J. Basic. Appl. Sci. Res.

, 4(3)31-41, 2014 ISSN 2090-4304

Journal of Basic and Applied
2014, TextRoad Publication
Scientific Research
www.textroad.com

Effects of Catalysts(Mg and Fe) on Kinetics of Biomass Gasification Using

CO2 as Gasifying Agent
1
Abid Farooq, Moinuddin Ghauri, 2 Mujtaba Hussain Jaffery and 3Khurram Shahzad
1
Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore-Pakistan
2
CREPS, Department of Electrical Engineering, COMSATS Institute of Information Technology, Lahore-Pakistan
3
Centre for Coal Technology, University of the Punjab, Lahore-Pakistan
Received: May 4 2013
Accepted: June 8 2013

ABSTRACT

The effect of two catalysts (Mg and Fe) on CO2 gasification reactivity and kinetics at different temperatures (300K-
1400K) were studied. The derived model equations were computed using MATLAB. It was found that the reaction
rate increased with the addition of catalyst as well as the time for the conversion also reduced comprehensively. The
gasification reactivity of biomass improved with the addition of catalyst in a sequence Mg>Fe till 400K and Fe>Mg
after 400K. As Fe shows the maximum reaction rate and the minimum reaction time for 100% conversion at given
temperature.
KEYWORDS: Biomass, Modeling, Catalytic Biomass Gasification, Gasifying Agent, Gasification Kinetics

1. INTRODUCTION

The use of renewable source such as biomass has been increasing for heat and power generation for future
energy supply and for limiting CO2 emissions. From the recent past the attention has been paid to biomass as a
renewable and non polluting source of energy which can partly reduce fossil fuel which is diminishing increasingly.
Because of their attractive properties(negligible sulphur , nitrogen and metal contents) woody biomass has gained an
importance and suggested as an imported biomass source. Biomass referring to all the forms of plant based material
that can be converted into usable energy is a renewable source of energy.[1][2]
Pakistan being agricultural country also produces reasonably abundant quantum of biomass. Major sources
include agricultural residues, plant trimmings, wood and sawdust. Efficient utilization of this resource can provide
reasonably sufficient and sustainable energy for power generation through deploying gasification technology.
Several attempts have been made for the production of carbon monoxide from biomass with CO2 as gasifying
agent.
Corella and Sanz, have gasified biomass in a circulating fluidized bed gasifier using air as gasifying medium.
They have also given correlations for other reactions but this seems to be the only one giving reasonable answers
with initial values used in this work. Schar in the correlation is the specific area of char.[3]
Kajitani et al. found kinetic parameters for different coal chars by experimenting CO2 gasification in an
entrained bed gasifier. This experiment is done in pressurized conditions. [4]
Mani et al. have gasified wheat straw in thermo gravimetric apparatus (TGA) using CO2 as the gasifying
medium. They introduced a form of equation that does not include partial pressures or concentrations.[5]
There have been extensive studies on the catalytic effects of metals on gasification. Alkali and alkaline earth
metals are particularly effective for gasification of chars and carbon. Calcium and potassium loaded cellulosic chars
showed enhanced reactivity for gasification in air.[6,7]. The reaction of graphitic carbon with CO2 was found to be
accelerated due to addition of small amount of CaCO3, MgCO3, BaCO3 and SrCO3[8]. Wang et al. have recently
reported steam gasification of coal char catalyzed by K2CO3 for enhanced production of hydrogen[9] and enhanced
catalysis of K2CO3 for steam gasification of coal char by using Ca(OH)2 in char preparation[10]. They reported that
the Ca(OH)2 added char and higher reactivity for the catalytic gasification than the raw char Ca(OH)2 played a role
in suppressing the interactions of K2CO3 with acidic minerals in coal during the gasification and in forming more
active oxygenated intermediate on the char surface.
However, relatively very little is known about the catalytic gasification of biomass char[11-14]. Catalysts are
also usually added to biomass or coal that has been first de-ashed using fluoride bearing acid to eliminate the
influence ash and this may destroy the structure of the raw material. There have been a limited number of studies on
the catalytic mechanisms of metals.

*Corresponding Author: Moinuddin Ghauri, Department of Chemical Engineering, COMSATS Institute of Information
Technology, Lahore-Pakistan. Email: drghauri@ciitlahore.edu.pk

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 Farooq et al., 2014

This study therefore aimed to improve our understanding of the metal catalyzed CO2 gasification of biomass
char i.e., study of the catalytic effect of metals on char gasification reactivity and conversion time.

