Progress in Energy and Combustion Science 36 (2010) 103–129

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

The valorization of plastic solid waste (PSW) by primary to quaternary routes:

From re-use to energy and chemicals
S.M. Al-Salem*, P. Lettieri, J. Baeyens
Centre for CO2 Technology, Department of Chemical Engineering, University College London (UCL), Torrington Place, London WC1E 7JE, UK

a r t i c l e i n f o a b s t r a c t

Article history: Polymers are the most versatile material in our modern day and age. With certain chemicals and
Received 18 May 2009 additives (pigments, concentrates, anti-blockers, light transformers (LTs), UV-stabilizers, etc.), they
Accepted 4 September 2009 become what we know as plastics. The aim of this review is to provide the reader with an in depth
Available online 4 October 2009
analysis regarding the recovery, treatment and recycling routes of plastic solid waste (PSW), as well as
the main advantages and disadvantages associated with every route. Recovery and recycling of PSW can
Keywords:
be categorized by four main routes, i.e. re-extrusion, mechanical, chemical and energy recovery. Re-
Plastic solid waste (PSW)
extrusion (primary recycling) utilizes scrap plastics by re-introducing the reminder of certain extruded
Thermolysis
Incineration thermoplastics (mainly poly-a-olefins) into heat cycles within a processing line. When plastic articles are
Direct combustion discarded after a number of life cycles, mechanical recycling techniques present themselves as a candi-
Poly-a-olefins date for utilizing a percentage of the waste as recyclate and/or fillers. Collectively, all technologies that
Life cycle convert polymers to either monomers (monomer recycling) or petrochemicals (feedstock recycling) are
referred to as chemical recycling. The technology behind its success is the depolymerization processes
(e.g. thermolysis) that can result in a very profitable and sustainable industrial scheme, providing a high
product yield and a minimal waste. Nevertheless, due to their high calorific value and embodied energy,
plastics are being incinerated solely or in combination with municipal solid waste (MSW) in many
developed countries. This review also presents a number of application and technologies currently being
used to incinerate plastics. Cement kilns and fluidized beds are the two most common units used to
recover energy from PSW or MSW with high PSW content. It is concluded that, tertiary (chemical
methods) and quaternary (energy recovery) are robust enough to be investigated and researched in the
near future, for they provide a very sustainable solution to the PSW cycle.
Ó 2009 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
1.1. Plastic solid waste (PSW) issue: generation and quantities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
1.2. Re-use and major sorting techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
1.3. Source reduction and primary recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
1.4. Mechanical (secondary) recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

Abbreviations: ABS, acrylonitrile butadiene styrene; API, Alliance for the Polyurethane Industry; ASR, automotive shredder residues; BFBs, bubbling fluidized beds; BTX,
benzene, toulene and xylene (aromatics); CAPE, carboxylated polyethylene; CCGT, combined cycle gas turbine; DEFRA, Department of Environment and Rural Affairs (UK);
DMSO, dimethylsulfoxide; FRs, flame retardants; GCC, Gulf Council Countries; GHGs, greenhouse gases; HCV, high calorific value; HDPE, high density polyethylene; IWM,
integrated waste management; LCA, life cycle assessment; LDPE, low-density polyethylene; LHV, lower heating value; LLDPE, linear low-density polyethylene; MAPE,
maleated polyethylene; MBCs, mass burn combustors; MDPE, medium density polyethylene; ME, mean error (%); MSW, municipal solid waste; MSWI, municipal solid waste
incinerator; MSWIP, municipal solid waste incineration plants; PA 6, nylon 6 or polyamide 6; PAH, polyaromatic hydrocarbons; PAHs, polycyclic aromatic hydrocarbons; PBT,
polybutylene therephalate; PC, polycarbonate; PE, polyethylene; PET, polyethylene therephalate; PMMA, poly (methyl methacrylate); POM, polyoxomethylene; PP, poly-
propylene; PS, polystyrene; PSW, plastic solid waste; PU, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; R&D, Research and Development; RDFCs,
refuse-derived fuel combustors; RHDPE, recycled high density polyethylene; SE, sum of error; TBE, tetrabromoethane; TDM, titanium-derived mixture; TGA, thermogra-
vimetric analysis/analyser; UPR, unsaturated polyester; VCC, viable cascade controller; XRF, X-ray fluorescent; PCDFs, polychlorinated dibenzofurans.
* Corresponding author. Centre for CO2 Technology, Department of Chemical Engineering, School of Process Engineering, University College London (UCL), Torrington Place,
London WC1E 7JE, UK. Tel.: þ44 (0) 207 679 7868; fax: þ44 (0) 207 383 2348.
E-mail address: s.al-salem@ucl.ac.uk (S.M. Al-Salem).

0360-1285/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2009.09.001
104 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

2. From PSW to petrochemicals via chemical means . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .107

2.1. Principles, parameters and R&D activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2. Pyrolysis (thermal cracking in inert atmospheres) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2.1. Case study #1: thermal cracking kinetics modelling in an isothermal mode of high density polyethylene (HDPE) . . . . . . . . . . . . . . . . . 108
2.2.2. Case study #2: dynamic micro-pyrolysis of high density polyethylene (HDPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .111
2.3. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2.4. Concluding remarks on pyrolysis and gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.5. Hydrogenation (hydrocracking) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.6. Treatments of chemical nature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3. Energy recovery: quaternary treatments of PSW via combustion processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.1. Background information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.2. Co-incineration (direct one stage, two stage and fluidized bed combustion process of waste) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .118
3.3. Rotary and cement kiln combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3.4. Blast furnace application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.4.1. Simplified design approach for pulverized particle injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.4.2. Blast furnace combustion characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3.5. Environmental concerns and management issues of PSW incineration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4. Towards a more sustainable practice through recognizing PSW as a feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
4.1. Life cycle assessment (LCA) implementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2. Integrated solid waste management (ISWM) in PSW management systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
5. Conclusions and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

1. Introduction translated into resource savings throughout the polymers life cycle
(Fig. 3). Examples of such are the energy savings achieved in food
1.1. Plastic solid waste (PSW) issue: generation and quantities and goods transportation, saving in the process an average of 30% of
fuel consumption. Value from PSW should be recovered through
Plastic materials production has reached global maximum either recycling or energy and fuel recovery. Residual waste from
capacities levelling at 260 million tonnes in 2007, where in 1990 different recycling processes (i.e. refuse-derived fuel, RDF) should
the global production capacity was estimated at an 80 million be treated separately, either by thermo-chemical means or by
tonnes [1]. It is estimated that production of plastics worldwide is incineration. Energy is then recovered as heat, which can be used
growing at a rate of about 5% per year [2]. Over the past seventy for power generation. PSW recycling processes could be allocated
years, the plastic industry has witnessed a drastic growth, namely to four major categories [5], re-extrusion (primary), mechanical
in the production of synthetic polymers represented by poly- (secondary), chemical (tertiary) and energy recovery (quaternary).
ethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene Each method provides a unique set of advantages that make it
terephthalate (PET), polyvinyl alcohol (PVA) and polyvinyl chloride particularly beneficial for specific locations, applications or
(PVC). Plastics also contribute to our daily life functions in many requirements. Mechanical recycling (i.e. secondary or material
aspects. Household goods nowadays are mainly composed of recycling) involves physical treatment, whilst chemical recycling
plastic or plastic reinforced materials, from packaging, clothing, (i.e. tertiary encompassing feedstock recycling) produces feedstock
appliances and electrical and vehicle equipments, to insulations, chemicals for the chemical industry, and energy recovery involves
industrial applications, greenhouses, automotive parts, aerospace complete or partial oxidation of the material, producing heat,
and mulches. In 1996 the total plastics consumption in Western power and/or gaseous fuels, oils and chars besides by-products that
Europe was estimated at 33.4 million tonnes, whilst in 2007 it was must be disposed of, such as ash.
estimated at 48.3 million tonnes, increasing by an average of 4% per Due to the high resistance of plastics, the rapid market changes
year. This results in the high estimate of almost 60% of plastic solid and introduction of open loop recycling concept (i.e. manufacturing
waste (PSW) being discarded in open space or landfilled worldwide products from a number of articles of less quality) [36], chemical
[2,3]. In the EU member states, directive 2008/98/EC of the Euro- recycling is gaining more importance. Like all recycling processes,
pean parliament states that no less than 30% of PSW should be technical, economic feasibility and overall commercial viability of
utilizes for re-use or recycling use. The directive clearly states that advanced recycling methods must be considered in each step of the
by 2020, all solid waste streams (including plastics) should be recycling chain. Collection, processing, and marketing are each
diverted towards thermal and/or mechanical treatment and energy critical to the success of chemical recycling and energy recovery. In
recovery, reducing the percentage of solid waste being landfilled to polyolefins thermolysis (thermo-chemical treatment aimed at
a minimal. degrading the polymer under controlled temperatures), products
Polymerization and plastic conversion has its toll on every obtained mainly depend on cracking reactions in the gas phase.
economy. The UK used approximately 4.5 million tonnes of locally Thermolysis produces three different phases: a solid phase (char,
produced plastic during the year 2000 and 4.68 million tonnes 5–25 wt%), a liquid phase (tars, 10–45 wt%) and a gas phase [6].
during 2001 [4]. It is estimated that the plastic sector accounted for Gasification and pyrolysis technology worldwide are predicted to
7.5% of the UK demand for chemicals in 1998. Figs. 1 and 2 show the grow by 30% until 2015 [7–9]. First products yielded are usually in
UK market consumption by sector and polymer type in 2007, the range of C20 to C50. These products are cracked in the gas phase
respectively. to obtain lighter hydrocarbons, as ethene and propene, which are
Most plastic items sold become waste either within a year or unstable at high temperatures and react to form aromatic
a single life cycle (one use or trip). Yet still, waste polymeric articles compounds as benzene or toluene. If the residence time is long,
present themselves as an advantageous feedstock. That is mainly coke, methane and hydrogen form [10]. Long residence times of
due to their versatility and light weight. In addition, low weight is volatiles in reactors and high temperatures decrease tar production
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 105

