[Sarkar and Chowdhury, 3(6): June, 2014]

ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852

IJESRT
INTERNATIONAL JOURNAL OF ENGINEERING SCIENCES & RESEARCH
TECHNOLOGY
Studies on Catalytic Pyrolysis of Mustard Press Cake with NaCl
1*

Aparna Sarkar1 , Ranjana Chowdhury *

Chemical Engineering Department, Jadavpur University, Kolkata 700032, India
[email protected], [email protected]
Abstract

Under this present investigation, non-catalytic and catalytic pyrolysis of mustard press cake (MPC) was
conducted in a 50 mm diameter and 640 mm long semi-batch pyrolyser in the temperature range of 673K to 1173K
in a nitrogen atmosphere. Effects of temperature on yields of products, namely, char, pyro-oil and gas obtained from
primary pyrolysis of MPC have been investigated. The kinetic rate constants of volatiles and char formations were
determined in the temperature range under the study. The activation energies and pre-exponential factors were
determined. The catalytic effects of NaCl on the pyrolysis of MPC have also been investigated at three different
temperatures namely, 673K, 773K and 873K. Catalyst loading was varied from 5-15% (w/w biomass). The product
yields of catalytic and non-catalytic pyrolysis of MPC was compared. The activation energies of catalytic pyrolysis
have been observed to be low in comparison to non-catalytic ones.
Keywords: Mustard press cake, Catalytic and Non-catalytic pyrolysis, NaCl catalyst, Reaction kinetic, Product yield

Introduction
In current business scenario, conventional
fossil fuels as energy resources will be extinct within
40-50 years due to the abruptly increasing price of
crude oil and fluctuating economic growth rate of
India. On the other hand, greenhouse gases mainly,
CO2, contribute to the global climate changes. But
due to the rapid growth of population the demand of
energy is continuously increasing in India. Therefore,
the recovery of energy from renewable sources is
necessary. Nowadays biomass is considered as major
renewable sources to produce the potential energy in
near future. Since biomass contains negligible
amount of sulphur, nitrogen and metal content, the
energy generated through biomass also reduces the
emission of CO2 and SO21. Generation of biofuel
from biomass may be through chemical, biochemical
and thermochemical processes. Among several
thermochemical conversion processes such as,
pyrolysis, combustion and gasification, pyrolysis
method has been introduced as most recent renewable
energy process for producing (1) char, which might
be used as solid smokeless fuels for barbeque,
activated carbon and an adsorbent or for landfilling,
(2) pyro-oil, which might be used as a fuel, an energy
carrier and a source of chemical and (3) the gaseous
product might be used for all energy requirements of
the pyrolysis plant due to its higher calorific value.
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The production of char, pyro-oil and gas might be

maximized just by the adjustment of pyrolysis
technique and reaction parameters.
The quality and composition of the pyro-oil
depends on the biomass composition and its
extractive content. Therefore, higher yield of pyro-oil
may be obtained during pyrolysis of the agricultural
residues (biomass) due to its higher amount of
extractives and cellulose. Several research works
have already been reported regarding various aspects
of pyrolysis of agricultural residues namely, sesame,
mustard and neem de-oiled cake2, jatropha oil cake3,
olive residue4, rapeseed cake5, 6, pungam oil cake7,
sunflower oil cake8, safflower oil cake9, cotton seed
cake10, soyabean cake11 and mustard press cake12 etc.
The pyro-oil obtained from biomass could not be
used directly due to its high viscosity, corrosiveness,
poor heating value and relative instability. Therefore,
a upgrading process is required for removal of
oxygen content of the pyro-oil13, 14. Several methods
have already been examined for upgrading the pyrooil quality, namely, catalytic cracking of pyrolysis
vapors, hydrodeoxygenation, extracting chemicals,
and esterification etc. In recent year among these
methods the catalytic pyrolysis of biomass has been
receiving great attention due to its significant
processing

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and economic advantage over hydro-treating

in absence of H215. Catalytic pyrolysis of various type
of oil cake namely, rapeseed cake16-18, karanja seed19,
mohua seed cake20, sunflower oil cake21 and
sufflower oil cake22 have already been reported.
However, no works have been reported on the
catalytic pyrolysis of mustard press cake.
Under this present investigation, mustard
press cake (MPC) has been selected as a pyrolysis
feed stock. Catalytic and non-catalytic pyrolysis of
MPC was conducted in a packed bed reactor. Effects
of temperature on yields of products obtained from
catalytic and non-catalytic pyrolysis of MPC has
been investigated. The activation energies and preexponential factors of catalytic and non-catalytic
pyrolysis have been determined.

