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Procedia Environmental Sciences 35 (2016) 513 – 527

International Conference on Solid Waste Management, 5IconSWM 2015

Kinetics of Pyrolysis of Mixed Municipal Solid Waste- A Review

V. Chhabraa,b, Y. Shastria,*, S. Bhattacharyab*
a
Indian Institute of Technology Bombay, Mumbai, India
b
Monash University, Melbourne, Australia

Abstract

Municipal solid waste management is one of the major challenges faced by most of the developing countries like India. The
scarcity of land due to large population and increasing waste production due to urbanization impose a challenge to find
innovative methods for waste disposal. Thermal treatment is seen as an emerging technology which can help in reducing the
volume of the waste and also extract energy and value added products during processing of the waste. However, the raw material
mostly has low calorific value which causes problem for its thermal treatment. Pyrolysis, combustion and gasification are the
major thermal treatment processes. Pyrolysis, found more promising than other processes, is discussed in this paperin regards to
its kinetics and reaction conditions and products formed to understand and further develop the technology. Any improvement in
the treatment processes requires an understanding of the fundamentals of the reactions specific to the waste being treated. It is
concluded that suitable combination of reaction conditions along with reactor design needs to be formulated once the process
kinetics for the treatment of mixed municipal solid waste during pyrolysis is estimated.
©
© 2016
2016Published by Elsevier
The Authors. B.V. This
Published is an open
by Elsevier access article under the CC BY-NC-ND license
B.V.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility ofthe organizing committee of 5IconSWM 2015.
Peer-review under responsibility of the organizing committee of 5IconSWM 2015
Keywords:Pyrolysis, reaction kinetics, mixed solid waste, characterization;

1. Introduction

The solid waste is generated as a byproduct of most of the socio-economic activities. The waste generated from
different sectors like commercial, institutional, domestic is included in municipal solid waste (MSW). The
urbanization, industrialization and increase in population directly affect the MSW generated (Jain and Sharma,
2011). Globally, the volume of waste generated from urban centers of the world is around 1,300 million tonnes per
year (1.2 kg/capita/day) which is expected to rise to 2,200 million tonnes per year by 2025. The waste generated

* Corresponding author.
E-mail address:yshastri@iitb.ac.in

1878-0296 © 2016 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of 5IconSWM 2015
doi:10.1016/j.proenv.2016.07.036
514 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

from South and East Asia represents 33% of the world's total quantity. It is anticipated that the MSW generation rate
in Asia will reach to 1.8 million tonnes /day by 2025 (Srivastava et al., 2014).

For India MSW generation ranges between 0.3 kg/capita/day and 0.6 kg/capita/day, with the annual volumetric
increase in MSW generation is estimated to be 1.33 % per capita. Table 1 summarizes the per capita waste
generation in different populated cities of India along with the solid waste treatment techniques employed by the
municipalities in corresponding cities.

The MSW generated is rarely treated in India. 90% of waste is unscientifically dumped openly or landfilled
creating health and environmental issues (Sharholy et al., 2008). Landfills are rather a temporary storage place, and
hence waste needs to be treated to convert it into valuable product, that is waste to product (WtP) or waste to energy
(WtE). Waste to energy processes such as biological treatment or thermal treatment utilize the energy potential in
waste to reduce CO2 and other pollutants emission to atmosphere (Helsen and Bosmans, 2010). Biological
treatments have an advantage of reducing the mass and volume of waste, yet they take time to decompose products
which may extend from few months to years. Also, bio treatment is low temperatures treatment, which does not
destroy the pathogens completely. The other Waste to energy techniques are thermal techniques such as
incineration, gasification and pyrolysis. The thermal treatment plants in India have not performed well so far in
India, yet this work focuses on thermal treatment owing to its advantage over biological treatment and landfilling.

