465℃ and 310℃. The second peak temperature of polymer and

microalgae blend is higher than that of polymer. The most likely reason to explain this

phenomenon is tar formation of microalgae which occurs at temperatures higher than 400℃.
As it can be seen from the DTG curve of polymer and wood blend, the first temperature peak

which is 350℃ corresponds to wood maximum pyrolysis temperature and the second

temperature peak which is 471℃ corresponds to polymer maximum pyrolysis temperature.

Presence of polymer decreases the peak temperature of wood. On the contrary, wood enhances

peak temperature of polymer because of earlier tar formation of wood in comparison with

polymer.

Finally, pyrolysis behavior of microalgae, polymer and wood mixture is investigated through TG

and DTG analyses. Two divided groups of peaks can be seen in this case, too. The first peak

occurs at 347℃ and it is concerned to microalgae and wood pyrolysis together. As it was

mentioned earlier, microalgae and wood affect each other and as a result the peak temperature of

them together is higher than peak temperature of microalgae and lower than wood peak

temperature. The second peak is corresponded to polymer pyrolysis. On the first hand,

degradation of polymer occurs at higher temperature and its peak temperature is higher than

wood and microalgae. On the second hand, because of tar formation of wood and microalgae the

peak temperature of polymer in blend increases in comparison with pure polymer.

(a)
 120

C. vulgaris:W
100 C.vulgaris:PP
W:PP
C. vulgaris:W:PP

80
TG (wt.%)

60

40

20

0
50 100 150 200 250 300 350 400 450 500 550
Tempe rature (C)

(b)
0.2

-0.2

-0.4
DTG (wt.%/C)

-0.6

-0.8

C. vulgaris:W

-1 C.vulgaris:PP

W:PP

-1.2 C. vulgaris:W:PP

-1.4
50 100 150 200 250 300 350 400 450 500 550
Temperature (C)

Figure 2. (a) TG profiles of mixtures at L = EF℃/GHI, (b) DTG profiles of mixtures at L = EF℃/GHI

Table 3.Characteristic of TG analysis of mixtures at a heating rate of EF℃/GHI

a b b c c d e
Tin T1 T2 Dmax1 Dmax2 Tmax Tf Total weight loss (wt.%)
Materials
J%. / J%. /
C. vulgaris:W 150 247.30 --- 2.993 --- 346.09 450 74.4

C. vulgaris:PP 200 263.97 440.61 0.5689 2.402 472.02 480 89.62

W:PP 200 277.19 440.03 1.291 2.099 471.47 480 87.21

C. vulgaris:W:PP 200 251.44 448.18 1.635 1.33 474.88 480 84.32

a
initial decomposition temperature
b
temperature of the first and second DTG peak
 c
the maximum reaction rate of the first and second DTG peak
d
temperature of the DTG peak
e
terminated temperature of the second stage

To investigate the synergistic or inhibitive interaction between materials, practical and calculated

values of weight loss are obtained and compared. The calculated weight losses are obtained from

the following equation:

MN0ON?O0PQ = R !S JS (14)

where xi is the mass fraction coefficient and wi is the weight loss. According to this equation, the

total weight loss at a certain temperature is the sum of weight loss of each individual component

by its fraction (Peng et al., 2015), (Chen et al., 2012).

Variation of MN0ON?O0PQ and MPTUPVSWPX0O against temperature at ( = 20℃/ are presented

in Figure 3a-b for different mixtures used in this study. If experimental weight loss is higher than

theoretical weight loss, the interaction is synergistic. It is clear that MPTUPVSWPX0O is less than

MN0ON?O0PQ at any mixture. As a conclusion, the interaction between materials exists and is

inhibitive rather than synergistic during the decomposition process of materials. As it is shown in

Figure 3a, two curves do not reveal a clear deviation below 380℃. The differences between

experimental and calculated values do not grow as fast as it is above the temperature 380℃. The

behavior of microalgae-polymer and polymer-wood mixtures is similar to microalgae-wood

mixture during the pyrolysis process and has inhibitive effect during the decomposition process.

