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Fuel 227 (2018) 21–26

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Fuel
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Full Length Article

Carbonization and combustion characteristics of palm fiber T


a a,⁎ a a b c
Xinyu Wang , Ming Zhai , Zhentong Wang , Peng Dong , Wei Lv , Ruichun Liu
a
School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China
b
School of Mechanical & Power Engineering, Harbin University of Science and Technology, Harbin 150080, Heilongjiang Province, China
c
Babcock & Wilcox Beijing Company Limited, Beijing 100029, China

A R T I C LE I N FO A B S T R A C T

Keywords: The carbonization of palm fiber with a muffle furnace was investigated by thermogravimetric analysis. The
Biomass experimental results showed that palm fiber char has better combustion properties than those of palm fiber. The
Palm fiber palm fiber char yield decreases with the increase in carbonization temperature. From 200 °C to 300 °C, the mass
Carbonization loss rate of palm fiber char is 45.97%. As the carbonization temperature increases, the high heat value of palm
Palm fiber char
fiber char increased by 41.39%. The palm fiber char exhibited lower moisture and volatile, higher energy density
Combustion rate
and heating value. With the rise in temperature, the H/C and O/C decreased from 14.31 and 76.01 to 0.15 and
5.80, respectively. As the carbonization temperature increases, the ignition temperature and the average com-
bustion rate increase, accordingly. The maximum combustion rate of the palm fiber char at 400 °C is 2.87 mg/
min. The comprehensive combustion index increases by approximately 12 times from 200 °C to 400 °C.

1. Introduction combustion characteristics of bamboo char, and concluded that this


char had higher energy density and higher heating value (HHV), lower
Today, fossil fuels are being exhausted, and the degradation of the hydrogen to carbon (H/C) and oxygen to carbon (O/C) ratios, and more
ecological environment, as well as increasing energy and environ- stable combustion with higher thermal efficiency compared with
mental problems have restricted the development of the world bamboo. Lu K. M. et al. [12] investigated the properties of oil palm fiber
economy, and therefore, it is imperative to develop new clean alter- and eucalyptus pretreated with nitrogen and air atmospheres at tem-
native energy [1,2]. Biomass includes wood and wood waste, crop and peratures of 250–350 °C for 1 h. Based on energy and solid yield and
byproduct waste, livestock waste, city solid waste, and aquatic plant introducing an energy-mass co-benefit index (EMCI), oil palm fiber
waste [3], which has lower ash and almost no sulfur. The utilization of pretreatment under nitrogen at 300 °C provided the solid fuel with
biomass for energy should be vigorously developed because the dis- higher energy density and less volume compared to other temperatures.
charge of pollutants can be efficiently reduced during the process [4,5]. Idris J. et al. [13] proposed a self-sustained carbonization system based
As one of the biomass thermochemical conversion technologies [6], on oil palm biomass and tested it at the pilot scale. The obtained HHV
carbonization technology refers to the process whereby biomass is he- was between 23 and 25 MJ/kg with low gaseous emissions. Qi J. et al.
ated and forms biochar after thermal decomposition under anoxic [14] investigated carbonization of biomass at different temperatures
conditions [7]. The disadvantages of biomass such as difficulty in (300–800 °C). Based on ultimate analysis, they provided an estimation
transportation, low melting temperature, and caloric value can be ef- method for higher heating value for torrefied/carbonized biomass. Cao
ficiently improved, the energy density and storage characteristics of J. et al. [15] investigated the kinetics of lignin carbonization by a
biomass can be efficiently advanced, and the heat and energy of car- Thermo-Gravimetric Analyzer coupled with a Fourier Transform In-
bonized products can replace non-renewable fossil fuel [8]. By this frared Spectrometry (TG-FTIR). The amorphous carbon basically
technology, biomass material has the advantages of being readily formed in the temperature of 500–900 °C with an activation energy of
combustible and having low bulk density and high caloric value after 70 kJ/mol. Álvarez, A. et al. [16] used thermal analysis and analysis
carbonization, and it also can be used as a fertilizer, to decrease water with the Coats-Redfern method to determine the kinetic parameters of
pollution, and for soil remediation [9]. 28 typical biomass samples and proposed a two-stage reaction model.
Combustion characteristics are very important for the direct utili- The model was not suitable for use with the Flynn-Wall-Ozawa (FWO)
zation of biomass, which is why combustion characteristics of biomass method or the Kissinger-Akahira-Sunose (KAS) method to solve the
are widely studied around the world [10]. Liu, Z. et al. [11] studied the dynamic parameters of biomass combustion. Determination of most of