Table 1: Waste generation & handling techniques in different populated cities of India per capita(Jain and Sharma, 2011), (KharvelAnnepu, 12)

Population (as per 2001 Waste generated Available waste treatment technique and
Name of city
census) (kg/capita/day) capacity of plant (as per 2010)
Gangtok 29,354 0.44 Composting (50 TPD)
Daman 35,770 0.42 —
Jammu 369,959 0.58 —
Dehradun 426,674 0.31 426,674
Chandigarh 808,895 0.2 Composting, Biomethanation, RDF (500 TPD)
Bengaluru 4,302,326 0.39 Composting (450 TPD)
Chennai 4,343,645 0.62 Composting
Kolkata 4,572,876 0.58 Composting (700 TPD)
Delhi 10,306,876 0.58 Composting (825 TPD), biomethanation, RDF
(1350 TPD)
Greater Mumbai 11,978,450 0.45 Composting (370 TPD)

2. Thermochemical processes

Thermal treatment of the solid waste reduces the mass by 70–80% and volume by 80–90% (Lombardi et al.,
2015). The time required for treating the waste thermally takes only minutes or hours, and forms a stable odour free
product, free of pathogens. Environmentally, thermal treatment is better than biological or landfills. Landfills emits
methane (four times more effective greenhouse gas as compared to CO2) during the anaerobic digestion of waste,
while thermal treatment releases only CO2 and other gases such as CO, methane having high calorific value is
extracted for energy recovery(Shah, 2011). As stated by Sharholy et al., (2008) all waste to energy thermochemical
techniques have been tried and tested in developed countries with positive results. These are yet to get off the
ground in India largely because the financial viability and sustainability is still being tested.

The available technologies for thermochemical treatment of waste are pyrolysis, gasification, plasma
gasification and incineration. Table 1 shows a schematic diagram of the products formed by thermally treating the
waste by different techniques. Each of the technique is discussed in the following section.
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 515

Fig. 1. Schematic representation of pyrolysis, gasification and combustion stages (Adapted from Arena, 2012)

Pyrolysis represents a process of thermal degradation of the waste in the total absence of oxygen at temperature
range of 300 Cࡈ to 850 ࡈC. The thermal degradation is associated with two sets of decomposition namelyprimary
decomposition of the solid fuel and secondary reactions of volatile condensable organic product (tar) into low-
molecular weight gases and char. The reaction products are gaseous product, a pyrolytic liquid, and char, with ash as
an undesirable residue.The other unwanted products formed are flue gases which need treatment, making the
pyrolysis process more expensive. Also, high amounts of inorganic constituents such as potassium in the raw
material cause fouling or bed agglomeration (Di Blasi, 2008).However, the advantages of pyrolysis process are that
the majority of the product formed is liquid oil, which has high calorific value of about 38MJ/kg (Velghe et al.,
2011). Also, the liquid fuel is easy to transport. Third, lesser volume of flue gases per kg of waste is produced in this
process as compared to gasification and incineration, which reduce the flue gas treatment capital cost (Helsen and
Bosmans, 2010).

Gasification is a process where a substance is partially oxidized. The oxidizing agent (air, oxygen or hydrogen)
is added in sub-stoichiometric amount as compared with the amount required for the complete combustion of the
substance (Brown, 2011). The oxidation of substance is an exothermic (air/oxygen as oxidizing agent)or
endothermic (hydrogen oxidation medium) process and the end products are syngas and char, with tar and ash as by-
products.

The gasification with air produces a syngas with calorific value between 4 and 7 MJ/m3, with pure oxygen the
heating value of gas is 10 to 15 MJ/m3 and hydrogen increasing the heating value of produced gas to 15–20 MJ/m3.
The advantage of gasification is production of heat for kilns or boilers. The major problem of gasification is the
production of tar (Brown, 2011).

