Applied Energy 87 (2010) 101108

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Pyrolysis and gasication of food waste: Syngas characteristics

and char gasication kinetics
I.I. Ahmed *, A.K. Gupta
The Combustion Laboratory, University of Maryland, Department of Mechanical Engineering, College Park, MD 20742, United States

a r t i c l e

i n f o

Article history:
Received 4 May 2009
Received in revised form 12 August 2009
Accepted 14 August 2009
Available online 13 September 2009
Keywords:
Food waste gasication
Char gasication kinetics
Catalytic effect of ash
Compensation effect

a b s t r a c t
Characteristics of syngas from the pyrolysis and gasication of food waste has been investigated. Characteristic differences in syngas properties and overall yields from pyrolysis and gasication were determined at two distinct high temperatures of 800 and 900 C. Pyrolysis and gasication behavior were
evaluated in terms of syngas ow rate, hydrogen ow rate, output power, total syngas yield, total hydrogen yield, total energy yield, and apparent thermal efciency. Gasication was more benecial than pyrolysis based on investigated criteria, but longer time was needed to nish the gasication process. Longer
time of gasication is attributed to slow reactions between the residual char and gasifying agent. Consequently, the char gasication kinetics was investigated. Inorganic constituents of food char were found to
have a catalytic effect. Char reactivity increased with increased degree of conversion. In the conversion
range from 0.1 to 0.9 the increase in reactivity was accompanied by an increase in pre-exponential factor,
which suggested an increase in gasifying agent adsorption rate to char surface. However, in the conversion range from 0.93 to 0.98 the increase in reactivity was accompanied by a decrease in activation
energy. A compensation effect was observed in this range of conversion of 0.930.98.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Dumping food waste in a landll causes environmental problems. By volume, the dumped landll waste causes the largest contribution to methane gas production [1]. It causes odor as it
decomposes to cause public annoyance in addition to forming
germs, and attracting ies and vermin. Another serious problem
of food wastes is the generation of landll leachate. Landll leachate is liquid that leaks from the landll and enters the environment. Once it enters the environment the leachate is at risk for
mixing groundwater near the site which then transports to some
distances. Furthermore it has the potential to add biological oxygen demand (BOD) to the groundwater. BOD measures the rate
of oxygen uptake by micro-organisms in a sample of water at a
temperature of 20 C and over an elapsed period of ve days in
the dark.
Food wastes have high energy content. Consequently, it offers a
good potential for feed stock for gasication in power plants. Food
waste gasication helps to solve two major problems at the same
time. Gasication of food waste reduces landll problems and
helps to recover energy at the same time. Characteristics of food
waste gasication and pyrolysis have been investigated in terms
of syngas yield, hydrogen yield, energy yield and apparent thermal
* Corresponding author. Tel.: +1 301 405 5311.
E-mail address: islam@umd.edu (I.I. Ahmed).
0306-2619/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2009.08.032

efciency. The results show that food wastes offers a good potential for thermal treatment of the waste with the specic aim of
power generation.
The average proximate analysis of food wastes is 80% volatile
matter, 15% xed carbon, and 5% ash. The volatile matter can be
easily destructed in a relatively short period of time, extending
from 8 to 12 min at reactor temperatures from 700 to 1000 C. Energy recovery from volatile components in food wastes can be
recovered using a simple pyrolysis process. However, in order to
consume the residual xed carbon after the pyrolysis, the sample
must undergo a gasication process. Gasication of a food waste
sample includes a pyrolysis part and a char gasication part. Char
gasication reactions are slower than that of pyrolysis and consequently, is the rate limiting step in the overall gasication process.
The ash present in the sample does not react with the gasifying
agent. The ash can be collected after cooling and cleaning the syngas, and then recycled for its further use in industrial processes.
Since the char gasication process is the rate limiting step, it is
important to quantify the kinetic parameters of char gasication.
Char gasication has been investigated by a large number of
researchers. Some of the important parameters investigated include the origin of the char sample, gasifying agent, total pressure,
variation of partial pressure of gasifying agents, geometric changes
of the sample during gasication, and catalyzed char gasication.
One of the most important parameters which have been investigated is the catalytic effect of ash content on char gasication.