Corresponding author.
E-mail address: zhaiming@hit.edu.cn (M. Zhai).

https://doi.org/10.1016/j.fuel.2018.04.088
Received 6 April 2018; Received in revised form 14 April 2018; Accepted 17 April 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
X. Wang et al. Fuel 227 (2018) 21–26

the biomass combustion properties is concentrated in parameter opti- 800 200


mization and system process control, especially in the combustion 300
process and dynamics parameters [17,18]. Therefore, to study com- 700 400
bustion characteristics, the thermochemical behavior of biomass should 500
600
be studied first. 600
Oil palm is a typical biomass commonly found in western Africa, 500
700

Temperature
southeast Asia, Latin America, and India [19,20]. Palm fiber is a by-
400 800
product obtained after oil extraction of oil palm, and the reserve of
palm fiber is very rich and it is potentially a low-cost material for 300
production of energy densified carbonaceous products [21,22]. Palm
shells and palm fiber, which are byproducts of the oil extraction pro- 200
cess, are also being increasingly accepted by new energy companies as 100
environmentally friendly material. Palm fiber can be used for fuel [23],
but it is difficult to control the combustion process as a result of the 0
presence of water and a high degree of moisture. In the process of
0 10 20 30 40 50 60 70 80
carbonization, the volatile compounds of biomass are reduced, and the
Time min
carbon content increases [24]. Therefore, carbonization is an efficient
way to improve its combustion. Because of a lack of research, it is ne- Fig. 1. Temperature variation in the furnace.
cessary to study the combustion characteristics of palm fiber char. The
range of temperature for carbonization is 200–800 °C, which is of sig- with a 200-mesh sieve. The carbonization temperature was determined
nificance to the design and operation of palm fiber combustion and the by the final temperature in the furnace. There were three stages of
design and operation of the combustion system. heating during the total carbonization time of 75 min, consisting of first
and second stages of 15 min, while the third stage was 30 min. The
2. Materials and methods temperature variation in the furnace is shown in Fig. 1.
The experimental procedure was as follows. Palm fiber was filled
2.1. Materials and sealed in a weighed crucible. The crucible was put in the center of a
furnace and heated according to the temperature variation set. After the
Palm fiber was used in the experiment for the current study that was heating was finished, the sample was taken out of the furnace at 150 °C
conducted in Jiangsu Province of China. The proximate and ultimate and placed in a dryer to cool to room temperature. The sample was
analysis (Proximate Analyzer: 5E-MAG6700, Changsha Kaiyuan weighed again. The yield of biochar (φm) refers to the ratio of the mass
Instruments, PRC; Ultimate Analyzer: vario MACRO cube, Elementar, of the sample after carbonization (m2) and before carbonization (m1),
Germany) is shown in Table 1. The particle size distribution of the which is shown in Eq. (1).
biomass feedstock used in carbonization and combustion experiments is
m2
less than 0.074 mm. φm = × 100%
m1 (1)