Plasma gasification is a newly developed gasification technology which operates at high temperature upto
15,000 ࡈC. The heat is supplied to the gasifier from one or two electric arc. The high temperature decreases the
sensitivity of gasification process towards the feed quality (feed rate, moisture content) and the gasifying agent
(Gomez et al., 2009).
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The most commonly used thermal process, incineration, fully oxidise the waste at high temperature which
exceeds air above 850ࡈC to form flue gases and ash. The combustion process takes place in the gas phase in fractions
of seconds and simultaneously releases energy, as it is an exothermic process. The main stages of the incineration
process are: drying and degassing; pyrolysis and gasification; and oxidation(Helsen and Bosmans, 2010) as seen in
Figure 1. The major advantage of the combustion process is that it is commercially well established technology and
the power plant can burn the waste to extract the heat energy inexpensively and efficiently to generate electricity.

However, the major disadvantage of this thermal technology is that it becomes highly inefficient if a high
moisture waste is burnt (Brown, 2011).

Table 2 compile the reaction conditions of all the thermochemical treatment technologies discussed.The
selection of amongst these thermal processes has been done on the basis of thermal efficiency of the process and the
economic feasibility as stated in Table 4.

Table 3 compares all the available thermochemical processes. The plasma arc gasification as seen produces the
maximum energy to the grid, followed by gasification, pyrolysis and incineration in the same sequence.However,
plasma gasification, is operated under extreme condition with high temperatures and pressures as observed in Table
2. This increases the risk involved with the operation and also increases the installation cost. Table 3 shows the cost
related to plasma gasification, which is maximum amongst the other technologies. Thus we focus on the techniques
operated under atmospheric pressure and temperature range below 1000 ࡈC.

Table 2: Typical reaction conditions and products from pyrolysis, gasification, incineration & plasma-based processes (Helsen&Bosmans, 2010)

Pyrolysis Gasification Incineration

Temperature[ ࡈ C] 300—850 >650 >850
Pressure[bar] 1 1െ45 1
Atmosphere Inert/nitrogen Gasification agent Gasification agent
air, O2,H2O air, pure O2,H2O
Gas Phase H2, CO, H2O, N2, HCs H2, CO, CO2, H2O, N2, CH4 CO2, O2,H2O, CH4
Solid Phase Ash tar, ash tar, ash
Liquid phase Pyrolysis oil and water

Table 3: Parameters for assessment of thermal processes (Young, 2010)

Pyrolysis Plasma
Parameter Incineration Gasification Pyrolysis
/Gasification Gasification
Capital investment ̈́115,997,700 ̈́80,337,800 ̈́86,936,900 ̈́102,593,400 $101,583,800
Energy production [kWh/ton MSW] 544 685 571 685 816
Plant capacity [tons MSW/day] 500 500 500 500 500
Operational cost $8,216,600 $6,871,800 $7,193,700 $6,871,800 $7,483,400

Comparing incineration, gasification and pyrolysis; incineration has the minimum energy extraction and maximum
capital cost involved. Hence, gasification and pyrolysis are the most appropriate technologies for the waste
treatment. Gasification is highly developed technology with saturation in its advancements (Helsen and Bosmans,
2010). Any advancement in the process adds a small scope to increase its efficient as compared to pyrolysis, which
is an emerging technology. Thus pyrolysis is chosen for the review and further experimental work as it is seen as the
most promising technology for future. The production of oil during the pyrolysis process is a huge advantage which
makes the fuel easy to transport. Also, pyrolysis process ensures more environment safety than other thermal
treatment plants where the quality of productscan be kept under fine control (Chen et al., 2014).
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 517

3. Pyrolysis

As discussed, pyrolysis is found to be the most promising thermochemical process for the waste treatment. For the
further development of this process, this section describes the reaction kinetics and mechanism of the process and
the factors affecting the rate.