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I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

Catalytic effect of ash on char gasication has been investigated for

several biomass samples. Kinetics of food waste char gasication
did not draw the attention of researchers in this eld. Since food
waste has considerable ash content, its catalytic effect must be
investigated. Results show that ash has a positive effect on char
reactivity. Kinetic parameters have been calculated for different
degrees of conversion. Values of kinetic parameters were found
to be affected by the degree of conversion. Quantitative analysis
of kinetic parameters dependency on sample conversion has been
examined here. Quantifying the catalytic effect of ash on char
kinetics will help assist improving gasiers design with better controlled parameters for input and operational conditions, such as,
operating temperature, gasication condition, gasifying support
media, rate of feedstock to the gasier. In conjunction with uid
dynamic simulations, improved expressions for reaction rates will
help provide better estimate on char particles residence time in the
reactor by providing an accurate conversion-time relationship.
Consequently, for a desired feed rate of feedstock into the reactor
and for known gasier operational conditions an accurate reactivity expression will lead to a close estimate of the gasier size and
conguration. If a constant reactivity value is used in reacting ow
simulations for feedstock having time dependant reactivity, misleading information on char particles residence time will be obtained. This will consequently result in a departure gasier size
from the true design size and conguration. For example, if a constant reactivity value is used for chars having ash catalytic effect,
such as the case examined here, the designed gasier size will be
over estimated since the reactivity of char was fond to increase
with the degree of conversion.
2. Background
Tancredi et al. [2] investigated the catalytic effect of ash on char
gasication for eucalyptus wood chars. The ash content in char was
of the order of 1.45% on mass basis. The reactivity of the char increases monotonically with conversion. At low and intermediate
conversion, it can be attributed to the increase in surface area as
gasication proceeds. At high conversion levels a steeper increase
in reactivity has been observed, which cannot be explained by
the development of surface area. This region of the reactivityconversion curves can be better explained as the result of an increase in catalytic effect of the metallic constituents (mainly Na
and K) present as inorganic matter in the chars. Here CO2 was used
as the gasifying agent. Activation energies determined were found
to vary within a narrow range of 230257 kJ/mol. Arrhenius plots
showed parallel lines for different degrees of conversion. Parallel
line of Arrhenius plot indicates similar activation energies. The increase in reactivity was mainly due to an increase in pre-exponential factor. In a similar study by Montesinos et al. [3], steam
gasication and CO2 gasication of grape fruit skin char were
investigated. They also observed an increase in reactivity at high
values of conversion. However, a different trend of activation energies values was observed; in the case of CO2 gasication, as the
conversion increased, a decrease in activation energy was observed. On the other hand an increase in activation energy was observed in case of steam gasication. This increase in activation
energy was also, observed by Marsh et al. [4]. The decrease in activation energy values in the case of CO2 gasication was accompanied by a decrease in pre-exponential factor as well. This behavior
is called the compensation effect [5]. Montesinos et al. obtained a
value of isokinetic temperature of 1150 K. The isokinetic temperature is the temperature at which all reactivities are equal for different conversions. An isokinetic temperature of 1449 K was obtained
by Dhupe et al. [6] for CO2 gasication using catalyzed sodium lignosulfonate. Feistel et al. [7] found this temperature to be 1425 K,
obtained using potassium-catalyzed steam gasication.