2.2. Experimental setup In this study, a thermogravimetric analyzer (Mettler-Toledo DGA,


USA) was adapted to conduct tests. The test conditions of thermo-
There are three types of carbonization devices (external heat, in- gravimetric analysis are as follows:
ternal heat, and self-ignition). For the external heat and internal heat
ones, the heat source heats the biomass directly or indirectly. Self-ig- (1) Temperature range: 25–800 °C
niting devices have the lowest energy consumption. Its heat comes from (2) Heating rate: 15 °C/min;
the combustion of gases generated by the thermal decomposition of (3) Test atmosphere: O2;
biomass during the carbonization process. To avoid the phenomenon of (4) Gas flow: 50 ml/min;
incomplete carbonization in self-ignition carbonization devices, this (5) Quantity of the micro-sample: 10 mg
experiment adopted sub-stage carbonization according to the three (6) Balance accuracy: 0.1 μg
stages of distillation (drying stage, distillation stage, and insulation (7) Crucible capacity: 900 µL
stage).
An electric furnace was used, and the suitable heating temperature Through TG-DTA, the ignition temperature (Ti), maximum com-
range used was from room temperature to 800 °C. The temperature bustion rate (Vm) and the temperature corresponding to that rate (Tm),
accuracy of ± 5 °C. Firstly, the sample was ground and then screened average combustion rate (Vmean), burnout temperature (Th), and com-
prehensive combustion characteristic index (S) could be obtained.
Table 1 The graphed ignition temperature Ti formed a vertical line down the
Proximate and ultimate analysis of palm fiber. peak of the DTG curve, and the vertical line intersected with TG curve
Contents value Unit
at a point and made a tangent line at the point. The horizontal ordinate
of the tangent line and the focus of the smooth curve after dehydration
a
Aad 4.13 % is the ignition temperature Ti. The maximum combustion rate is the
Vad 73.5 % point with the most significant change in the TG curve, and the cor-
FCad 20.11 %
Mad 3.11 %
responding temperature is the maximum combustion rate Tm:
Cad 48.44 % Average combustion rate Vmean
Had 6.93 % The formula is shown in Eq. (2):
Oad 36.82 %
Nad 2.05 % Vmean = (w1−w2)/ t (2)
Sad 0.11 %
Qnet,d 19.86 MJ/kg
where w1 is the weight of the sample when the ignition point was
reached, w2 is the weight of the sample when burnout temperature was
Qnet,d: net calorific value, dry basis. reached, and t is the interval between two temperatures.
a
ad: air-dry basis. Burnout temperature Th refers to the temperature when the DTG

22
X. Wang et al. Fuel 227 (2018) 21–26

Table 2 30
Mass of the palm fiber and yield of palm fiber char after carbonization (on a dry
ash free basis).
T (°C) m1 (g) m2 (g) φm (%) 27

Higher heating value(kJ/kg)


200 2.9837 2.4957 83.64
300 3.2283 1.2162 37.67
400 2.8004 0.6898 24.63 24
500 2.8485 0.6043 21.22
600 3.0127 0.5938 19.71
700 3.5685 0.6519 18.27
800 2.9344 0.4269 14.55 21

curve is 0 after complete combustion of fuel. The calculation formula of 18


the comprehensive combustion characteristic index is as follows, and
the value can be used as a basis for judging the combustion char-
acteristics behavior: 15
V ×V 0 200 400 600 800
S = m 2 mean
Ti × Th (3) Carbonization temperature( )
Fig. 2. Higher heating value of palm fiber char with carbonization temperature.
3. Results and discussion
80
3.1. The effects of carbonization temperature on the yield of palm fiber char
70
In Table 2, the average yield of palm fiber char is 83.64%, 37.67%,
24.63%, 21.22%, 19.71%, 18.27% and 14.55%, respectively from 200
60
to 800 °C of carbonization temperature. The char yield decreases with
increasing carbonization temperature. From 200 to 500 °C, the mass Volatile
50
loss of palm fiber is large, which is the main stage of mass loss in the Ash
entire carbonization process. Above 500 °C, the mass decreases due to Fixed Carbon
40
the bond cleavage of CeO and CeH in lignin.
Content

The variation rate of yield of palm fiber char also decreases with
30
increasing carbonization temperature. The char yield decreases by
45.97% from 200 to 300 °C. The variation rate of char yield is ap-
proximately 25% above 400 °C, but from 700 to 800 °C, the variation 20
rate of char yield rapidly increases due to the deep carbonization stage
with an increased specific surface area of the char. 10