3.1 Slow and fast pyrolysis

Pyrolysis process can be operated at different heating rates. The fast pyrolysis is characterized by high heating rate
along with high heat transfer in the reactor, short residence time of the products in vapour phase(below 2s), and
rapid cooling of vapours to form liquid product (Bridgewater, 1999).Slow pyrolysis or conventional pyrolysis is
characterized by slow heating rate, and high residence time of vapour products. The slow pyrolysis is thus
characterized by comparable yields of gaseous, liquid and vapour products (Di Blasi, 2008).Table 4 presents the
conditions that distinguish between fast and slow pyrolysis (Motasemi and Afzal, 2013).

Experimentally, the different heating rates are obtained by controlling the heat transfer rate to the reactor. More the
heat transfer rate, higher the heating rate. Kong et al., (2014) describes the experimental setup and the difference in
composition of the products formed during both slow and fast heating of biomass such as wood, leaf, and bark at
500 ࡈC in a fixed-bed reactor.

This section gave a preview of the operation conditions of pyrolysis process. The following section discusses the
reaction mechanism, its kinetics and end products composition. The kinetics can explain and predict the end
products obtained by pyrolysis of MSW under different reaction conditions which are described here.

Table 4: Pyrolysis classification

Pyrolysis technology Residence time (s) of vapours formed Heating rate ( ࡈC /s) Temperature ( ࡈC)
Slow 450-550 0.1 – 1 227 - 677
Fast 0.5- 10 10-200 577 - 977

3.2 Experimental analysis-Thermogravimetric analyses (TGA)

Thermogravimetric analysis (TGA) is a standard method employed to study the decomposition reactions. The
thermogravimetry measures the weight loss during the pyrolysis for dynamic or static (isothermal) conditions.
DiBlasi(2008)state that for TGA analysis, slow heating rates are preferred for a sufficiently small mass of the
sample, so that a kinetic control is established. An experimental run is performed at a fixed heating rate in presence
of inert gas such as N2, and a graph is plotted between the normalize weight of the sample(m/m0) vs. the temperature
as seen in Figure 2. This curve is known as a TG curve, which is differentiated to obtain a differential
thermogravimetric (DTG) curve. Figure 3 shows a DTG curve, which is a plot of rate of change of sample mass vs.
temperature at a particular heating rate. Sudden peaks in DTG curve correspond to the decomposition of the fraction
of the sample, which means that reaction occurs at those temperature points. Generally two peaks are obtained in a
DTG curve for pyrolysis of waste; the first and the second peak correspond to primary and secondary decomposition
reactions (García et al., 1995).Many studies(Wu et al.,1997), (Lin et al., 1999), (Grammelis et al., 2009), (García et
al., 1995), (Hu et al., 2015), (Garcia et al., 1995), (Seo et al., 2010), (Font et al., 1995), have been performed to
study the kinetics of MSW using TGA analysis.

The DTG curve obtained for MSW is divided into five zones. Zone 1, 224-360 ࡈC corresponds to the
decomposition of cellulose and PVC. Grammelis et al., (2009), states that plastic components except PVC are stable
and there decomposition starts at higher temperatures (Zone 3). Zone 2, 360-455 ࡈC, corresponds to the
decomposition of lignin and PVC. The PVC decomposes in two zones, the first peak corresponds to
dehydrochlorination of PVC and the second peak results in the evolution of toluene and alkyl aromatics. In zone 3,
455-500 ࡈC, the remaining plastics are decomposed. The zone 4, 500-832 ࡈC corresponds to the decomposition of any
518 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

ࡈ starts to decompose the inorganics such as CaCO3.

remains of cellulose in the waste. The final zone 5 at 1000 C

3.3 Reaction Mechanism

The reaction mechanism of MSW can be simulated by considering that the overall process is formed by two
independent reactions (Garcia et al., 1995) as seen in Figure 4.

x Primary Reaction: Decomposition of cellulosic fraction 310-380 ࡈC

x Secondary Reaction: Decomposition of the non-cellulosic fraction over a wide range of temperatures(200-
500 ࡈC).