Gokarn and Muhlen [8] investigated the gasication of char

using two types of catalysts and a mixture of both the catalysts.
The investigated catalysts were calcium lignosulfonate and sodium
lignosulfonate. The carbon matrix was saturated by calcium lignosulfonate at 10% by weight. However, this saturation did not affect
the catalytic effect of sodium lignosulfonate in the mixed catalytic
system.
Li and Cheng [9] investigated the catalytic gasication of coal
char using Na2CO3 and K2CO3 as catalysts. Effect of catalyst loading
was investigated. Increase in catalysts loading was found to be
effective until 25% by weight of K2CO3 loading and 20% by weight
of Na2CO3 loading. Further increase in catalysts loading resulted in
a decrease in char reactivity. The results of reactivity versus conversion plots showed an increase in char reactivity initially. Further increase in conversion showed a decrease in char reactivity.
They attributed this decrease to the char pores blocking the catalyst at high degrees of conversion. A compensation effect was observed and an isokinetic temperature of 1289 C for Na2CO3 and
1466 C for K2CO3 were obtained.
Food wastes, especially which have high percentage of vegetable oil and animal fat, provide a good potential for production of
liquid fuels though transesterication. Transesterication is the
process of exchanging the organic group R00 of an ester with the organic group R0 of an alcohol. The process is widely used to produce
biodiesel fuels from vegetable oils and animal fats. The process is
often catalyzed by an acid or a base.
Other than acid or base catalysts, enzyme or heterogeneous catalysts might be used as well. Among the mentioned catalysts, alkali
catalysts are more effective. However, if the oil has high free fatty
acid (FFA) content, higher than 3% (approximately), acid catalyzed
transesterication is used rather than a base catalyst [10,11].
Drawbacks of alkaline or acid catalysis process include: (a) it requires considerable amounts of energy; (b) separation of glycerol is
difcult; (c) the alkaline catalyst has to be removed from the product, free fatty acid and water interfere with the reaction. On the
other hand, enzymatic catalysts have the advantage of effectively
acting as catalyst in the transesterication of triglycerides in either
aqueous or non-aqueous systems. Besides, free fatty acids contained in waste oils and fats can be completely converted to alkyl
esters. However, production cost of enzymatic catalysts is signicantly higher than that of an alkaline catalyst [10].
It is to be noted that the conversion rate increases with reaction
time and temperature. At xed reaction time the increase in temperature provides the same effect of increased conversion [10].
Al-Widyan and Al-Shyoukh [11] conducted an experimental
investigation of the transesterication of waste palm oil into biodiesel fuel. Acidic catalyst has been used due to the high free fatty
acid content of 1015%. Effect of catalyst concentration and alcohol
levels, amongst other parameters, has been investigated.
The results show that at any given catalyst concentration and
reactor temperature, specic gravity decreases exponentially with
time and ends up with an asymptotic value. However, higher catalyst concentrations, results in obtaining the terminal value of specic gravity in much shorter times. Higher the excess alcohol levels
consistently led to desirable lower values of specic gravity
throughout the reaction time.
He et al. [12] investigated the continuous production of biodiesel fuel from vegetable oil using supercritical methanol process.
Reactor temperature, pressure, alcohol to oil ratio and residence
time was varied in order to determine conditions for maximum
production rate. The optimal reaction condition under constant
reaction temperature process was found to be 40:1 molar ratio of
alcohol to oil, 25 min of residence time, 35 MPa and 310 C. At
these conditions, the maximum production yield was 77% for a
constant reaction temperature. Side reactions of unsaturated fatty
acid methyl esters (FAME) were observed when reaction tempera-

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

ture exceeded 300 C, which led to a loss in unsaturated fatty acid

methyl esters (FAME). They proposed a new methodology to avoid
the loss of FAME at high temperatures, through gradual heating of
the reactants along the reactor to a high temperature. With the
new reaction technology, the methyl esters yield reached more
than 96%.
3. Experimental
Fig. 1 shows a photograph of the laboratory scale experimental
facility used to examine the pyrolysis and gasication of food
wastes. Steam is generated from the stoichiometric combustion
of hydrogen and oxygen. Steam generated is then introduced into
the superheater section to form the gasifying agent at the desired
condition. The temperature of the gasifying agent heater is kept
at the same temperature as that of the main reactor in which sample material was allowed to undergo gasication. Steam is then
introduced into the main reaction chamber that contained the
hydrocarbon sample. The syngas owing out from the main reaction chamber is sub-divided into two paths; one passes to the sampling line while the other is passed through the exhaust system.
The bypass line has a non-return valve and a ow meter to assure
the desired unidirectional ow out from the reactor. The syngas
sample is then introduced to a condenser followed by a low pressure lter and a moister absorber (anhydrous calcium sulfate). This
procedure assured that the sample is dry prior to its introduction
into a gas analyzer. The ltered and dried syngas is then analyzed
using a GC or a mass spectrometer.
3.1. Syngas characteristics experiments
The syngas characteristics were determined using a Micro gas
chromatograph (GC). The syngas ow is introduced to a three
way valve that allowed for either lling sampling bottles or introducing the syngas directly to the micro GC for detailed analysis of
the gas. The sampling bottles are used only when short sampling
intervals are needed (0.51 min). Direct sampling and analysis
were carried out by the GC when longer sampling time intervals
were required.
A constant ow rate of inert gas (nitrogen) is introduced with
the oxygen ow, in case of gasication. However, only nitrogen is
used for all experiments carried out during pyrolysis. The nitrogen

103

is detected by the GC and used to determine the ow rate of different syngas species by comparing the species mole fraction to that
of the nitrogen mole fraction.
3.1.1. Experimental conditions for syngas characteristics





Sample: 35 g of food waste.