Nomenclature R* free radical

R2 regression coefficient
Ao collision theory dependent variable (s1 T1/2) Regb Reynolds number (Eq. (29))
b heating rate ( C min1) S source term
hbg heat transfer coefficient S/ surface area in Eq. (15) (cm2)
j shape factor T temperature (K)
lg thermal conductivity (kW m1 K1) T operating temperature ( C)
m viscosity (Pa s) t reaction time, seconds
CD drag coefficient of a single coke particle Tm melting point, ( C)
d diameter (m) xa aromatics mass fraction
Eo overall activation energy (kJ/mol) xc char mass fraction
Ea activation energy (kJ/mol) xg gas mass fraction
f (ag,Regb) function of the void fraction and Reynolds number of xi lumped product mass fraction
the interface between gas and coke bed xl liquid mass fraction
Fgb drag force of coke bed acting on gas phase (N m3) xp polymer mass fraction
G gas phase product in Eq. (13) xw wax mass fraction
H* unpaired electron ri density of material i (gm cc1)
ki kinetic rate constant to form/interact with product i q generalized variable
ko overall rate constant (s1) a volume fraction
m0 mass of sample in Eq. (15) (mg)
n reaction order Subscripts
Nu Nusselt number b coke bed phase
P particle g gas phase
P* virgin polymer (radical) mass fraction in Eqs. (14), (15) i phase i
Pr Prandtl number c 99.5% conversion

but increase char formation [11]. The main disadvantage of plastic
pyrolysis and gasification is that it is necessary to control the
content of impurities and chloride in the feedstock, as well as, the
risk of bad fluidization because of particle agglomeration [12]. It is
believed that increasing temperatures above 500  C and prolonging
the gas residence time, result in a reduction in tar content of the gas
product from both pyrolysis and gasification of PSW, ASR, MSW and
even mixtures of coal, biomass and PSW [13–15]. In fact, at
temperatures above 800  C larger paraffins and olefins produced
from decomposition of plastics are cracked into H2, CO, CO2, CH4
and lighter hydrocarbons [16]. As a result of methyl-group
abstraction from aromatics and decomposition of paraffins, C2H4
and C2H2 are typically reported to increase with temperature [17].
The abstraction methyl groups and hydroxyl groups from aromatic
structures imply that the aromatic fraction does increase with
temperature even though the total amount of tar decreases. H2-
abstraction from light hydrocarbons and cross-linking reactions
may also produce PAH. The aim of this review is to provide the
reader with an in depth analysis and information regarding the
recovery, treatment and recycling routes of PSW. It also provides
recent data, experimental results and modelling concepts of
thermo-chemical treatment (pyrolysis) of polymers, demonstrated
in two case studies. This work also reflects on the current tech-
nologies and ways of utilizing PSW as feedstock in many developed
and developing countries.

Fig. 2. UK average plastic consumption by polymer type. Other include: PC, PBT, PA,
Fig. 1. UK average plastic consumption by market sector [4]. PMMA, POM, PUR, PC/ABS, UPR [4].
106 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

Virgin Polymer
Feedstock

Melting & Processing

Raw Material

Polymerization
Extraction &
Conversion
Processes:
USE
Crude
Oil

Re-Use
Chemical Recycling

Mechanical Recycling
(Tertiary)

(Secondary)
Fuels

Energy Recovery (Quaternary)

Fig. 3. Treatment methods related to the production cycle of polymers [5].