Fig. 2. Typical behavior of TG curve for an individual component. The curve is plotted between the normalized weights of the sample(m/m0) vs.
the temperature

Fig. 3. Typical behavior of DTG curve for an individual component.Sudden peaks in DTG curve correspond to the decomposition of the fraction
of the sample, which means that reaction occurs at thosetemperature points
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 519

3.3.1 Primary Reaction

Garcia et al., (1995)represents the primary decomposition reaction of the waste sample by Equation 1. The
decomposition is a single reaction with no competitive selectivity towards any of the products formed. Where, k is
the reaction rate constant for decomposition of waste sample to form char (Sp), tar(Tp) and gaseous(Gp) products. a ,
b and c are the yield coefficients (kg of product formed/kg of reacted biomass).
Sample o k aG p  bT p  cS p (1)

3.3.2 Secondary Reactions

The tar obtained from primary decomposition reactions cracks during the secondary decomposition reaction.
Equation 2 correlated the thermal decomposition of tar.
k
bTp o s eG s  fS s , (2)

whereGs is the representation of total gases and Ss is the total char and refractory tar produced during
tar(produced from primary decomposition) decomposition. e and f are the corresponding yield coefficients
(referring to the initial biomass since the coefficient b has been considered in the equation; and ks is the reaction rate
constant (Garcia et al., 1995).

However, poly-ethylene(PE) cracking takes place through two parallel reactions as seen in Equation 3 (Garcia
et al., 1995).
k s1
BTp o Gs
ks2 (3)
BTp o Ss ,

Where, B is the coefficient of tar containing PE; and k s1 and k s2 are the reaction rate constant for the two
parallel decomposition reaction to form gaseous and solid (char and refractory tar) product respectively (Garcia et
al., 1995).

Fig. 4. Representation of the reaction paths for waste pyrolysis

520 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

3.3.3 End product composition

x Slow Pyrolysis
The slow pyrolysis yields highest solid product up to 550 ࡈC when the char decomposition is complete. Slow
degradation also favours the production of solid char (Demirbas et al., 2002). The char obtained has carbon content
of around 62-80 wt% and oxygen content of 12-32 wt% as measured by Velghe et al., (2011). The carbon content in
the char increases with rising temperature for both slow and fast pyrolysis. However, slow pyrolysis forms a char
with less oxygen content as compared to fast pyrolysis, because of higher retention time and slower heating rate
(Velghe et al., 2011).

The liquid product formation is not favoured during slow pyrolysis. The liquid oil separates spontaneously in a
water rich phase and an oily product. The water rich phase contains 66 wt% water, and aliphatic acids up to 31%,
22% aromatic hydrocarbons, 16% furan components and 11% aromatic acids. The heat of combustion value of these
oils is 44 MJ/kg which is comparable to gasoline. However, due to less oil yield and higher water content of the oil
the net energy efficiency of oil infeasible for practical applications (Velghe et al., 2011).

The gaseous product obtained during slow pyrolysis is more than that obtained during fast pyrolysis. The
composition of the gaseous product varies with temperature as mentioned before (Bridgwater et al., 2007). Table 5
describes the amount of each product produced during the slow and fast pyrolysis process.

Table 5: Pyrolysis products composition (Bridgwater et al., 2007).

Pyrolysis technology Liquid (wt %) Char (wt %) Gas (wt %)

Slow 50 25 25
Fast 75 12 13

x Fast Pyrolysis
Fast pyrolysis maximizes the production of liquid products (Demirbas and Arin, 2002). A short residence time
and a high heating rate during fast pyrolysis cause incomplete degradation of the solid waste. The liquid product is
formed has long aliphatic chains of poly-ethylene-co-propylene making it waxy in nature (Velghe et al., 2011). It
has calorific value of 37-38 MJ/kg. Apart from liquid products, the yield of gas product is not high in fast pyrolysis.
However, with temperature, the proportion of the gaseous mixture remains similar. The gas is rich in hydrocarbons
(C1-C9) and along with them CO and methane are also collected (Velghe et al., 2011). The solid product, char
obtained by fast pyrolysis also has less yield and shows a higher amount of oxygen than char obtained by slow
pyrolysis due to the high heating rate and limited retention time (Duman et al., 2011).