Reactor temperature: 800 and 900 C.
Inert gas: 2.6 LPM of nitrogen.
Gasifying agent: 8 g/min of steam.

3.2. Char kinetics experiments

Char-steam reactions are slower than that of pyrolysis reactions; consequently it is the rate determining step in the overall
gasication process.
3.2.1. Char preparation
For char preparation, both the main and gasication conditioning reactors were heated up to 900 C. A continuous ow of argon
was introduced to both reactors during and after heating. Then a
sample was introduced to the main reactor through a fast connection located at the reactor exit. The sample was kept at this temperature of 900 C for an hour. In order to insure that the
pyrolysis process has been completed with the sample, a sample
of the exit gases was analyzed. The charring process is considered
complete when the analyzed exhaust contained only Argon in the
stream ow.
3.2.2. Reactivity determination procedures
In order to examine the catalytic effect of ash the char gasication a mass spectrometer was used. Data from the mass spectrometer was used to calculate the reactivity of carbon in the sample
char. Carbon in the sample will evolve in the form of carbon-monoxide through the water gas reaction (C + H2O => CO + H2) and in
the form of carbon dioxide through the water gas shift reaction
CO H2 O () CO2 H2 . Consequently, monitoring the evolution
of CO and CO2 ow rate helps to calculate the carbon consumption
rate from the sample. Helium was used as an inert gas in the reactivity experiments to avoid the confusion between CO and N2 in
the mass spectrometer. The mass spectrometer was used to measure the ow rate of CO and CO2 obtained by relating the partial

Fig. 1. A photograph of the experimental facility.

104

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

pressure of CO and CO2 with the partial pressure of Helium. For this
purpose the ow rate of Helium was kept constant at a known ow
rate. From the carbon ow rate-time, relationship one can calculate
the total yield of carbon and instantaneous sample mass inside the
reactor at time (t).

section of the discussion. The second part is concerned about the

kinetics of char gasication from food waste with specic focus
on the catalytic effect of ash.

3.2.3. Experimental conditions for kinetics experiments

Fig. 3 shows the evolution of syngas ow rate with time at two

distinctly different high temperatures of 800 and 900 C. Syngas
ow rate starts with a high value which is attributed to the rapid
devolatilization of volatile components from the sample. This is
then followed by sudden decrease in ow rate, and nally followed
by a long period of low ow rate. The low ow rate period is attributed to the char gasication. Syngas ow rate due to char gasication decreases monotonically until char is consumed and only ash
is left over. The area conned between the pyrolysis curve and gasication curve represents the syngas yield from the char gasication. The increase in reactor temperature increased syngas ow
rate and decreased the gasication period. The syngas ow rate
from paper at the same temperatures was higher in terms of maximum value of ow rate. The maximum ow rate from paper gasication [13] was 5.5 g/min and 10 g/min at temperatures of 800
and 900 C, respectively. However the maximum ow rate from
food waste gasication was found to be 4 and 7.6 g/min at temperature of 800 and 900 C, respectively. The gasication period for
paper was 50 and 18 min at 800 and 900 C. However, gasication
period for the food waste was 105 and 38 min at same temperature
of 800 and 900 C, respectively. The experimental conditions for
the paper and food waste gasication were kept the same.
Fig. 4 shows the evolutionary of hydrogen ow rate from food
waste gasication and pyrolysis at two different temperatures of









Sample: 35 g of food waste.

Inert gas for charring: 6.4 g/min of argon.
Charring temperature: 900 C.
Charring period: 1 h.
Reactor temperature: 750, 800, 850 and 900 C.
Gasifying agent: 8 g/min of steam.
Trace gas: 1.1 g/min of helium.

4. Results and discussion

The characteristic of syngas from food waste pyrolysis and gasication have been investigated. Food waste is a char-based sample. Results from char-based samples (samples containing
volatile matter and char, such as paper [13], cardboard [14,15],
woodchips and food waste) follow, qualitatively similar trend. Syngas is characterized by a high ow rate initially, due to pyrolysis,
and then followed by a small ow rate which lasts for longer period, which is due to char gasication. The progress of the food
waste sample through pyrolysis and gasication processes is
shown in Fig. 2. Syngas characteristics may differ from a quantitative point of view. The differences and similarities between food
waste and previously investigated samples is presented in the rst

Food waste
(Simulated as dog food)
(~35 grams)

4.1. Syngas characteristics

Char + Ash
Ash (~5.75%)
(~20.75%) Char gasification
o
(~35 min @ 900 C)

Pyrolysis
(~15 min @ 900oC)

Gasification
(~38 min @ 900oC)
Fig. 2. Progress of food waste sample through pyrolysis and gasication.