Kinetic Analyses
The rate of gas-solid reaction in a chemical reaction can generally be expressed by the following equation.[15]
= . (1 ) (1)

Where k is a reaction rate constant(s-1) and n is the reaction order. The Arrhenius equation can be expressed as
follows[16]
= [ . ] (2)
Where A is a frequency factor(s-1), E is the activation energy(kJ/mol-1), R is a constant and T is the gasification
temperature(K).
Table 1.Ultimate analysis of chars[17]
Char Sample C H O N S
Mg-char 63.85 3.74 13.68 0.03 0.13
Fe-char 68.33 2.12 11.41 0.39 0.06

Table 2 .CO2 gasification kinetic parameters of different chars [17]

Char samples n E(kJ/mol) A(s-1)
Mg-char 0.4433 81.9 4.96
Fe-char 0.3598 84.2 8.66

The reactivity depends upon the conversion as well as on the temperature and gas composition. For most chars
of coal, lignite and peat reactivity decrease with increasing conversion, whereas for most chars of biomass it
increases. It can also exhibit a maximum or a minimum. So, if a representative kinetic is reported, it should be
referred to a specific conversion value. Different values such as 5% and 50% have been used. In the present study,
the reactivity at 10 to 100% at temperature range of 300-1400K is taken as representative.

Figure1: Process flow diagram

2. METHODOLOGY

Assumptions made in the modeling investigations work are as appended below. The flow diagram using describing
the gasification process in one unit is shown in figure 1.
Assumptions
The following assumptions were made for the gasification process
Biomass is preheated to reaction conditions.
Biomass is represented by char.
Ash in biomass is considered as inert and do not participate in chemical reactions.
CO2 is the only oxidizing agent for gasification.

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 J. Basic. Appl. Sci. Res., 4(3)31-41, 2014

CO2 temperature is increased to 1400K through electric/solar furnace.

The reaction endothermic part is compensated through CO2 heating.
When materials enter the reactor conversion is zero when time (t) is zero.
Mg and Fe are chosen as catalysts

3. RESULTS AND DISCUSSIONS

The developed set of gasification model for the production of carbon monoxide in a gasification system by
reducing carbondioxide using catalysts(Mg, Fe). Figures(2-13) show the effect of catalysts on conversion time with
increasing temperature of 300K-1400K. The results indicate the maximum effect of Mg from at 300K-400K in a
sequence of Mg>Fe. After 400K the whole behaviour changes with the maximum effect of Fe in a sequence of
Fe>Mg. Lower temperature favours Mg while the higher temperature favours Fe. Figure 14 shows the effect of
catalysts with increasing temperature on rate constant with the maximum rate constant achieved by Fe catalyst.
Figure 15 shows the maximum escalation in reaction rate achieved by Fe catalyst in a sequence of Fe>Mg.

At 300K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
time(s) 13
x 10
Figure2:Effect of time on conversion at constant temperature

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 Farooq et al., 2014

At 400K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
time(s) 9
x 10
Figure3:Effect of time on conversion at constant temperature

At 500K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 0.5 1 1.5 2 2.5 3 3.5 4
time(s) 7
x 10
Figure4: Effect of time on conversion at constant temperature

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 J. Basic. Appl. Sci. Res., 4(3)31-41, 2014

At 600K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 2 4 6 8 10 12 14
time(s) 5
x 10
Figure5: Effect of time on conversion at constant temperature
At 700K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 2 4 6 8 10 12 14
time(s) 4
x 10
Figure6: Effect of time on conversion at constant temperature

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 Farooq et al., 2014

At 800K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 0.5 1 1.5 2 2.5
time(s) 4
x 10
Figure7: Effect of time on conversion at constant temperature
At 900K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 1000 2000 3000 4000 5000 6000
time(s)

Figure8: Effect of time on conversion at constant temperature

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 J. Basic. Appl. Sci. Res., 4(3)31-41, 2014

At 1000K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
time(s)

Figure9: Effect of time on conversion at constant temperature

At 1100K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 100 200 300 400 500 600 700 800
time(s)

Figure10: Effect of time on conversion at constant temperature

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 Farooq et al., 2014

At 1200K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 50 100 150 200 250 300 350 400
time(s)

Figure11: Effect of time on conversion at constant temperature

At 1300K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 20 40 60 80 100 120 140 160 180 200
time(s)

Figure12: Effect of time on conversion at constant temperature

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 J. Basic. Appl. Sci. Res., 4(3)31-41, 2014

At 1400K
1
Mg-char
0.9 Fe-char

0.8

0.7

0.6
Conversion

0.5

0.4

0.3

0.2

0.1

0
0 20 40 60 80 100 120
time(s)

Figure13: Effect of time on conversion at constant temperature

0.2
Mg-char
Fe-char
0.15

0.1

0.05
k

-0.05

-0.1
300 400 500 600 700 800 900 1000 1100 1200 1300 1400
Temperature

Figure14: Effect of Temperature on rate constant

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 Farooq et al., 2014

-3
x 10
3
Mg-char
Fe-char
2.5

2
reaction rate(mol/s)

1.5

0.5

0
200 400 600 800 1000 1200 1400
Temperature

Figure15: Effect of temprature on reaction rate

4. CONCLUSIONS

The result of this study led to the following conclusions

Two metal catalysts (Mg, Fe) can increase the gasification reactivity of biomass char keeping temperature
constant.
Lower temperature (300K-400K) favors the Mg in a sequence of Mg>Fe.
Higher temperature after 400K it favors the Fe in sequence of Fe>Mg.
The reaction time decreases with increasing temperature and it decreases even more with the addition of
catalyst at the same temperature.
Catalysts increase the reaction rate at the same temperature.

Acknowledgment:
The authors declare that they have no conflicts of interest in this research.

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