3.2. The effects of carbonization temperature on the heating value of palm 0


0 200 400 600 800
fiber char
Carbonization temperature
The heating value is the most important parameter for evaluating
Fig. 3. Proximate analysis of palm fiber and its char.
the combustion characteristics of the fuel. The higher heating value of
palm fiber char is shown in Fig. 2, where 0 °C indicates that the palm
fiber did not undergo carbonization. The heating value of palm fiber is where FCad is the mass fraction of fixed carbon, %; Mad is the mass
lower than that of the carbonized product, and the higher heating value fraction of moisture, %; Aad is the mass fraction of ash, %; and Vad is the
of palm fiber increases from 19.86 to 28.08 kJ/kg with carbonization mass fraction of volatility, %.
temperature. The heating value of palm fiber is the same as that of palm The variation proximate analysis is shown in Fig. 3, where 0 °C
fiber char at 200 °C. With the increase in carbonization temperature, means the palm fiber without carbonization. With the increase in car-
the heating value of palm fiber char rapidly increases, and then the rate bonization temperature, the volatile matter gradually decreases. The
decreases above 400 °C. This occurs because the low heating value gas precipitation rate of volatile matter is rapid from 200 to 500 °C, but it
initially separates out during cellulose pyrolysis, and mass dramatically smoothly declines above 500 °C, which indicates the end of pyrolysis.
decreases, but the energy density apparently increases along with the The ash content increases with the carbonization temperature due to
heating value. With the increase in temperature, pyrolysis produces the volatile matter and moisture precipitation. The ash content in the
substances such as combustible gas and tar, which remove some heat, palm fiber is only 4.13%, but at 800 °C, it increases to 17.63%. The
and therefore, the increasing rate of the heating value slows down. content of fixed carbon increases with the carbonization temperature. It
is constant below 200 °C but dramatically increases from 200 to 400 °C
due to the volatile matter and moisture precipitation, and the increase
3.3. The effects of carbonization temperature on proximate analysis of palm
rate gradually decreases above 400 °C. Because pyrolysis ends above
fiber char
400 °C [25], components such as lignin slowly decompose, and there-
fore, the content of fixed carbon slowly increases. Compared with the
Air drying was used for the experiment of ash, moisture, and volatile
curve of the heating value, the trend of heating value and fixed carbon
matter. Fixed carbon was obtained by calculation, which is shown in
content is similar.
Eq. (4):
FCad = 100−(Mad + Aad + Vad ) (4)

23
X. Wang et al. Fuel 227 (2018) 21–26

110
0.0
70
100

60 90 -0.5

Derivative mass loss/%


80
50
C -1.0

Mass loss/%
70 0 DTG
H
O 60 200 DTG
40 400 DTG -1.5
N 50 600 DTG
Content

S
30 40 800 DTG -2.0
0 TG
30
200 TG
20 -2.5
20 400 TG
600 TG
10 10
800 TG -3.0
0 100 200 300 400 500 600 700 800 900
0 Temperature/
0 200 400 600 800 Fig. 6. Thermogravimetric curve of palm fiber and palm fiber char.
Carbonization temperature
Fig. 4. Ultimate analysis of palm fiber and its char. in palm fiber char. The H/C and O/C in palm fiber char are lower than
that in palm fiber, which indicates that carbonization improves fuel
quality and reduces energy loss.
3.4. The effects of carbonization temperature on the ultimate analysis of
The curves of the nitrogen and sulfur content remained unchanged,
palm fiber char
but the total mass of palm fiber decreased in the carbonization process,
which showed that the mass of nitrogen and sulfur decreased with the
The main elements of palm fiber are carbon, hydrogen, oxygen,
increase in temperature. Carbonization changes the quality of biomass
nitrogen, and sulfur, where carbon, hydrogen, and sulfur are combus-
fuel, and the content of nitrogen and sulfur decreases.
tible elements, but the primary sources of heating are from carbon and
hydrogen. Hydrogen has the highest heating value, but the amount of
hydrogen in palm fiber is low. Carbon and hydrogen bond to a variety
3.5. The effects of carbonization temperature on the combustion
of hydrocarbons in biomass, and carbon is in the form of fixed carbon.
characteristics of palm fiber char
Oxygen can react with other elements, but during combustion, its
content is tiny compared with the oxygen in the air. Fig. 4 shows the
Fig. 6 shows the TG and DTG curves of palm fiber char combustion
ultimate analysis of palm fiber and its char, where 0 °C means the palm
at different carbonization temperatures. The combustion characteristic
fiber without carbonization. From the comparison of fixed carbon and
curve is mainly divided into three stages: the first stage is drying, and
carbon content shown in Figs. 3 and 4, the trends are similar. With the
for palm fiber and palm fiber char of 200 °C at 100 °C, the weight loss
increase in temperature, carbonization intensifies, and the carbon in
rate of the TG curve is slight, and there is a small peak of the com-
palm fiber char is mainly in the form of fixed carbon. The carbon
bustion rate on the DTG curve, while the combustion rate of palm fiber
content is proportional to the heating value of the palm fiber or its char.
char at other carbonization temperatures slightly changes. This occurs
With the increase in carbonization temperature, the hydrogen
because when the carbonization temperature reached 400 °C, most
content decreases due to the pyrolysis of hydrocarbon and the combi-
moisture in the palm fiber has been separated out and there is little
nation of oxygen and hydrogen. Because of the oxygen content in the
moisture left. The second stage is combustion, which is mainly con-
palm fiber, the char continuously decreases, and the quality of the fuel
centrated in the range of 200–500 °C. The volatile matter and fixed
continuously increases. The hydrogen bonds in organic compounds
carbon underwent concentrated combustion at this stage, there was an
break with hydroxyl to form H2O, CO, CO2, phenol, and alcohol, which
apparent decrease in the weight loss rate of the TG curve, and the
carry oxygen at high temperatures, and therefore, the oxygen content
maximum peak value of the combustion rate appeared on DTG curve.
decreases. Fig. 5 shows the variation of H/C and O/C with temperature
The DTG curves of palm fiber and palm fiber char of 200 °C gradually
decreased, and the combustion rate slowly increased at this time. The
16 DTG curve of palm fiber char changed to a broken line at one point
H/C 80
O/C under other temperatures, and the combustion rate rapidly increased at
14
70 this point; this is mainly due to low carbonization temperature, and the
12 volatile matter accounted for a more significant proportion at this time.
60 During the combustion process, the volatile matter initially separated
10
and burned, and then the fixed carbon started to combust. When the
Atomic H/C ration