Gasification at 800C

Pyrolysis at 800C

Gasification at 900C

6
g/min

g/min

4
3

Pyrolysis at 900C

5
4
3

0
0

15

30

45
60
75
Time (min)

90

105

10

20

30

Time (min)

Fig. 3. Syngas ow rate from gasication and pyrolysis at 800 C (left) and 900 C (right).

40

50

105

0.08

Gasification at 800C

0.08

0.06

Pyrolysis at 800C

0.06
g/min

g/min

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

0.04

Gasification at 900C
Pyrolysis at 900C

0.04
0.02

0.02

0
0

15

30

45

60

75

90

105

10

20

30

40

50

Time (min)

Time (min)

Fig. 4. Hydrogen ow rate with time from gasication and pyrolysis at 800 C (left) and 900 C (right).

140
Output power (kJ/min)

Output power (kJ/min)

140
120
100

Gasification at 800C

80
pyrolysis at 800C
60
40
20

120
Gasification at 900C

100

Pyrolysis at 900C

80
60
40
20
0

0
0

15

30

45

60

75

90

105

10

20

30

40

50

Time (min)

Time (min)

Fig. 5. Output power from gasication and pyrolysis at 800 C (left) and 900 C (right).

800 and 900 C. Gasication yields more ow rate of hydrogen

than pyrolysis. This is a direct result of using steam as the gasifying
agent. Reactions resulting in this increase include water gas reaction, water gas shift reaction and steam tar reforming. The increase
in temperature accelerates hydrogen evolution for both pyrolysis
and gasication; however the total yield remains the same, see
Fig. 7. Peak values of hydrogen ow rate from paper gasication
[13] were 0.077 and 0.175 g/min at 800 and 900 C, respectively,
which are almost double the values obtained from the gasication
of food waste.
Fig. 5 shows the output power form food waste gasication and
pyrolysis at 800 and 900 C. One can see form Fig. 5 that initially
output power is totally attributed to pyrolysis. The area conned
between the pyrolysis and gasication curves represents the extra
energy gained from the gasication of char.
Figs. 6 and 7 show the total syngas and hydrogen yield, respectively, from food waste during pyrolysis and gasication at 800 and
900 C. Hydrogen yield from food waste was 1.6 g at both the
temperatures. The total hydrogen yield from paper gasication
[13] was about the same value (1.5 and 1.6 g) at reactor temperature 800 and 900 C.
Figs. 8 and 9 show the energy yield and apparent thermal efciency, respectively. The apparent thermal efciency was calculated based on a heating value of 6528 Btu/lb [16]. The increase
in temperature increased energy yield and apparent thermal efciency for both pyrolysis and gasication. These results are similar
to that found from gasication and pyrolysis of paper [13]. However, food waste yields more energy and better apparent thermal
efciency as compared to paper. Energy yield and apparent thermal efciency from paper gasication were 345 and 0.68 at

35

Syngas yield (g)

30

Gasification
Pyrolysis

25
20
15
10
5
0
800

900
Temperature (oC)

Fig. 6. Syngas yield from gasication and pyrolysis of food waste.

800 C and 405 and 0.84 at 900 C. On the other hand, energy yield
and apparent thermal efciency from food waste gasication were
425 and 0.8 at 800 C and 468 and 0.9 at 900 C.

4.2. Char gasication kinetics

The char gasication reaction is slowest in the overall gasication process. So, it is important to quantify how fast this process is.
The main constituent of char is carbon and main reaction in the
char gasication process is the water gas reaction C H2 O >
CO H2 . The carbon-monoxide may undergo a water gas shift

106

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

1.8

H2 yield (g)

1.6

Carbon conversion

Gasification
Pyrolysis

1.4
1.2
1
0.8
0.6
0.4
0.2

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

900C
850C
800C
750C

0
800

30

60

900
Temperature (oC)

90
120 150
Time (min)

180

210

Fig. 10. Conversion versus time for temperatures 750, 800, 850 and 900 C.