Materials and methods

Materials
Mustard press cake (MPC) sample has been
collected from a local oil mill situated near Jadavpur
University, Kolkata. The proximate and ultimate
analyses of mustard press cake have been listed in
table 1. The ultimate analyses have been done using
CHNSO analyser (2400 series-II, Perkin Elmer, U. S.
A.). Calorific value of raw materials has also been
determined using bomb calorimeter, i.e. 14.56
MJ/Kg.
Table 1. Proximate and ultimate analyses of feed stock

Property
Moisture content
Volatile matter
Ash content
Fixed carbon
C
H
N
S
O

Wt %
14.34
63.49
7.7
14.47
40.26
6.03
6.46
1.11
46.14

discussed in previous study done by Chowdhury et

al.,23 and Sarkar et al.,12.
Catalytic Pyrolysis
The MPC was impregnated with NaCl
(Merck purity >99 %) by quenching of the MPC with
the NaCl solution and by subsequent, evaporation of
the moisture in the hot air oven. The catalytic
pyrolysis of MPC was carried out in the same
pyrolyser23, 12 at temperatures of 673K, 773K and
873K with 5 % NaCl, (w/w). Catalyst loading was
varied from 5-15% (w/w MPC).

Pyrolysis kinetics
Pyrolysis of MPC sample proceeds through
complex reactions in series, parallel or combination
of both. Under the present study a parallel reaction
model has been attempted to describe pyrolysis
kinetics of MPC. The reaction kinetics of volatile and
char have been elaborately discussed in pyrolysis of
coconut shell24, vegetable market waste25 and textile
wastes23. The reaction pathway of pyrolysis
according to the present model is as follows,

Results and Discussion

Effect of pyrolysis temperatures on product yield

Volatile (Gas
+ tar)

kc

Char

k
MPC

Active complex

After completion of catalytic and noncatalytic pyrolysis of mustard press cake, the solid
residue was collected from the reactor. From the
kinetic model24, 25, the amount of unreacted sample
and the char yield were determined. The condensable
part of volatile was considered as pyro-oil. The gas
yield was calculated by subtracting the amount of
pyro-oil from the yield of volatiles.

Experimental
Non-catalytic Pyrolysis
The non-catalytic pyrolysis experiment of
MPC was conducted in a 50 mm diameter and 640
mm long cylindrical stainless steel fixed bed
pyrolyser in the temperature range of 673K to 1173K.
The experimental procedure has already been

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ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852

Non-catalytic pyro-product yield

The yields of char, pyro - oil and gases
obtained from non-catalytic pyrolysis of MPC in
relation to the process conditions are shown in figure
1.

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ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852
The char yield obtained by the non-catalytic and
catalytic pyrolysis of MPC has been shown in figure
2.

Figure 1. Percentage of product yields obtained at one

hour from non-catalytic pyrolysis of mustard press cake
(MPC) at different temperatures

The char yield decreased from 37 35%

when the temperature was increased from 673 to
1173K. The decrease in the char yield with pyrolysis
temperature is to be attributed to an increasing devolatilization of the solid hydrocarbons in the char.
Partial gasification of the carbonaceous residue is
also possible26.
On the other hand, the bio-oil yield
increased from 39 to 46 % when the temperature was
increased from 673K to 973K. Above this
temperature, the yield of bio-oil decreased. In case of
castor seed27, mustard cake2, polanga seed cake28
similar trend of bio-oil have been reported. At 1173K
the yield of bio-oil was 35%. Appearance of a
maximum in the trend of yield of pyro oil against
temperature may be due to the commencement of
further cracking of tar molecules to lower gaseous
molecules at higher temperatures.
The gas yield obtained from MPC gradually
decreased from 39 18% respectively with the rise of
temperature from 673K to 973K. Above this
temperature the gas yield suddenly increased from
22% to 29% with the rise of temperature from 1073K
to 1173K. The increase in gaseous products may be
due to the secondary cracking of the pyrolysis
vapours at higher temperature. Nevertheless, as
already mentioned, the secondary decomposition of
the char at high temperatures may also give noncondensable gaseous products, owing to a
heterogeneous reaction between the char and gaseous
components such as H2O26.

Figure 2. Distribution of weight fraction of char yield at

different temperature and at different concentration of
NaCl

It can be seen that char yield decreased with

the rise in pyrolysis temperature. From the close
observation of the data it also appears that the
catalyst has significant effect on char yield. The yield
of char increased significantly with the addition of
catalyst at various concentrations.
In case of non-catalytic pyrolysis, the char
yield decreased from 37.72 36.21% when the
temperature was increased from 673 to 773K. In case
of catalytic pyrolysis at 773K the amount of char
yield were 27%, 28% and 33% at different
concentrations of NaCl, namely, 5%, 10% and 15%
respectively. This decrease in char yield during the
studies of catalytic pyrolysis of MPC was related to
the higher ratio of heat carrier to biomass resulting in
higher volatilization rate of biomass particles29.
Similar trend has been observed by previous
researchers during the studies of hydrothermal
treatment of biomass30 and catalytic pyrolysis of
woody biomass31.
Pyro-oil yield
The yields of pyro-oil obtained from noncatalytic and catalytic pyrolysis of MPC at three
different temperatures and at three different
concentrations of NaCl have been shown in figure 3.