Inhibition effect of microalgae- polymer and polymer-wood blends starts at 340℃ and 380℃ and

finishes at 490℃ and 490℃, respectively. As it was mentioned, polymer decomposes completely

during the process. Decomposition of polymer completes at around 500℃. As a result, there is

no polymer in the decomposed mixture at this temperature. Therefore the inhibitive or

synergistic effect cannot be seen in temperature above 490℃. The behavior of microalgae-wood-
polymer blend is a little bit different from the other blends. There is a synergistic effect between

300-400℃ and then the behavior is inhibitive between 400-490℃.

(a)
110

100
Experimental C.vulgaris:W
Calculated C.vulgaris:W
90
Experimental C.vulgaris:P
Calculated C.vulgaris:P
80

70
TG (wt.%)

60

50

40

30

20

10
50 100 150 200 250 300 350 400 450 500 550
Temperature (C)

(b)
110

100

Experimental C.vulgaris:W:P
90 Calculated C.vulgaris:W:P
Experimental W:P
80
Calculated W:P

70
TG (wt.%)

60

50

40

30

20

10
50 100 150 200 250 300 350 400 450 500 550
Tempe rature (C)

Figure 3.Comparison between experimental and calculated weight loss at L = EF /GHI; (a) C.vulgaris:

Wood and C. vulgaris: Polymer (b) C. vulgaris: Wood: Polymer and Wood:Polymer
3.3. Effect of heating rate
The TG and DTG profiles of the mixture at several heating rates (( = 10, 20, 40℃/) are

shown in Figure 4. It can be seen from the TG profile that higher heating rate leads to more

decomposition of mixture while ( reduction leads to lower decomposition. According to DTG

curves, two divided groups of peaks can be obtained at different heating rates and as it was

mentioned earlier first peak belongs to simultaneous degradation of wood and microalgae and

second peak belongs to polymer degradation. The mass losses of mixtures at

β = 10, 20 and40℃/min are 85.85%, 84.32% and 87.35%, respectively. It could be concluded

that when ( increases, a considerable variation of mass loss is not observed. It means (

enhancement does not affect mass loss of mixtures. From the DTG profile, a lateral transition of

peaks towards the higher temperatures can be seen. This phenomenon is observed for many fuels

(Chen et al., 2012). In fact, increasing ( tends to postpone the thermal decomposition process of

mixtures and materials break down at higher temperatures.

(a)

110

100
10 C/min

90 20 C/min
40 C/min
80

70
TG (wt.%)

60

50

40

30

20

10
50 100 150 200 250 300 350 400 450 500 550
Temperature (C)
 (b)

-0.2

-0.4
DTG (wt.%/C)

-0.6

-0.8

-1
10 C/min

20 C/min
-1.2 40 C/min

-1.4
50 100 150 200 250 300 350 400 450 500 550
Tempe rature (C)

Figure 4. (a) TG and (b) DTG profiles of C. vulgaris, wood and polypropylene mixture at

L = ZF, EF, [F℃/GHI

3.4. Kinetics analysis

The kinetics methods explained in section 2.4 are used to determine kinetic parameters.

Activation energy values are calculated at different heating rates of 10, 20 and 40 ℃/min and

tabulated in Table 4. Mentioned E values are determined according to equation (8) and (9) (FWO

and KAS method) at selected values of  (0.2 ≤  ≤ 0.8) which are shown in Figure 5. Alpha

enhancement decreases E at first and an increase followed on. The values of E exhibit a great

dispersion without any clear trends. Pyrolysis of biomass is a complicated process involving

several reactions. Each reaction has its activation energy. The variation of E with alpha could be

associated with mentioned reactions taking place during the process. Besides, the R2 values of

linearization procedure are listed in Table 4. It can be observed that R2 values are within the wide

interval of 0.6899-0.9906. It is shown that within0.3 ≤  ≤ 0.6, the R2 values are lower than 0.9
which means that the points are not fitted well in mentioned interval. The E average calculated

by FWO is slightly higher than that calculated by KAS. Besides, the variation trends of E

obtained by two methods were the same. Chen et al. (Chen et al., 2012) showed that activation

energy for pure C. vulgaris by KAS and FWO methods is 335.69 and 329.51kJ/mol,

respectively. In the other work, Wu et al. (Wu et al., 2015) showed that the activation energy of

polypropylene is 189 kJ/mol. The activation energy of wood calculated by Tranvan et al.