Fig. 7. Hydrogen yield from gasication and pyrolysis of food waste.

2.50E-01

900C
850C
800C
750C

2.00E-01
-1

400

Energy yield (kJ)

Gasification
Pyrolysis
r (min )

500

300

1.50E-01
1.00E-01

200

5.00E-02

100

0.00E+00

0
800

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Carbon conversion

900
Fig. 11. Char reactivity versus conversion for temperatures 750, 800, 850 and
900 C.

Temperature (oC)
Fig. 8. Energy yield from food waste during gasication and pyrolysis.

1
0.8

, where m is the mass

Carbon reactivity was dened as r  m1 dm
dt
at time (t). History of carbon mass inside the reactor was calculated
is the carbon mass ow
from the carbon ow rate history. While, dm
dt
rate measured by the mass spectrometer. Fig. 11 shows the change
of carbon reactivity with conversion. Carbon reactivity increases
monotonically with conversion until conversion value of 0.7 followed by a steeper increase in reactivity. The steepness at lower
temperature plots may not be observed because of the r values
scale. The food waste char contains 27.7% ash, most of which is
salt. The inorganic components in char are the main reason of reac-

Apparent thermal efficiency

Gasification
Pyrolysis

0.6
0.4
0.2

X = 0.1
X = 0.3
X = 0.5
X = 0.7
X = 0.9

-1.5

0
800

900

-2

Temperature ( C)
-2.5

X = 0.2
X = 0.4
X = 0.6
X = 0.8

ln (r)

Fig. 9. Apparent thermal efciency of food waste during gasication and pyrolysis.

reaction CO H2 O () CO2 H2 . Therefore, the carbon reactivity

in the char can be inferred from the molar ow rate of carbonmonoxide and carbon dioxide. A mass spectrometer has been used
to calculate the CO2 and CO ow rate. From the CO and CO2 ow
rate, the total carbon yield and carbon conversion history can be
determined. Fig. 10 shows the carbon conversion versus time at
temperatures of 750, 800, 850 and 900 C. The plots are characterized by an initial constant slop. The results show that lower is the
temperature longer is the conversion time.

-3
-3.5
-4
-4.5
-5
0.00085

0.0009

0.00095

0.001

1/T (K-1)
Fig. 12. Arrhenius plot at different degrees of conversion from 0.1 to 0.9.

107

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

Table 1
Activation energies and pre-exponential factor at different degrees of conversion for X = 0.10.9.
Carbon conversion

Arrhenius equation lnr lnA  RE T1

Activation energy, E (kJ/mol)

Pre-exponential factor, A (min1)

0.1

lnr 8:5228  13424 1T

111.6071

5028.113

0.2

lnr 7:7939  12501 1T

103.9333

2425.76

0.3

lnr 7:7964  12386 1T

102.9772

2431.832

0.4

lnr 8:6576  13241 1T

110.0857

5753.709

0.5

lnr 9:2199  13751 1T

114.3258

10096.05

0.6

lnr 9:1941  13579 1T

112.8958

9838.908

0.7

lnr 9:3624  13603 1T

113.0953

11642.3

0.8

lnr 10:337  14501 1T

120.5613

30853.33

0.9

lnr 11:124  15133 1T

125.8158

67778.48

-1

X = 0.93

X = 0.94

-1.5

X = 0.95

X = 0.96

X = 0.97

X = 0.98

X = 0.93
X = 0.94
X = 0.95
X = 0.96
X = 0.97
X = 0.98

0
-1
ln (r)

ln (r)

-2
-2.5

-2

-3

-3
-3.5
-4
0.00085

-4

0.00090

0.00095

0.00100

-1

Fig. 13. Arrhenius plot at different degrees of conversion from 0.93 to 0.98.

tivity increase, since they have a catalytic effect. From the reactivity information, kinetic parameters, activation energy E and preexponential factor A, were calculated. A rst order reaction model
has been used. Fig. 12 shows the Arrhenius plot from which the
activation energies and pre-exponential factors at different degrees
of conversion (X) have been calculated. Results of the linear ttings
of ln(r) versus 1/T, pre-exponential factors and activation energies
for conversion values from 0.1 to 0.9 are shown in Table 1. From
Fig. 12 one can see that the Arrhenius plots show almost parallel
lines with increasing intercept with conversion. Parallel lines indicate constant values of activation energy. Values of activation energies in this range of conversion (0.10.9) were found to uctuate
around an average of 113 kJ/mol. However, values of pre-exponential factor increase with conversion. The trend of activation energies and pre-exponential factors indicates that the increase in
reactivity in this range of conversion is attributed to increase in
pre-exponential factor. In theory, the pre-exponential factor or frequency factor, A, depends on how often molecules collide with
each other and whether the molecules are properly oriented or
not. Although in solid reactions, the pre-exponential factor and