3.4 Reaction Kinetics Estimation

The results obtained from TGA analysis are used for the kinetic parameter estimation. The rate of conversion of
mass with time is expressed by rate law in the literature (Singh et al., 2012),(Zheng et al., 2009),(Sorumet al., 2001),
(Wu et al., 1997).

The rate of conversion of mass can be described as:

dD §E· n
= Aexp¨ ¸(1  D ) (4)
dt © RT ¹

In Equation 8, A and E are frequency factor and activation energy, respectively and D is the conversion of
waste material which is defined by Equation 5
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 521

m0  m
D= . (5)
m0  mchar

In Equation 5, m0 is the initial mass of the sample, m and mchar are the actual sample mass and char yield
(including ash), respectively (Sorum et al., 2001).

Many methods have been used in literature for solving Equation 8. The methods are described as below.

3.4.1 Non linear least square algorithm

The kinetic parameters (A,E,n) are estimated by nonlinear least square(NLS) algorithm as discussed by Sorum
et al. (2001). The reaction is assumed to be first order reaction for simplification. The algorithm minimizes the value
of the objective function S DTG as defined in Equation 6.
2
N ª§ dm ·exp § dm ·calc º
S DTG = ¦«¨ ¸ ¨ ¸ » (6)
«© dt ¹ j © dt ¹ j ¼»
j =1 ¬

dm exp dm
Where, ( ) is the value experimentally measured and plotted as DTG curve; and ( ) calc is the calculated
dt dt
value obtained by numerical solution of the kinetics differential equation 1 with the given set of parameters.
dm
Subscripts j denotes discrete value of ( ).
dt
3.4.2 Avrami Erofeev equation

Zheng et al. (2009) described Avrami-Eroffev equation to describe the pyrolysis behaviour of all the
components. For each peak the rate expression is written as
n
1  D i = exp(kiW i ). (7)

Where, W is the residence time.

Taking natural algorithm of Equation 7 results in
ln[1  D i ] = ni lnW  constant (8)

The plot of ln[1  D i ] vs. ln W gives a straight line. The slope gives the order of reaction (n i ). The rate
constant k is then calculated from Equation 7 .

3.4.3 Modified integral Coats–Redfern method for non isothermal reaction conditions

The Equation 8 is used as the basic kinetic equation for this model. Singh et al., (2012). use the integral Coats–
Redfern method (Eftimie and Segal, 1987) to add the temperature variation too in the reaction kinetics.

The reaction temperature is expressed by Equation 9,

T = T0  E .t (9)
where T 0 is the initial temperature (K) and E is the heating rate (K/min).
522 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

The Equation 3 and Equation 8 are combined to form Equation 10 as below

dD A §  E · n
= exp¨ ¸(1  D ) (10)
dT E © RT ¹
The final integral equation to be plotted is Equation 11
a dD AR E
ln ³ n 2
= ln  (11)
0 1D ) T EE RT
The left side of Equation 11 is plotted against 1/T. The slope of the straight line gives the activation energy (E).
The reaction order is taken as 1 to calculate other kinetic parameters. The model is said to fit well with the
experimental model (Singh et al., 2012).

4. Raw Material and End Product Characterization

This section describes the various techniques used for the characterization of the pyrolysis end products and the
raw materials. Techniques used for the characterization are inductively coupled plasma  atomic emission
spectrometry (ICP AES), X ray fluorescence (XRF), X ray diffraction (XRD), scanning electron microscope,
BET analysis, and gas chromatography (GC), and GC-MS analysis.
Table 6 and Table 7 show the techniques for physical property calculation, like the surface area, the elemental
analysis; and the spectroscopic methods for the characterization of the materials respectively.