1.2. Re-use and major sorting techniques
Re-using plastic is always noted as a preferable choice to recy-
cling as it uses less energy and fewer resources, conserves fossil
fuels since plastic production uses 4–8% of global oil production, i.e.
4% as feedstock and 4% during conversion [18,19] and reduces
carbon-dioxide (CO2), nitrogen-oxides (NOx) and sulphur-dioxide
(SO2) emissions. Sorting of plastics is an essential step in the
recycling loop. A number of techniques have been developed in
order to separate and sort PSW [20,21]. In the case of rigid plastics,
heavy medium separation is usually applied [22]. This is achieved
by adding a modifier to water or by using tetrabromoethane (TBE).
However, this process is considered costly and can lead to
contamination of the recovered plastics [22,23]. Density sorting
methods are not particularly helpful in PSW sorting, because most
plastics are very close in density. To enhance the effectiveness of
density separation, hydrocyclones (utilizing centrifugal forces) are
commonly used to enhance the material wettability [24]. Another
major technique employed in PSW sorting is by triboelectric
separation. Materials with a size between 2 and 4 mm are settled in
a rotating drum to allow charging and sorting [25]. X-ray fluores-
cent (XRF) spectroscopy (suitable for plastics with flame retardants
(FRs)) is also employed in the recycling industry [26–29].
1.3. Source reduction and primary recycling
Primary recycling, better known as re-extrusion, is the re-
introduction of scrap, industrial or single-polymer plastic edges
and parts to the extrusion cycle in order to produce products of the
similar material. This process utilizes scrap plastics that have
similar features to the original products [30]. Primary recycling is
only feasible with semi-clean scrap, therefore making it an
unpopular choice with recyclers.
Currently, most of the PSW being recycled is of process scrap
from industry recycled via primary recycling techniques. In the UK,
process scrap represents 250,000 tonnes of the plastic waste and
approximately 95% of it is primary recycled [31]. Primary recycling
can also involve the re-extrusion of post consumer plastics.
Generally, households are the main source of such waste stream.
However, recycling household waste represents a number of chal-
lenges, namely the need of selective collection. Kerbside systems
are required to collect relatively small quantities of mixed PSW
from a large number of sources. This poses a resource drain and
involves significant operating costs in many countries.
1.4. Mechanical (secondary) recycling
Mechanical recycling is the process in which PSW is used in the
manufacturing of plastic products via mechanical means, using
recyclates, fillers and/or virgin polymers [5,32]. Mechanical recy-
cling of PSW can only be performed on single-polymer plastic. The
more complex and contaminated the waste, the more difficult it is
to recycle it mechanically. One of the main issues that face
mechanical recyclers is the degradation and heterogeneity of PSW.
Since chemical reactions that constitute polymer formation (i.e.
addition, condensation, etc.) are all reversible in theory, energy or
heat supply can cause photo-oxidation and/or mechanical stresses
which occur as a consequence. Length or branching of polymer
chains and/or cross-linking can also occur from the formation of
oxidized compounds and/or harsh natural weathering conditions
[5,33–36]. A number of products in our daily lives come from
mechanical recycling processes, such as grocery bags, pipes,
gutters, window and door profiles, etc. The quality is the main issue
when dealing with mechanically recycled products. Extrusion
profiling and quality of resultant products are the main concerns in
utilizing thermoplastics in mechanical recycling in R&D projects
[37–41].
Recycling PSW mechanically (on an industrial scale) involves
a number of treatments and preparation steps to be considered.
Generally, the first step involves size reduction of the plastic to
a more suitable form (pellets, powder or flakes). This is usually
achieved by milling, grinding or shredding [6,36,42]. The most
general scheme was described by Aznar et al. [6]. The steps
involved are usually in the following manner: shredding, separa-
tion, washing and extrusion. In the case of polymer foams (e.g. PU),
powdering takes place in the preparation stages. A desired particle
size is less than 0.2 mm, achieved by two-roll milling, cryogenic
grinding or precision knife cutting [43–46].
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
2. From PSW to petrochemicals via chemical means
2.1. Principles, parameters and R&D activities
Collectively, all technologies that convert polymers to either
monomers (monomer recycling) or useful petrochemicals (feed-
stock recycling) are referred to as chemical recycling [5]. Products
of chemical recycling have proven to be useful as fuel. The tech-
nology behind its success is the depolymerization processes that
can result in a very profitable and sustainable industrial scheme,
providing a high product yield and a minimal waste. Under the
category of chemical recycling advanced process (similar to those
employed in the petrochemical industry) appear, e.g. pyrolysis,
gasification, liquid–gas hydrogenation, viscosity breaking, steam or
catalytic cracking and reduction in blast furnaces [5]. Thermolysis
and catalytic degradation, have been receiving much attention
lately as a route of producing various fuel and petrochemical frac-
tions. In particular, polyethylene (PE) has been targeted as
a potential feedstock for fuel (gasoline) producing technologies.
There is also a growing interest in developing value added products
such as synthetic lubricants via PE thermal degradation. The
development of value added recycling technologies is highly
desirable as it would increase the economic incentive to recycle
polymers [47]. Condensation polymers such as polyethylene tere-
phthalate (PET) and nylon undergo degradation to produce
monomer units, i.e. feedstock or monomer recycling [48], while
vinyl polymers such as polyolefins produce a mixture containing
numerous components for use as a fuel. Various degradation
methods for obtaining petrochemicals are presently under inves-
tigation, and conditions suitable for pyrolysis and gasification are
being researched extensively [49].
Several methods for chemical recycling are presently in use,
such as direct chemical treatment involving gasification, smelting
by blast furnace [50] or coke oven [51], and degradation by lique-
faction [52]. Catalytic cracking and reforming facilitate the selective
degradation of waste plastics. The use of solid catalysts such as
silica-alumina, ZSM-5, zeolites, and mesoporous materials for these
purposes has been reported. These materials effectively convert
polyolefins into liquid fuel, giving lighter fractions as compared to
thermal cracking. The main advantage of chemical recycling is the
possibility of treating heterogeneous and contaminated polymers
with limited use of pre-treatment. If a recycler is considering
a recycling scheme with 40% target or more, one should deal with
materials that are very expensive to separate and treat. Thus,
chemical recycling becomes a viable solution [53]. Petrochemical
plants are much greater in size (6–10 times) than plastic
manufacturing plants. It is essential to utilize petrochemical plants
in supplementing their usual feedstock by using PSW.
Advanced thermo-chemical treatments of PSW in the presence
of heat under controlled temperatures (thermolysis) provide
a viable and an optimum engineering solution. Not only have they
recovered healthy monomer fractions up to 60% in past reports
[54], but they produce valuable petrochemicals that could be
summarized as gases (rich with low cut refinery products and
hydrocarbons), tars (waxes and liquids very high in aromatic
content) and char (carbon black and/or activated carbon) [34].
Thermolysis processes can be divided into advanced thermo-
chemical or pyrolysis (thermal cracking in an inert atmosphere),
gasification (in the sub-stoichiometric presence of air usually
leading to CO, CO2 and H2 production) and hydrogenation (hydro-
cracking) [55].
Appropriate design and scale (of operation and economy) are of
paramount importance when it comes to thermal treatment plants.
Thermal degradation behaviour in laboratory scale enables the
assessment of a number of important parameters, such as thermal
107
kinetics, activation energy assessment (energy required to degrade
materials treated and product formation) and determining refer-
ence temperatures of the half life of polymers and maximum
degradation point achievable. It is also important to perform pilot
scale experiments utilizing a number of rectors and unit operation
before commencing with an alteration on a performance scale [32–
34]. This will also aid in the determination of the mode of the
material processing of the thermal plant (i.e. pulsating, continuous,
batch, etc.). Pyrolysis (depolymerization in inert atmospheres) is
usually the first process in a thermal plant, and is in need of
appropriate end-product design. This could be achieved via the
understanding of the systems kinetics on a micro- (TGA) and pilot
(bench scale unit) scales. Systems kinetics will not only develop
appropriate models that will predict systems products and their
interaction, but through solving the derived mathematical
expressions, will predict the product interaction behaviour. This
will assist in reducing side reaction and undesired by-products on
an industrial scale. Developing rate expressions of the materials
being treated will then be utilized in determining the optimum unit
operation to be used and its required supply of power and proper
media of operation, in the case of pyrolysis, the sufficient amount of
inert atmosphere in the pyrolyser, or the ratio of steam to oxygen in
a gasifier [73].
2.2. Pyrolysis (thermal cracking in inert atmospheres)
Thermal degradation processes allow obtaining a number of
constituting molecules, combustible gases and/or energy, with the
reduction of landfilling as an added advantage [56]. The pyrolysis
process is an advanced conversion technology that has the ability to
produce a clean, high calorific value gas from a wide variety of
waste and biomass streams. Fig. 4 summarizes the pyrolysis process
advantages schematically.
The hydrocarbon content of the waste is converted into a gas,
which is suitable for utilization in either gas engines, with associ-
ated electricity generation, or in boiler applications without the
need for flue gas treatment. This process is capable of treating many
different solid hydrocarbon based wastes whilst producing a clean
fuel gas with a high calorific value. This gas will typically have
a calorific value of 22–30 MJ m3 depending on the waste material
being processed. Gases can be produced with higher calorific values
when the waste contains significant quantities of synthetic mate-
rials such as rubber and plastics. Solid char is also produced from
the process, which contains both carbon and the mineral content of
the original feed material. The char can either be further processed
onsite to release the energy content of the carbon, or utilized offsite
in other thermal processes. The char could also be utilized in
producing activated carbon (e.g. Shell processÒ) with the
Pyrolysis process
advantages
Operational Environmental Financial
i. Utilizing residual i. Reduces landfilling. i. Easily marketed
char. ii. Reduces GHGs and products.
ii. No flue gas clean- CO2 emissions. ii. Products could be
up is required. used to produce
electricity and heat.
Fig. 4. Some pyrolysis process advantages.
108 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