9
1/T (K-1)

1/T (K )

10
-4
x 10

Fig. 14. Arrhenius plot for conversions from 0.93 to 0.98 showing the isokinetic
temperature and isokinetic reactivity.

activation energy do not have the physical signicance as in gas

reactions [5] a logical reasoning can be introduced to explain the
increase in pre-exponential factor. Ash may have increased the
adsorption rate of steam to the char surface and consequently,
raised the reaction rate.
Fig. 13 shows the Arrhenius plot for conversions from 0.93 to
0.98. A compensation effect was observed here, where there is a
simultaneous decrease in activation energy and pre-exponential
factor with increase in conversion, see Table 2. The simultaneous
decrease in activation energy and pre-exponential factor is called
the compensation effect or isokinetic effect [5]. In a compensation effect behavior, Arrhenius plots should intersect at a singe
point at the isokinetic temperature and isokinetic reactivity. Since
the plots do not intersect in the examined temperature range, an
extrapolation for the linear ttings was used to nd the isokinetic
temperature and reactivity. The extrapolation is shown in Fig. 14.
Since the lines do not intersect exactly at a single point, the
weighted average of 15 intersections was used to nd the isokinetic temperature and reactivity. According to Agrawal [5] in order to

Table 2
Activation energies and pre-exponential factors at different degrees of conversion from 0.93 to 0.98.
Carbon conversion

Arrhenius equation lnr lnA  RE T1

Activation energy, E (kJ/mol)

Pre-exponential factor, A (min1)

0.93

lnr 10:905  14795 1T

123.0056

54447.92

0.94

lnr 10:761  14600 T1

121.3844

47145.79

0.95

lnr 10:579  14362 1T

119.4057

39300.79

0.96

lnr 9:8673  13517 1T

112.3803

19289.19

0.97

lnr 9:3667  12861 1T

106.9264

11692.47

0.98

lnr 8:8081  12120 1T

100.7657

6688.2

I.I. Ahmed, A.K. Gupta / Applied Energy 87 (2010) 101108

ln (A)

108

12
11
10
9
8
7
6
5
4
3
2
1
0
-1 0
-2

in gasifying agent adsorption rate to char surface. However, in

the conversion range from 0.93 to 0.98 the increase in reactivity
was accompanied by a decrease in activation energy. A compensation effect was observed in this range of conversion, from 0.93 to
0.98. Isokinetic temperature obtained from Arrhenius plots for X
from 0.93 to 0.98 was 1001 C.

ln(A) = 0.000095*E - 0.801003

Acknowledgment
This research was supported by the ONR and is support is gratefully acknowledged.

25

50

75

E (kJ/kmol)

100
125
Thousands

Fig. 15. ln(A) versus E for the conversion from 0.93 to 0.98.

validate the presence of correct compensation effect, the linear plot

of ln(A) versus E should have a slop of 1/RTiso, were Tiso is the isokinetic temperature and an intercept of ln(riso), where riso is the isokinetic reactivity. ln(A) versus E is shown in Fig. 15. From the slop
value in Fig. 15, the isokinetic temperature should be 991 C
and ln(riso) should be 0.801. Tiso and ln(riso) values obtained from
Fig. 14 are 1001 C and 0.72 respectively, which is close to the
values obtained from Fig. 15. So, in summary, compensation effect
is observed by the end of conversion but was not observed before
conversion degree of 0.9.
5. Conclusions
Gasication yielded enhanced production of syngas, hydrogen
and energy as that obtained from pyrolysis. However the time required for gasication is more as compared to pyrolysis. As compared to paper gasication at the same conditions, food waste
needed more time to complete the gasication process. Inorganic
constituents in food char were found to have a catalytic effect. Char
reactivity increased with degree of conversion. In the conversion
range from 0.1 to 0.9 the increase in reactivity was accompanied
by an increase in pre-exponential factor, suggesting an increase

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