Table 6: Physical property measurement techniques

Ultimate Analysis Elemental analysis ( C, H, N)

Proximate Analysis moisture, ash content, volatiles, fixed C
Calorimetery Heat of Combustion
BET Surface area characterization

Table 7: Spectroscopy for material characterization

Methods Usage Advantages Limitation Use in pyrolysis Ref.

ICP-AES Direct liquids, Good Accuracy Not for direct solid Inorganic (Pb, Co, Mn) Velghe et al., (
multielements 2011)
XRF Metals, glass, ceramics Less standard Sample ൐ 1g Inorganics Velghe et al., (
deviation 2011)
XRD Crysatal structures Non-destructive Only for highly ordered crystals Ash Characterization Yang et al.,
technique (2014)
SEM Morphology & surface ൏ 10cm Structure of ash Yang et al.,
composition (2014)
FTIR Organic Compounds Overcome dispersion Spectrum not specific for a compound Pyrolysis oil Velghe et al., (
characterization 2011)
GC/TCD Organic gases Accurate results Only volatile gases Syngas characterization Buah et al.,
(2007)
GC-MS Organic liquid Reliable analytical False positives and false negatives are Pyrolysis oil Liu et al. ,
results possible. characterization (2012)
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 523

5. Conclusion

The municipal solid waste is a huge problem for developing countries today. The methods of landfilling and
open dumping, commonly used in these countries, are being replaced due to difficulty of finding new space for
landfills. In addition, landfills are not an acceptable solution socially. The thermochemical conversion technologies
for processing the waste are found to be the fastest to reduce the volume of the waste and extract energy from waste.

Thermochemical technologies include incineration, gasification and pyrolysis; and amongst these, pyrolysis is
reportedas the best suited technology. The most desirable product obtained from pyrolysis is the pyrolysis oil which
can be used as fuel owing to its high calorific value (38 MJ/kg). The liquid fuel can be easily stored and transported.
The solid product(char) is also reported as a potential solid fuel resource, but it could be contaminated with heavy
metals and organic pollutants. To maximize the yield and composition of these desired products, the factors
affecting the product composition need to be studied and developed by studying the reaction kinetics.
Experimentally, fast pyrolysis (characterized by high temperature along with fast heating rate) enhances the yield
and quality of pyrolysis oil. The characteristics of the oil can be measured by GC-MS which provides accurate
results. Other techniques such as GC is used for gas characterization; and XRD and XRF for solid product
characterization.

The study of the pyrolysis process is experimentally performed in a pyroprobe to obtain the TGA curve. The
pyrolysis destruction takes place in two steps, primary and secondary reactions to produce pyrolysis oil, char and
syngas as the end product. The rate parametes can be estimated using the various algorithms in the literature such as
non-linear least square algorithm, Avrami-Erofeev equation or modified integral Coats-Redfern method.

However, the pyrolysis technique still finds a lag between experimental studies and scaling up of the technique.
For further development of pyrolysis technique for mixed MSW, the kinetics need to be measured reliably and a
proper combination of reactor design with appropriate experimental conditions is necessary to overcome the
problem of low calorific value and the contamination of the waste.
524 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

A. Appendices

Table 8: Kinetic constants for pyrolysis reaction

Experimental
Feedstock Temp (oC) Reaction Model Kinetics Constants Ref.
System
Coated Asample of known 627 Kinetic Model: Primary Reaction Wu and C,
printing and mass was placed Activation energy (kJ (1997)
writing paper on a small quartz mol-1): 182
disk Preexponential factor (
2 cm in diameter s-1) : 8.9e+12
and 1 mm thick, Reaction order: 1.5
Weighting factor, F :
0.81

Kinetic Equations: Secondary Reaction

Activation energy (kJ
mol-1): 105
Preexponential factor (
s-1) : 9800
Reaction order: 2
Weighting factor, F :
0.19