application of steam, typically in an onsite FBR. Tars (waxes, bio-oil
and liquids) resulting from pyrolysis consist of a complex mixture
of organic compounds (5–20 carbons) and are very rich in
aromatics (single ring structure). Thus, the derived oils maybe used
as fuels or petroleum refinery feedstock after upgrading (e.g. steam
or hydrogen cracking, quenching, middle cut distillation).
Pyrolysis has been investigated as a viable route of recycling by
a number of researchers for the case of PSW treatment or other
waste including biomass [57] and rubbers [58]. Surveying the
literature reveals a number of studies on polymers and PSW
pyrolysis, summarized in Table 1.
An engineering approach to improve the waste incineration
efficiency is to separate pyrolysis from actual combustion and
burnout processes of the waste [59]. In industrial scale treatment
schemes, external separation requires pyrolysis reactors whilst
firing products (e.g. char, waxes, etc.). Table 2 summarizes the main
technologies and processing lines employing industrial pyrolysis
units.
2.2.1. Case study #1: thermal cracking kinetics modelling in an
isothermal mode of high density polyethylene (HDPE)
2.2.1.1. Summary. One of the main materials present in significant
quantities in MSW streams is polyethylene (PE). Numerous kinetic
studies have been conducted in the past, focusing on reaction
mechanism but rarely considering product formation and interac-
tion analysis. In this section, we will present a novel kinetic
approach of the thermal cracking mechanism of high density
polyethylene (HDPE). The product formation analysis was consid-
ered from an engineering perspective using lumped product anal-
ysis, and kinetics parameters were evaluated accordingly [34].
2.2.1.2. Literature survey. A number of studies have been carried
out on polyolefins thermal cracking in inert (pyrolysis) and/or
partially oxidized atmospheres (e.g. step pyrolysis, gasification).
Previous reports focused on kinetic parameters estimations by
means of different techniques and experimental conditions [77,78].
Thermogravimetry is the most commonly used technique for the
determination of kinetic parameters, although the experimental
conditions utilized are very different, involving broad ranges of
temperature, sample amount, heating rates (in the case of dynamic
runs), reaction atmospheres and pressures. Almost all of previously
published literature shows a power law equation to describe the
thermal cracking of polymers and perform isothermal and/or
dynamic experiments.
Previous studies demonstrate simple approaches, with little or
no attention paid to product formation. In a study conducted by
Williams and Williams [79], six thermoplastics were pyrolysed in
a static batch reactor with a N2 atmosphere under a constant
heating rate to a final temperature of 700  C. These were low and
high density polyethylene (LDPE and HDPE, respectively), poly-
styrene (PS), polyethylene terephalate (PET), polypropylene (PP)
and polyvinyl chloride (PVC). The product yield for the mixture was
given in terms of gas, char, oil and HCl (from PVC). The description
of the influence of the pyrolysis temperature (500–700  C) on the
yield of the derived products from LDPE was given in a follow-up
study [80]. A noticeable increase in the gas yield with the
temperature was reported. McCaffrey et al. [81,82] studied the
thermal degradation of linear low-density polyethylene (LLDPE) at
moderate temperatures (425–450  C) by using a pyrolysis process
to produce liquids that could be used as synthetic lubricants, with
a yield of 82.5% of the initial charge to the reactor used. The balance
of the reaction products was a residue and a non-condensable gas
fraction, with yields of 9.5 and 8.0%, respectively. In polyolefin
upgrading, a number of studies used various techniques to ther-
mally degrade the materials investigated. Thermogravimetric
analysis (TGA) remained the main source of information, although
often carried out at temperatures below 450  C. Hence, the
extrapolation of these results to the design of the reactors operating
at higher temperatures is speculative.
It has been stated by McCaffrey et al. [81,82] that polyethylene
(as well as other vinyl polymers) degrade via a four step free radical
mechanism: radical initiation, de-propagation (as opposed to
propagation in the case of polymerization), intermolecular and
intramolecular hydrogen transfer followed by b-scission (initial
step in the chemistry of thermal cracking of hydrocarbons and the
formation of free radicals) and, lastly, radical termination. b-Scis-
sion and hydrogen abstraction steps often occur together in a chain
propagation sequence. That is, a radical abstracts a hydrogen atom
from the reactant to form a molecule and a new radical [82]. A bond
b is then broken to the radical centre (b-scission) to regenerate an
abstracting radical and to produce a molecule with a double bond (a
molecule with a double bond involving the carbon atom that had

Table 1
Summary of pyrolysis and inert atmosphere chemical treatment studies on virgin/waste plastics in micro-, bench and pilot scales.

Reference Summary
Al-Salem et al. [34] Micro-study of a commercial grade high density polyethylene (HDPE) isothermal pyrolysis in a N2 atmosphere. Lumped product analysis
was performed and a kinetic model was proposed based on primary and secondary product interactions.
Kaminsky et al. [12] A pyrolysis study in a fluidized bed which showed very good heat and material transfer. The configuration used allowed shorter residence
times at moderate operating temperatures.
McCaffrey et al. [60] Investigation of the degradation of PE and PS mixtures in co-pyrolysis processes.
Wong and Broadbelt [61] The interactions of different polymers during pyrolysis using a combination of experiments and mechanistic modelling to develop
a quantitative understanding of the synergistic effects present during co-processing were studied.
Mastellone et al. [62] Preliminary series of experiments to investigate the polymer-to-particles interactions inside a pyrolyser and effects of main operating
variables on the yield and composition of products of the fluidized pyrolysis of a recycled PE grade. In the range below 650  C, the
amount of BTX and other aromatics was just appreciable.
Horvat and Ng [63] Two-step novel pyrolysis of wasted PE articles. PE is heated in the first step, under N2 atmosphere, to a range of 400–450  C to
produce PE oil, and then developed the fundamental aspects of the oil was hydrogenated at 30–90  C to produce a diesel type liquid fuel.
Nishino et al. [64–66] Selective degradation of polyolefins (LDPE, HDPE and PP) to petrochemicals using Ga-ZSM-5 has been reported.
Fink [67] Pyrolysis (in argon atmosphere) of plastic in contact with liquid steel in a bench scale reactor. Products recovered included dissolved
carbon in steel, soot, tars and rich gases.
Wallis and Bhatia [68] Investigating the pyrolysis behaviour of high density polyethylene (HDPE) below 400  C.
Bilbao et al. [69] Micro-isothermal and dynamic TGA experiments were conducted on PU to determine apparent kinetic parameters. The significance of using
the values of solids lost at a given temperature was analyzed.
Mastral et al. [70,71] Pyrolysis in a fluidized bed was performed on high density polyethylene (HDPE) to investigate the effect of residence time and product
distribution analysis was performed. At 640  C the main product obtained was a waxy cream coloured material (wax). The yield of this
product varied from 79.7 wt% at 0.8 s to 68.5 wt% at 1.5 s.
Ceamanos et al. [72] Kinetic parameters were evaluated based on HDEP pyrolysis. Order of magnitude varied between overall rate constants determined by
dynamic and isothermal runs using a thermobalance reactor.
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 109

Table 2
Main pyrolysis units and technologies on an industrial scale summary.

Name Unit operation Summary Reference

PYROPLEQÒ Rotary drum - Pyrolysis at 450–500  C with gas combustion at 1200  C. [59]
process - Typical feed to the process is PSW (post consumer mixtures).

Akzo process Circulating fluidized - Proven to be successful for PSW, rich in PVC. With a capacity of 30 kg/h (fast pyrolysis). [73]
bed (two reactors) - Main outputs: HCl, CO, H2, CH4 and, depending on the feedstock composition, other
hydrocarbons and fly ash.

ConThermÒ Rotary drum This process pyrolyses shredded fuels such as MSW and automotive shredder residues [59]
technology (ASR) as well as up to 50% post consumer plastics at 500–550  C in 100 kt/year.

NRC Melt furnace - Main inputs: PVC waste (cables, flooring, profiles, etc.). [59]
- No other PSW type is fed to the processing, which results in calcium chloride, coke,
organic condensate (for use as fuels) and heavy metals for metal recycling, as products.

PKA pyrolysis Rotary drum - The technology comprises a modular pyrolysis and gasification concept at high temperatures. [59,74]
- The process starts with a pre-processing step involving separation, screening and shredding
of different kind of wastes such as MSW, ASR, spent tyres, industrial and plastic waste as well as
contaminated soil. The pyrolysis takes place at 500–550  C for about 45–60 min.
- The yield is a de-dusted and homogenised CO/H2 rich fuel gas.
PyroMelt Melt furnace - This process combines pyrolysis and slagging combustion yielding an eluation-resistant, recyclable [75]
granulated slag.
- Pyrolysis takes place prior to the combustion process and the resulting gas is subjected to
multiple scrubbing steps
using pyrolysis oil.

BP polymer Circulating - This process cools the gas from the range of 500–600  C down to 120–150  C. [73]
cracking process fluidized bed - After a series of pilot trails (between 1994 and 1998), a plant was established in Scotland
with a capacity of 25,000 tonnes/year.
- Size reduction is required for the feed, which is then fed to a heated fluidized bed reactor
(operating at 500  C) in the absence of air. 85% by weight of the plastic that enters the process
is passed on as hydrocarbon liquid, and the remaining 15% is gas at ambient temperature.