(Tranvan et al., 2014) was 130 kJ/mol. Comparing their results with those obtained in this work,

it can be concluded that co-pyrolysis decreases activation energy of process. In general, a

reaction with lower activation energy needs a lower reaction temperature or shorter reaction

duration.

(a)
 (b)

Figure 5. Linear correlation for (a) ^I(L) and (b) ^I(L/_ E ) versus 1/T with several` for

mixture of microalgae, wood and polymer

Table 4.Activation energy values at L = ZF, EF aIb [F ℃/GHI by KAS and FWO method
KAS method FWO method
sample  2
E(kJ/mol) R E(kJ/mol) R2
C. vulgaris:W:PP 0.2 174.394 0.9381 184.4 0.9423
0.3 86.440 0.8546 96.758 0.8778
0.4 77.505 0.6899 88.219 0.7336
0.5 68.763 0.6968 80.057 0.7533
0.6 117.543 0.839 129.715 0.861
0.7 193.400 0.9816 206.129 0.9828
0.8 200.550 0.9906 213.486 0.991
Average 131.228 - 142.678 -

Feedstock used in this article belongs to solid materials and their pyrolysis process is in accord with solid

reaction kinetics (Wu et al., 2015). A frequently used mechanism function is:

 ( ) = (1 − )X (15)

Its integrated form is:

)( ) = c1 − (1 −  )d>X e/(1 − ) (16)

By substituting this into equation (10), it is transformed to:

c1 − (1 −  )d>X e $ (17)
)( ) = = ;(<)
1− (%

To obtain optimal value of n, it is increased from 1.1 to 2 with increment of 0.1. Then plot of

fd>(d>+)ghij 6
verses ;(<)using linear least square fitting procedure is utilized. The most
d>X 38

suitable n is the value that for which the intercept is closest to zero and R2 is the highest. The

most suitable value of n, corresponding value of pre-exponential factor (A) and the highest R2 at

different heating rates are determined and listed in Table 5.

Table 5.n and A calculated at heating rates of ZF, EF aIb [F ℃/GHI by master plot method
Sample ( R2 n A(s-1) A(s-1) Average value
C. vulgaris:W:PP 10 0.9335 1.1 1.00E+9 4.67E+8
20 0.9214 2.00E+8
40 0.9521 2.00E+8

4. Conclusions

Kinetics and thermal behavior of C. vulgaris, wood, polypropylene and their mixtures were

studied using TGA. The main decomposition stage of C. vulgaris and wood was second stage

while polymer was decomposed almost in one stage. C. vulgaris and wood enhance peak

temperature of polymer because of their earlier tar formation. Interaction between materials

inhibited the thermal decomposition process in all cases except in co-pyrolysis of microalgae,

wood and polymer which there was synergistic effect between 300-400℃ . Increasing ( tends to

postpone the thermal decomposition of mixtures while it does not affect mass loss of mixtures.

Acknowledgment

The authors are grateful for the financial supports from Amirkabir University of Technology,

Tehran, Iran.
Appendix A. Supplementary data

Supplementary data associated with this article can be found in the online version.

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Highlights

• Thermal behavior of co-pyrolysis of microalgae, wood and polymer was investigated.

• Mixture of microalgae, wood and polymer decomposes at two stages.

• Addition of polymer decreases peak temperature of wood and microalgae.

• Co-pyrolysis of microalgae, wood and polymer shows a synergistic effect.