Atomic O/C ration

50
8 carbonization temperature is increased, there is little residue consisting
40 of devolatilization of volatile matter, and a small amount of volatile
6 matter and fixed carbon almost combusted at the same time during the
30
combustion stage remains. Therefore, the combustion rate sharply in-
4
20 creased at a certain point. The third stage is the burnout stage; the TG
2 curve tended to be a particular value. At this time after the burnout, the
10 residual ash content is measured, and the DTG curve tended to be 0.
0
The TG curve of palm fiber and palm fiber char of 200 °C still slowly
0
0 200 400 600 800 decreased in the burnout stage because the residual volatile matter
Temperature slowly separated out in the burnout stage and then burned out.
Table 3 shows the combustion characteristic parameters of palm
Fig. 5. Variation of O/C and H/C in palm fiber and its char. fiber and its biochar. With the increase in carbonization temperature,

24
X. Wang et al. Fuel 227 (2018) 21–26

Table 3
Combustion characteristic parameters of palm fiber and palm fiber char.
Sample Ti (°C) Vm (mg/min) Tm (°C) Th (°C) Vmean (mg/min) S × 108 (mg2 min−2 °C−3)

Palm fiber 259.68 1.0448 324.22 442.83 0.3724 1.3029


200 °C palm fiber char 285.71 1.4744 327.45 472.83 0.2758 1.0535
400 °C palm fiber char 290.63 2.8700 331.76 376.19 1.3988 12.6342
600 °C palm fiber char 305.33 2.5539 329.19 371.01 1.6977 12.5354
800 °C palm fiber char 308.15 2.4397 316.34 347.27 1.8315 15.772