BASF process Furnace - The conversion of the PSW into valuable petrochemicals takes place in a multi-stage melting [76]
and reduction process.
- In the first stage the plastic is molten and de-halogenated to preserve the subsequent plant
segments from corrosion.
- Minor amounts of the feed come available as NaCl or CaCl2 effluent. Liquefied plastic waste is
heated to over 400  C and cracked into components of different chain lengths producing
gases (20–30%) and oils (60–70%).

NKT process Circulating - The process is based on an initial pre-treatment step that involves separating light plastics [73]
fluidized bed (PP, PE, etc.) and other materials, e.g. wood, sand, iron, steel, brass, copper and other metallic pollutants.
- The PSW waste is then fed to a reactor at a low pressure (2–3 bars) and a moderate temperature (375  C).

been the radical centre). It has been reported that sample size and
surface area to volume ratio of the melt have a significant influence
on the rate and relative importance of the various mechanisms of
polymer degradation. In pyrolysis, which is normally done on
micro-scale, only random initiation and intermolecular transfer
were reported to be important. Conversely, on milligram scale of
polyethylene charges and samples, intermolecular transfer of
hydrogen atoms via abstraction by free radicals was considered to
be the predominant transfer mechanism to produce volatiles
[81,82]. A simple mechanistic kinetic model able to describe the
radical chain pyrolysis taking place in the liquid phase was pre-
sented by Ranzi et al. [83], assuming, thermal degradation of
polyolefins to be a typical radical chain mechanism: initiation,
H-abstraction, b-scission and radical recombination.
2.2.1.3. Experimental, kinetic parameters estimation and mod-
elling. As is mentioned above, the reaction mechanism considered
for the thermal decomposition of polyethylene can be the cause of
the disparity of the results. Hence, validation and obtaining reliable
engineering data with high regression is of paramount importance.
This case study considers pure high density polyethylene (HDPE,
Tm ¼ 133  C) Belgian commercial grade supplied by Ravago Plastics
(Arendonk, Belgium). Product analysis has been carried out by
means of a Hewlett Packard 6890 chromatograph coupled with
thermal conductivity (TCD) and flame ionization (FID) detectors,
being connected online to the balance by means of a thermostated
line. Furthermore, lump product identification has been carried out
by means of a mass spectrometer (Shimadzu GCMS-QP20 I OS).
99.9% pure nitrogen was used in the pyrolysis process with a flow of
50 ml min1. HDPE pellets were milled to below 0.1 mm (in diam-
eter) and 15 mg was used for each individual TGA run (avoiding
mass and heat transfer resistances). Pyrolysis products were lum-
ped into gases (C1–C4), liquids (non-aromatic C5–C10), single ring
aromatics (C5–C10), waxes (>C11) and char. Fig. 5 illustrates the
product distribution of HDPE thermal degradation as a function of
operating temperature. The figure shows the lumped product
distribution (wt%) obtained from TGA with respect to temperature
( C) for 99.5% conversion. It should be noted that char was only
formed in significant quantities at 700  C (z4 wt%). Products at
500, 550 and 600  C were used to derive the thermal cracking
model of polymer degradation fraction (xp) with time. The effect of
temperature was clear on the time required to achieve 99.5% of
HDPE and the fast pyrolysis process showed great response with
time. Temperature had also a clear effect on product distribution.
Operating under higher temperatures reduced wax yield, however,
increased the gas yield. Char yield was minimal (<0.1%) except
under 700  C where it was measured to be 3.9 wt%. It was also
evident that a higher operating temperature reduces the time for
maximum conversion.
Numerous attempts have been undertaken to develop a thermal
degradation scheme, usually via a simple approach of parallel
reactions from HDPE to product [5,65,79–83]. Yet differences were
110 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

90
Waxes (>C11) based on mass concentrations and balances, and rate equation
Gases (C1-C4) analysis [85–87]. Eqs. (3)–(8) show the kinetic rate equations
80 Liquids (non-aromatics C5-C10) derived for the mechanism proposed, for polymer, gas, liquid, wax,
Aromatics (C5-C10)
70 aromatic and char balances consecutively:
60
dxp =dt ¼ xp ½k1 þ k2 þk3 þ k4 þ k5  (3)
xi (%wt)

50

40 dxg =dt ¼ xp ½k1  (4)

30
dxl =dt ¼ xp ½k2  þ xw ½k6  (5)
20

10 dxw =dt ¼ xp ½k3   xw ½k6 þ k7  (6)

0
400 450 500 550 600 650 700 750
Temperature (C)
dxa =dt ¼ xp ½k4  þ xw ½k7  (7)

Fig. 5. Full product distribution obtained from TGA experiments within the experi-
mental temperature range (450–700  C).
always present due to variations in polymer’s characteristics
(molecular weight, presence of weak links, additives, etc.) and
differences in experimental conditions from which kinetic data are
calculated [80–83]. In addition, previous attempts were consid-
ering the rate equations from an abstract chemistry side rather than
lumped products that will simplify industrial flash and fast pyrol-
ysis applications. A model of the first order (n ¼ 1) is proposed
based on the experiments conducted. The model determines the
amount of liquids, gases, waxes, aromatics and char produced by
wt%. In addition, it estimates the kinetic rate constants and overall
activation energy via Arrhenius equation fitting. The mechanism
employed in the current study is illustrated in Fig. 6. The scheme is:
primary conversion of HDPE to liquids, gases, waxes, aromatics and
char; and then secondary conversion of waxes to liquids and
aromatics.
The mathematical model of the mechanism proposed was
solved using MatLab version 9.0. Assuming that initial conditions
were at time ¼ 0, the fractions of the polymer and products would
be as follows:
@t ¼ 0; xp ¼ 1 and x g ¼ xl ¼ xw ¼ xa ¼ xc ¼ 0
where t is the time (s), xp is the polymer mass fraction, and xg, xl, xw,
xa, and xc are the mass fractions of gases, liquids, waxes, aromatics
and char, respectively.
The second conditions would be at time t, described as follows:
 
@t ¼ t; xp < 1 and xg ; xl ; xw ; xa ¼ xc ¼ f t; xp
where again t is the time (s), xp is the polymer mass fraction, and xg,
xl, xw, xa, and xc are the mass fractions of gases, liquids, waxes,
aromatics and char, respectively. The derivation of the model was
⎡ ⎯⎯→
k1
[G] ⎤
⎢ k2 ⎥
⎢ ⎯⎯→ [L] ⎥ ⎡⎯⎯→
k6
[L]⎤
dxc =dt ¼ xp ½k5  (8)
where k1, k2, k3, k4, k5, k6, k7, respectively stand for the rate constant
of thermal degradation of (primary reactions): polymer to gases,
liquids, waxes, aromatics and chars; (secondary reactions): waxes
to liquids and aromatics. It was also assumed that all reactions were
irreversible with 99.5% conversion of HDPE. Time of initial guess
set-up in the MatLab program was equal to 0.001 s, solved by 4th
order Runga–Kutta method.
From the experimental data, the predicted conversion of xp was
obtained from the fitted data. Three equations were obtained at the
three given temperatures. The form of the equation is not related to
the occurring mechanism, but represents the best fit of the data.
The best fit (R2 ¼ 0.918) for the first temperature (i.e. 500  C) was
obtained using the classical diffusion equation reported below
(Eq. (9)) for component i:
 
a1 $xa2
yi ¼ a0  (9)
ð1 þ a1 $xa2 Þa3
where xi is the x-axis parameter and y is the y axis parameter
considered. a0, a1, a2 and a3 are the correction factors obtained by
solver function on EXCEL 2003 in our case minimising the sum of
(1) errors (SE).
As for the obtained model, it is represented by Eq. (10):
" #
0:207$t 0:74
xp ¼ 1:04   0:016 (10)
1 þ 0:207$t 0:74
where a0, a1, a2 and a3 were calculated as 1.04, 0.207, 0.74 and
(2)
0.016, respectively. Whilst the SE and average error were found to
be 0.08 and 0.01, respectively.
Following the same methodology for the other two tempera-
tures (550 and 600  C), exponential law governing equations rep-
resented the best fits with R2 ¼ 0.972 and 0.999 respectively. Eqs.
(11) and (12) show the models obtained for the polymer fraction at
550 and 600  C, respectively.
xp ¼ 1:225$expð0:02*tÞ (11)