Refuse- Thermogravimetri 500 Kinetic Equations: Primary Reaction Lin et al.,

derived fuel canalyzer (model E/R (s-1): 10065 (1999)
(RDF) SDT 2960 and Preexponential factor (
Thermal Analyst s-1) : 2.2e+8
2000, TA Reaction order: 1.9
Instruments) and
fixed bed reactor Secondary Reaction
E/R (s-1): 17010
Preexponential factor (
s-1) : 6.3e+10
Reaction order: 1.7
RDF consists Non-isothermal 223-312 Kinetic Equations: Four parallel independ Grammeli
mostly of TA Instruments reactions s et al.,
biogenic Q600 (2009)
components simultaneous Secondary Reaction
(45–65 wt%) TGA-DSC Activation energy
apparatus (kJ/mol): 112.3 ; 207 ;
54.9; 325.2
Preexponential factor (
min-1) : 8.3e+9;
2.3e+17; 3.8e+3;
3.1e+22

MSW from a Perkin-Elmer Variable C : cellulose Primary Reaction (for Garcia,

treatment TGA7 operating Nc : Non Cellulose cellulostic (1995)
plant in thermobalance conditions till T decomposition)
Alicante = 600oC, E/R (s-1): 16737
(Spain) heating rate Kinetics Model Rate constant (s-1):
100 oC/min 237.5

Secondary Reaction (for

Non cellulostic content
decomposition)
 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527 525

Experimental
Feedstock Temp (oC) Reaction Model Kinetics Constants Ref.
System
Kinetic Equations: E/R (s-1): 3748
Rate constant (s-1):
0.076

MSW METTLER Experiment The E average values of Hu et al.,

(Food waste : TOLEDO TGA/ were heated MSW by the OFW (2015)
37.16%, DSC1 from room method and the Starink
Fruit waste: thermogravimetric temperature to method were 225.3.7
10.58%, simultaneous 1000 C at kJ/mol and 228.8
Wood: thermal analyzer different kJ/mol respectively.
13.90%, heating rates of
Paper: 8.50%, 10, 20,
PVC: 23.36%, 30oC/min
Textles:
6.50%)

MSW from a Pyroprobe 1000; Temperature Kinetic Model: Primary Reaction Garcia et
treatment Fluidized bed varied from E/R (K): 5351 al. (1995)
plant in reactor 700 to 850oC Primary Reaction Rate constant ( s-1) :
Alicante 2214
(Spain).
Secondary Reaction
Activation energy
Secondary Reaction (kJ/mol): 11985
Rate constant ( s-1) : 12

Kinetic Equation: all reactions are assumed

first order reactions

RDF Isothermal Temperature range(oC): Seo et al.,

pyrolysis of the 224-360 ; 360-455; (2010)
samples was 455-500;500-832
carried out in a Activation energy
thermobalance (kJ/mol): 78.4 ; 37.4 ;
reactor (0.055 m- 142 ; 22.9
I.D. × 1.0 m-high). Pre-exponential factor
(s-1): 2.03e+10 ;
1.66e+6; 1.64e+14;
1.27e+6
526 V. Chhabra et al. / Procedia Environmental Sciences 35 (2016) 513 – 527

Experimental
Feedstock Temp (oC) Reaction Model Kinetics Constants Ref.
System

MSW Pyroproble MSW was For pyroprobe: Single reactions is assumed For Pyroprobe: Font et al.,
and thermobalance decomposed Activation energy (1995)
with the (kJ/mol): 44.76
Pyroprobe in Pre-exponential factor
the 500-900°C (s-1): 2214
temperature
range Thermobalance decomposition: two
parallel reactions are assumed For Thermobalance
Thermobalance Activation energy
: 25oC/min. till (kJ/mol): 136 ; 26.8
500oC Rate constant ( s-1) :
2.92e+9 ; 1.13

Acknowledgement

This work has been funded by JSW Steel and the authors would like to thank Dr. Kumar Iyer, JSW Steel for his
support.

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