Catalytic pyro-product yield

Char yield
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ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852
The percentage of gas yield decreased with
the rise of temperature in case of non-catalytic
pyrolysis of mustard oil cake. However, the gas yield
becomes higher when catalyst is used. The
justification is probably the same as in case of
decrease of tar yield of catalytic pyrolysis in
comparison to non-catalytic pyrolysis, i.e., due to the
increase in the rate of secondary tar cracking
reactions.

Figure 3. Distribution of weight fraction of pyro-oil yield

at different temperature and at different concentration of
NaCl

During the studies of non-catalytic

pyrolysis, the maximum pyro-oil yield of 41.17%
was obtained at 873K. In presence of catalysts,
decrease of tar yield of 6%, 11% and 18% in
comparison to non-catalytic pyrolysis has been
observed at 873K when the loading of NaCl is
maintained at 5%, 10% and 15% respectively. This
may be due to the increase of secondary tar cracking
reactions under the influence of catalysts.
Gas yield
The distribution of gaseous product at
different non-catalytic and catalytic temperatures and
at different concentrations of NaCl has been shown in
figure 4.

Activation energy and frequency factor

The values of frequency factors and
activation energies of the reactions of reactant
decomposition, volatile formation and char formation
are determined by regression analysis of the rate
constant of non-catalytic pyrolysis of MPC
determined in the temperature range of 673K to
1173K24, 25. The frequency factors and activation
energies of different reactions of catalytic pyrolysis
of MPC has also been determined in the temperature
range of 673K to 873K. All values have been
mentioned in table 2.
Table 2 Calculated Activation Energies and Frequency
Factors as per Arrhenius Law

Reac
tion
rate
const
ant

Activation
energy
(KJ/mol)

M
PC

k
kv
kc

16.
15
16.
47
15.
47

5
%
Na
Cl
9.1
2
11.
26
4.2
1

15
%
Na
Cl
7.3
7
9.6
4
3.3
5

Frequency
factor (min-1)

M
PC

0.2
63
0.1
75
0.0
87

5
%
Na
Cl
1.1
9
1.2
1
8.7
3

15
%
Na
Cl
2.7
3
3.0
1
14.
21

Correl
ation
coeffici
ent

1.0
1.0
1.0

From the analysis of the table, it is evident

that the activation energy and frequency factor
decreases and increases respectively with the increase
of catalyst loading. This clearly indicates the positive
influence of NaCl catalyst on pyrolysis rate of MPC
in the entire temperature range under study.

Conclusion
Figure 4. Distribution of weight fraction of gas yield at
different temperature and at different concentration of
NaCl

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In this present study, the mustard press cake

was chosen as a pyrolysis feed stock to produce pyrooil and char. The effect of temperature (673K to

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873K) on product yields has been studied. This

parameter has shown significant influence on
pyrolysis product yields. The kinetic rate constants of
reactions responsible for volatile and char formation
were determined in the temperature range under the
study. The activation energies and pre-exponential
factors were determined. Catalytic pyrolysis of MPC
was carried out at three different temperatures
namely, 673K, 773K, 873K and at three different
concentrations of NaCl (5-15%). The product yields
obtained from MPC through catalytic and noncatalytic pyrolysis were compared. While the yields
of char and pyro-oil obtained during the catalytic
pyrolysis are lower than the non-catalytic pyrolysis,
the gas yield shows the opposite trend, i.e., higher
yield of gas is observed in presence of catalysts. The
activation energies of catalytic pyrolysis have been
observed to be low in comparison to non-catalytic
ones, signifying the overall increase of rate of
pyrolysis in presence of NaCl. Thus, NaCl may be
successfully utilized for the enhancement of pyrolysis
rate of MPC. Catalytic effect of NaCl is also
expected in case of pyrolysis of other similar feed
stocks.

ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852
7.

8.

9.

10.

11.

Acknowledgements
We gratefully acknowledge Council of
Scientific & Industrial Research (CSIR), India for
their financial support.

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Author Biblography
Ranjana Chowdhury*
She completed PhD (Engg.)
from Jadavpur University,
West Bengal, India in 1993.
Presently she is working as a
Professor in the Jadavpur
University. She has delivered
many invited lectures at
different
organizations,
international and national
conferences and symposia.
She has supervised more than
25 Master Degree projects. 11
Doctoral Degrees have been
awarded and works have been
in progress for 10 other
candidates. She has published
about 50 research articles in
national and international
journals of repute. Her
research interest is on novel
and
advanced
chemical
reaction
engineering,
bioprocess engineering, nonconventional energy and

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ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852

mathematical modeling of
chemical and bio- reactors.
Email:
[email protected]
Aparna Sarkar1
Aparna Sarkar was a senior
research fellow of Council of
Scientific
and
Industrial
Research (CSIR). She is
working under Prof. Ranjana
Chowdhury in the chemical
engineering department of
Jadavpur University. She has
attended five international
conferences. Two research
articles have been published
in
reputed
international
journals. Around 11 articles
have been accepted in
International
conferences.
Presently her research interest
is on pyrolysis of different
municipal
solid
wastes
(MSW) and spent engine oil
and mathematical modeling
of pyrolyzer.
Email:
[email protected]

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