⎢ ⎯→
[HDPE] ⎯
k3 ⎥ [W] ⎢ k ⎥ xp ¼ 0:99$expð0:99*tÞ (12)
⎥ ⎢⎣⎯⎯→ [A]⎥
[W]
⎢ 7
⎦ Exporting Eqs. (10)–(12) to the MatLab program, combined with
⎢ ⎯⎯→ [A] ⎥
k4 Eqs. (3)–(8), enables the determination of the kinetic parameters

⎢ k5 ⎥ for each degradation path. The models developed had a high fit

⎯⎯→
with respect to experimental results obtained by TGA analysis. It
⎢⎣ [C] ⎥⎦ was observed that time needed for total conversion decreases with
higher operating temperatures. A high match was obtained from
Fig. 6. Proposed thermal cracking scheme (first order, n ¼ 1) for HDPE based on the experimental and modelled cases at temperatures of 500, 550
depolymerization lumped product analysis. and 600  C, with an R2 ¼ 0.977, 0.989 and 0.991, respectively for the
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 111

polymer degradation fraction (xp). Fig. 7 shows the exported Table 3

modelled results for the predictions of polymer loss against Mean and sum of errors resulting from experimental and modelled results of the
proposed model of HDPE thermal degradation at different operating temperatures.
experimental results obtained at 500, 550 and 600  C.
The values plotted show a great influence on gases and waxes Operating temperature ( C) Sum of errors %Error mean
formation by pyrolysis (In the case of 500  C), demonstrated in this 450 1.1  105 1.1  106
case. A rapid change occurs in the gas yield at a residence time of 500 0.08 0.01
550 3.20 0.40
310 s. Two data ranges present themselves within the results at
600 1.89  105 2.63  106
190 s and 310 s. This could be attributed to the two molten stages 650 0.01 0.002
occurring for the HDPE particles in the thermobalance chamber 700 0.01 0.001
whilst being under flash pyrolysis [79]. Final results of the model
estimates were within 5% of the experimental results obtained by
the TGA. degradation by pyrolysis. For polyethylene, it was reported that Ea
Estimations of the error between experimental and modelled ranged between 192 and 301 kJ mol1. Whilst Horvat [47] reported
results at different operating temperatures dealt are presented in Ea to be in the range of 237–279 kJ mol1, in the range of 450–
Table 3. Pyrolysis starts occurring at temperatures as low as 400  C 470  C. Other authors reported total activation energy (Eo) in the
[62]. Previous researchers have reached a final temperature of range of 188–293 kJ mol1 [74–76]. Conesa et al. [77,88,89]
above 700  C, especially when working with circulating bed reac- proposed a very simple yet effective thermal degradation mecha-
tors [5]. nism based on isothermal TGA runs carried on HDPE samples. The
Minimal error was found for the case of HDPE thermal degra- behaviour has been modelled according to the mechanism pre-
dation. In order to obtain the kinetic parameters, the differential sented below in Eq. (13):
equations were solved and kinetic rate constants were calculated.
Table 4 shows the kinetic parameters estimated at the three k1
P / G1
different temperatures. The degradation path of the secondary
reactions contributing to the aromatics and liquids production was
k2 k3
evaluated by estimating the kinetic parameters separately. P / P* / G2 (13)
Apparent kinetic constant (overall) could be estimated by
where P is the virgin polymer, P* is the polymer free radical and G1
summing the k values of the primary reactions [84–87], resulting in
and G2 are the gas phase products of the primary reactions alone,
3.7  103, 24.3  103 and 50.5  103 (s1), at temperatures of
respectively.
500, 550 and 600  C, respectively. The activation energies (abso-
The first reaction is proportional to the amount of virgin poly-
lute) and pre-exponential factors were estimated for every primary
mer (P) on the surface of the melted material. The second reaction
product by 1st order Arrhenius equation fitting. An agreement with
is a bulk phase reaction and reaction 3 is proportional to the
previously reported estimations was observed [47,74–76]. The
amount of P* on the surface. The model presented is illustrated
liquids and aromatics fractions show very desirable estimates.
below:
Other than having the highest activation energies (Ea), they also
have the highest kinetic rate constant. This shows the influence of P
these two products within the mechanism proposed. This, dP=dt ¼ k1 ðS=m0 Þ$  k2 $P (14)
P þ P*
combined with the contribution from secondary reactions, influ-
ences the thermal degradation of HDPE to a large extent.   P*
Previous attempts reported in the literature shows conversion dP*=dt ¼ k2 $P  k3 S= $m0 (15)
P þ P*
orders between 0.86 and 1 with an overall kinetic rate constant
between 8  104 and 9  103 s1 in a moderate temperature where P and P* are represented in mass fraction, m0 is the mass of
range of 390–470  C [62]. It was also reported that operating sample (mg) and S is the surface area (cm2).
temperatures have a proportional effect on overall rate constant, Both the model by Conesa et al. [77,88,89] and the model pre-
which our results confirm. Earlier work by Mastellone [5], reports sented in this study are based on experimental TGA runs, and serve
the activation energy (Ea) of a number of polymer after thermal the same purpose of finding a realistic mechanism for HDPE
thermal degradation. Yet, the latter was based on a novel complex
engineering approach. Previous attempts were based on simple
decomposition schemes and radical concentration estimation that
will not serve in industrial schemes and reactor design. The model
presented by Conesa et al. [77,88,89] also estimated the Ea for each
of the three reactions (Eq. (13)) and found it to be 185, 271.1 and
221.5 kJ mol1. The overall activation energy (Eo) was estimated at
147.25 kJ mol1 based on the lumped product analysis approach.
The Eo resulted from data fitted (R2 ¼ 0.986) after estimating the
overall rate constant (ko, s1) at 500, 550 and 600  C, which was
found slightly lower than previous reports. This can be attributed to
the flash pyrolysis process used in this study, resulting in a low
residence time and achieving high operating temperatures. The low
Eo also points to the direction of achieving industrial flash pyrolysis
in reactors of full-industrial scale.

2.2.2. Case study #2: dynamic micro-pyrolysis of high density

polyethylene (HDPE)
Fig. 7. Model results of polymer weight loss obtained at 500, 550 and 600  C as 2.2.2.1. Summary. In order to meet with today’s industrial units,
a function of time (s). elevated heating rates are applied in pyrolysers, saving in the
112 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Table 4
Kinetic rate constants evaluated for the thermal cracking model showing k’s (s1) for the formation of gases, liquids, waxes, aromatics and char from HDPE (primary reactions),
and liquids and aromatics formations from waxes (secondary reactions).
Temperature ( C) k1 k2 k3
500 1.5  103 1.1  103 6  104
550 8  103 4.2  103 4.2  103
600 9  103 1  102 9  104
process resources and manpower. To that extent, a kinetic model
applied in elevated heating rates corresponding to the rapid decline
witnessed in the weight loss in elevated ramps, is presented in this
section. Results demonstrated agreed with previous reported
kinetic estimations at high heating rates [81–84].
High heating rates are being utilized in industry, especially in
co-pyrolysis of PSW and other MSW streams. Classical dynamic
TGAs present advantages over isothermal runs. Although, they
don’t simulate fast isothermal industrial pyrolysers (tc  120 s),
results over a wide temperature range are obtainable. In this
section, kinetic parameters estimation techniques and methods are
reviewed. A derived model for high heating rates is also presented.
2.2.2.2. Kinetic evaluation in dynamic mode. Previous studies have
considered a mass balance %error validation to verify dynamic
experimental runs. Eq. (16) expresses the %error described by
Grieco et al. [90]:
ðmC  ðms  mG  mtar ÞÞ
%3 ¼  100  2% (16)
ms
where %3 is the mass balance closure error and ms, mC, mG, mtar are
respectively the weight (mg) of sample, char, gases and tars
produced.
Polymers subjected to thermal cracking, mainly under the influ-
ence of a fixed heating rate, undergo complicated processes, such as
random chain scission, end chain scission, chain stripping, cross-
linking and coke formation. Apparent dynamic kinetics, useful for
engineering design, is the focus of this section. Dynamic kinetic rate
constants are dependent not only on factors such as atmosphere,
sample weight, shape and type, heating rate and flow rate, etc., but
also upon the mathematical treatment used to evaluate certain
parameters [91]. Dynamic kinetic studies utilize the basic rate
equation of the general kinetics theory. The weight loss of a polymer
is described as follows:
 n
dxp =dt ¼ A$ 1  xp $expð  Ea =RTÞ (17)
where xp is the fraction pyrolysed (loss) of a polymer, A is the
Arrhenius fitting pre-exponential factor (s1) and Ea is the activa-
tion energy (apparent) of a single path reaction (J mol1).
If the temperature rises with a constant ramp or a heating rate
(b) and the kinetic parameters at any weight loss fraction is
approximately equal to those of neighbouring the weight loss
fraction, then by differentiating Eq. (17) with respect to tempera-
ture (T) to obtain the second derivative, we can employ the ramp
expression described by Oh et al. [91] as b ¼ {\rm d}T/{\rm d}t,
resulting in the following equality expression:
! a linear regression of 0.929 (Fig. 10), the activation energy at the
 