the corresponding ignition temperature increased. The reason for this is According to the Arrhenius equation,
because with the increase in carbonization temperature, the volatile
E
content in the sample decreased, the fixed carbon content increased, k = Aexp ⎛− ⎞
⎝ RT ⎠ (6)
and the temperature of the corresponding ignition point increased.
−1
With the increase in carbonization temperature, the corresponding where A denotes the pre-exponential factor in s , E denotes activation
maximum combustion rate of palm fiber char increases at first and then energy of the reaction in kJ/mol, R denotes the gas constant
decreases. The maximum combustion rate is mainly influenced by the (R = 8.314 J/mol·K), and T denotes the thermodynamic temperature in
combustion rates of volatile matter and fixed carbon. Under the com- K.
prehensive influence of these factors, the combustion rate of palm fiber Moreover, under the constant heating rate of programming:
char at 400 °C is the maximum. The burnout temperature continuously dT
decreased with the increase in carbonization temperature. With the β=
dt (7)
increase in carbonization temperature, the fixed carbon content of palm
fiber char continuously increased at different temperatures and the the equation becomes:
volatile content decreased, while the ignition point of fixed carbon d∂ A E
= exp ⎛− ⎞ f (∂)
remained the same. The temperature and devolatilization temperature dT β ⎝ RT ⎠ (8)
of volatile matter are not the same, and its combustion temperature and
devolatilization temperature are also not the same. For palm fiber char, The reaction kinetics mechanism function:
the fixed carbon content is higher. The fixed carbon has undergone f (∂) = (1−∂)n (9)
concentrated combustion after reaching the ignition point, the residual
mass is little, and the corresponding combustion rate is slow because Therefore, Eq. (8) becomes:
the burnout temperature is the temperature corresponding to the d∂ A E
= exp ⎛− ⎞ (1−∂)n
combustion rate of −0.1 mg/min. Therefore, the area with the com- dT β ⎝ RT ⎠ (10)
bustion rate less than −0.1 mg/min region is designated as the burnout
area [26]. After separating the variables from both sides and integrating,
The comprehensive combustion index increased with the increase in Equation (8) becomes:
the carbonization temperature, which suggested that the combustion ∂ d∂ A T E
characteristic of palm fiber char improves. This occurs because with the ∫0 (1−∂)n
=
β
∫0 exp ⎛− ⎞
⎝ RT ⎠ (11)
increase in carbonization temperature, the volatile content decreased
with less favorable ignition characteristics. However, with the decrease The current study examines the combustion reaction as a first-order
of the burnout temperature, its influence is deeper, and combustion reaction, n = 1. Therefore, Eq. (11) becomes:
characteristics are improved. −ln(1−∂) A R 2RT E
= · ⎛1− ⎞ exp ⎛− ⎞
T2 β E⎝ E ⎠ ⎝ RT ⎠ (12)
3.6. The effects of carbonization temperature on the kinetic parameters of
Taking the natural logarithm of both side of the equation produces
palm fiber char
the following:

When studying the combustion characteristics, it is critical to de- −ln(1−∂) ⎤ A R 2RT ⎤ E


ln ⎡ = ln ⎡ · ⎛1− ⎞ −
termine the kinetic reaction parameters. The Coats-Redfern integral ⎣ T2 ⎦ ⎢
⎣β E⎝ E ⎠⎥
⎦ RT (13)
method is used to solve combustion reaction kinetic parameters and
complete further solution of the fuel mentioned above and its finished
2RT
≪ 1, and therefore, Eq. (12) becomes:
E
products. −ln(1−∂) ⎤ AR ⎤ E
The kinetic equation is as follows: ln ⎡ = ln ⎡ −
⎣ T2 ⎦ ⎢
⎣ βE ⎥
⎦ RT (14)
d∂
= kf (∂) The least squares method is used. A plot of yi against xi should be a
dt (5) AR
straight line with a slope −E/R because ln[ βE ] is nearly constant. It is
where ∂ denotes relative weightlessness, t denotes time, k denotes the necessary to obtain activation energy E, and frequency factor A.
reaction rate constant and f (∂) is a kinetics mechanism function. Combustion kinetic parameters of palm thread raw materials and their

Table 4
Combustion kinetic parameters of palm thread raw materials and its charcoal.
Sample Temperature range (°C) Activation energy E (kJ/mol) Frequency factor A (1/min) Correlation coefficient R

Palm fiber 259–442 44.40 8.633 × 10 5


0.97009
200 °C palm fiber char 285–472 53.61 5.06 × 105 0.97358
400 °C palm fiber char 290–376 121.03 2.61 × 1011 0.97374
600 °C palm fiber char 305–371 123.09 3.96 × 1011 0.99033
800 °C palm fiber char 308–347 122.15 6.68 × 1011 0.98551

25
X. Wang et al. Fuel 227 (2018) 21–26

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