dxs 1 maximum degradation (Em) was determined as 276.85 kJ mol1. By
E=RT ¼ ln $ (18)
dT Ao T 1=2 $ð1  xs Þn
where E is the apparent activation energy (J mol1), xs is the poly-
mer solid conversion fraction, T is the temperature (K) at time (t, s),
n is the polymer conversion order and Ao is the collision theory
dependant variable(s1 T1/2). Eq. (18) gives the estimate of the
activation energy at each data point corresponding to solid fraction
k4 k5 k6 k7
2  104 3  104 3  104 2  104
3.7  103 4.2  103 3.4  103 9  104
3  102 6  104 3  103 9  104
and temperature range, and the average activation energy could be
determined using the Coats and Redfern [92] approximation:
Pn
i¼1 Ei ðai  ai1 Þ
Eavg ¼ (19)
af
where Ei is the activation energy corresponding to point i and time
(t), ai is the weight loss fraction at point i and af is the weight loss
fraction at the final status of maximum degradation.
A valid approximation at maximum, non-catalytic thermal
degradation cracking has been presented by Oh et al. [91],
combining the heating rate (b) and the 1st order Arrhenius fitting
equation. Eq. (20) shows the Oh et al. [91] equation used for
maximum degradation estimates as a function of b.

3 Em 1 Em
lnb ¼ lnAo þ lnðTm Þ  ln þ  (20)
2 RTm 2 RTm
where Em is the activation energy at maximum degradation
conditions (J mol1) and Tm is the final temperature (maximum
degradation temperature) (K).
In order to estimate kinetic parameters over a range of
temperatures, the Ozawa–Flynn–Wall (OFW) isoconversion
method is still widely applied and used especially in elevated
heating rates. Ceamanos et al. [72] has expressed the OFW equation
in terms of heating rate (b) and solid conversion (xs):
lnðbÞ þ 5:33 þ lnð1  xs Þ ¼ lnðko E=RÞ  1:05ðE=R$TÞ (21)
By summing ln(b) and giving it an expression k, a linear relation
can be fitted between k þ ln(1  xs) vs. 1/T to estimate the activation
energy.
2.2.2.3. Experimental and proposed kinetic model. After milling the
polymer particles (HDPE, Tm ¼ 131  C, EQUATE, Kuwait), thermal
cracking in N2 atmosphere was achieved with a thermobalance
reactor, i.e. pyrolysis. A dynamic investigation was carried out
with a pre-set temperature of 550  C with four constant heating
rates (b ¼ 5, 10, 25 and 50  C min1) in the thermobalance (TGA
set-up) reactor illustrated in Fig. 8. The heating rates in dynamic
thermogravimetry demonstrate a number of advantages, mainly
polymer cracking behaviour over a range of temperature. Char
was recovered if a residual was remaining in the chamber after
each run. Fig. 9 shows the solid conversion of the HDPE polymer
over the pyrolysis heating range.
The solid conversion showed a rapid increase with the elevated
ramp of b ¼ 50  C min1. The Oh et al. [91] expression was used to
determine the activation energy at the maximum degradation of
the polymer, with respect to the four heating rates chosen. With
using an equality to set an objective function of E/RT and maxi-
mize the correlation coefficient between the two sides of Eq. (18),
the general kinetics theory parameters have been determined
(Table 5).
Employing Eq. (19) resulted in the estimation of the overall
activation energy (E), which in this case equalled 204 kJ mol1. The
OFW method is considered a very good estimate used in many
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 113

Air/N2 regulator

Gas/control display
Cooling air N2 inlet gas
Top
seal
Heating Element

Suspension wire

N2
jacket
Thermocouple

Sample holder

Reactor chamber Vents

Bottom seal

Fig. 8. Thermobalance reactor (TGA) schematic showing main parts.

previous kinetic parameters estimation studies [71,72]. By plotting
k þ ln(1  xs) against 1/T in Eq. (21), the activation energy was
determined by the OFW method. Fig. 11 shows the four heating rate
plots in the OFW expression with their corresponding heating rates,
regression coefficients.
Activation energies estimated from the OFW method were
different from the general kinetics theory approximation and were
increasing with heating rate (b). This has been reported previously
by Oh et al. [91]. Yet still, the overall activation energy is the main
objective from the methodology which was estimated to be
171.28 kJ mol1. The activation energy resulting from the dynamic
run using OFW expression has been reported in the past to be less
than other methods of kinetic parameters estimation. Nevertheless,
it is a very good way to give an estimate of the order of magnitude
of E. The OFW also estimates the activation energy at an individual
heating rate, which is one advantage it represents over other
methods.
Kinetic parameter estimations aid in the design of industrial
scale units. In industry, time and manpower are of major impor-
tance and need to be utilized efficiently. Understanding the
dynamic behaviour of polymer pyrolysis will aid in that respect. In
fact, a single step derived model for elevated heating rates
(b  50  C min1) can simplify the process design. In elevated
heating rates, the polymer loss occurs faster and more rapid. This
could be expressed by an exponential or a power law equation. In
the present case of HDPE, an exponential equation showed high
response to the experimental fractions measured by the TGA
(shown below).
xp ¼ 0:79 expð0:035$tÞ (22)
where xp is the polymer fraction (pyrolysable fraction in dynamic
mode) and t is the reaction time (s). Relating time and polymer
fraction is the optimum for reactor design since it gives operators
and industry involved personal the opportunity to investigate the
reaction condition at a given time. Fig. 12 shows the polymer
fraction (experimental and modelled) and solid conversion
(experimental and modelled) from HDPE.
The modelled case resulted in a SE of 2  103, with a correlation
coefficient (maximized) of 0.9533 between experimental and
modelled results of polymer fraction. It was noted that the
temperature range of HDPE pyrolysis was in agreement with
previous studies [70,71]. However, it is very important to derive an

1
β (0 C.min-1 ) 5

5
0.75 4
10
ln ( β ) (C0.min-1)

25
3
Xs

0.5 50

0.25 1

0
0
1.394 1.395 1.396 1.397 1.398 1.399 1.4 1.401
360 380 400 420 440
0
Temp. ( C) (1/T) x 103 (K-1)
Fig. 9. Solid conversion of high density polyethylene (HDPE) as a function of Fig. 10. Oh et al. [91] expression fitting showing heating rate (b) as a function of
temperature in the thermobalance reactor chamber. temperature.
114 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

Table 5 assuming that the polymer will result in gases and tars, ko could be
General kinetics theory parameters, %error between equality (Eq. (18)) and activa- expressed as k1 þ k2, representing the sum of gases and tars rate
tion energies estimated at each heating rate (b) for high density polyethylene
(HDPE).
constant, respectively. Taking the natural logarithm of both sides of
Eq. (23) and combining it with the Arrhenius equation results in the
Heating rate Temperature E/RT %Error Mean error following expression:
(b),  C min1 (K) (%) and activation
energy (kJ mol1)
 
5 635 38.80 1.23 ME ¼ 3.5% lnðko Þ ¼ lnðdxp =dtÞ þ ln xp ¼ Ea =RT  lnðPo Þ (24)
643 38.32 3.46 E ¼ 204.89 kJ mol1
651 37.85 2  105 where Po is the Arrhenius equation pre-exponential factor. For the
659 37.39 5.80
rapid decline in high heating rates this expression serves perfect in
668 36.89 7.26
677 36.40 1.91 activation energy estimations. Fig. 13 experimental and modelled
685 35.97 5.93 results were fitted to evaluate the activation energy of HDPE
10 637 38.00 0.52 ME ¼ 5.58%
dynamic cracking, which resulted in 213.619 kJ mol1 (exp,
647 37.41 0.72 E ¼ 201.26 kJ mol1 R2 ¼ 0.997) and 212 kJ mol1 (model, R2 ¼ 0.999).
657 36.84 10.43 The OFW relation showed a value of 256.71 kJ mol1 at the same
667 36.29 9.07 constant heating rate, whilst Oh relation showed an Ea value of
677 35.75 0.51
276 kJ mol1 but at a maximum degradation, i.e. At final status.
690 35.08 4.13
697 34.73 4.47 Variation between published data exist, due to different numerical
704 34.38 12.63 methodologies followed or type and class of material used. Order of
714 33.90 7.74 magnitude is what of concern based on the final estimate and
25 638 39.39 3.87 ME ¼ 2.24% considered the comparable result [72,92], since factors in graphical
649 38.72 4.24 E ¼ 200 kJ mol1 methods always obey the fitting and data used. The model derived
660 38.07 2.83 is suitable for industrial pyrolysis units since it obeys the behaviour
671 37.45 2  107
of polymers at an elevated heating rate.
682 36.84 2.67
693 36.26 1.38
704 35.69 0.81 2.3. Gasification
715 35.14 2.10

50 638 32.38 3.68 ME ¼ 1.07%

Thermolysis technology covers the gasification concept, in
656 31.49 0.35 E ¼ 171.77 kJ mol1 which air is used (in sub-stoichiometric ratio) as a gasification
674 30.65 0.61 agent to produce high calorific fuels [93]. The main advantage of
692 29.85 1.01 using air instead of O2 alone is to simplify the process and reduce
710 29.09 4  105
the cost. But a disadvantage is the presence of N2 (inert) in air
717 28.81 0.79
which causes a reduction in the calorific value of resulting fuels due
to the dilution effect on fuel gases. Hence, steam is introduced in
expression that could be used for activation energy estimation at
a stoichiometric ratio to reduce N2 presence. Several types of
high heating rates. The governing equation of polymer loss could be
gasification processes have already been developed and reported.
expressed as follows [34]:
Their practical performance data, however, have not necessarily
dxp =dt ¼ xp $ko (23) been satisfactory for universal application. A significant amount of
char is always produced in gasification which needs to be further
where ko is the overall kinetic rate constant representing the processed and/or burnt. Other gasification schemes (mainly in pilot
cracking scheme reactions, i.e. primary, secondary and tertiary. And scale) use a great deal of expensive pure oxygen, whilst others

y = 19835x - 22.182
10
y = 30877x - 36.893 R2 = 0.9451
9 R2 = 0.8979
y = 19265x - 22.344
8 R2 = 0.9741

6 y = 12429x - 12.458
R2 = 0.9191
κ + ln(1-xs)

3 HR= 5 HR= 10 HR= 25 HR= 50

0
0.00135 0.0014 0.00145 0.0015 0.00155 0.0016

1/T (K-1)

Fig. 11. Ozawa–Flynn–Wall fitting method (simplified) showing regression and fitting equations used in activation energies estimation for different heating rates (HR).
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 115

Te m p. (C)
365 383 401 419 437 444
1 1

0. 75 0. 75

Xp (Ex p) Xp (Mode l )

Xs
Xp

0. 5 Xs (Ex p) Xs (Mode l ) 0. 5

0. 25 0. 25

0 0
0 10 20 30 40 50
ti m e (s)

Fig. 12. Polymer fraction (xp) and solid conversion (xs) for HDPE, showing both experimental and modelled results.

necessitate considerable amounts of expensive materials such as
coke and limestone, and deposit much sludge from which metals
cannot be separated. An ideal gasification process for PSW should
produce a high calorific value gas, completely combusted char,
produce an easy metal product to separate ash from and should not
require any additional installations for air/water pollution abate-
ment. Early gasification attempts have been reported since the
early 1970s [94,95]. The gasification into high calorific value fuel
gas obtained from PSW was demonstrated in research stages and
results were reported and published in literature for PVC [96], PP
[97] and PET [98]. Also a need for utilizing as much waste as
possible to treat in co-gasification is something that captured the
attention of many researchers. Table 6 summarizes the main gasi-
fication technologies available to treat and/or co-gasify PSW.
In industrial application, co-gasification of a number of waste
streams (PSW, biomass, RDF, etc.) has been proven for its feasibility.
A typical co-gasification scheme will include a two-step process of
two adjacent gasification furnaces [8–83]. After pre-treatment (i.e.
shredding), the mixed stream will be introduced to an RDF moulder
(in which air sorting takes place and steam treatment). Oxygen and
steam will be introduced to the first gasifier operating at low
temperatures (outlet steam temperature of 1300  C) with circu-
lating sand at a temperature around 700  C (Table 6). In the second-
stage high-temperature gasifier, the gas from the low-temperature
20
R2 = 0. 9978 (Ex p)
ln(Xp)+ln(dx/dt)
gasifier is reacted with steam typically at a temperature of 1500  C
to produce a gas composed primarily of carbon monoxide and
hydrogen. At the furnace outlet, the gas is rapidly cooled to below
200  C to prevent the formation of dioxins and chlorides (based on
chlorine content on PSW). The granulated blast furnace slag also
produced is used in civil engineering and construction materials.
The gas then passes through a gas scrubber, and any remaining
hydrogen chloride is neutralized by alkalis and removed from the
synthetic gas. This synthetic gas is used as a raw material in the
chemical industry to produce chemicals such as hydrogen, meth-
anol, ammonia and acetic acid.
2.4. Concluding remarks on pyrolysis and gasification
At high temperatures (around 850  C), PSW pyrolysis yields
almost exclusively aromatics, C2H4 and CH4 [88,89]. The increase of
the aromatic fraction with increasing gas phase temperature is also
reported for PSW and MSW [102]. To crack polyaromatic hydro-
carbons, very high temperatures (>1200  C) and long residence
times are required [103,104]. Typical cracking products (H2, C2H4
and C2H2) increase with elevated operating temperatures [99]. In
PSW gasification, endothermic gasification reactions involving
steam and CO2 [105,106] and high heating rates create a char which
is more reactive and easier to deal with [106,107]. As a result of
these reactions, high gasification temperature has been reported to
increase the H2 concentration [108], gas yield [98] and sometimes
LHV [109] for a wide range of gasification configurations and
oxidizing media. Concluding, based on the previous findings, both
pyrolysis and gasification could be further utilized in industry in
a more engineered and designed end-product fashion. Up till now,

0 most pyrolysis and gasification processes applied on an industrial

0.00143 0.00153 scale lack a designed end-product manner. Both processes could be
Exp
improved by more appropriate up-scaling. Thermal decomposition
Model
schemes on the end-product (employing lumped product analysis)
-20
Best fit: Exp are an essential step to be developed and validated. Advances in
Best fit: Model that area will aid in the improvement of pyrolysis and gasification
reactors [22].
R2 = 0.9994 (Mode l)
2.5. Hydrogenation (hydrocracking)
-40
-1
1/ T ( K )
Hydrogenation by definition means the addition of hydrogen
Fig. 13. Dynamic experiments. Developed model fitting showing ln(xp) þ ln(dx/dt) as (H2) by chemical reaction through unit operation [110]. Many
a function of temperature (K1) for the experimental and modelled results. technologies employing PSW hydrogenation have failed or
116 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
disintegrated in pilot stages. The RWE process was one of these
terminated projects which employed hydrogenation after depoly-
merization of plastic waste. PSW was mixed with oil followed by
depolymerization (10 kg/h). HCl is removed afterwards for
contaminated PSW. RWE process operated in a temperature range
between 400 and 500  C. The main outputs were 80% oil, 10% gas
and solids. The Hiedrierwerke and Freiberg hydrogenation
processes are two other examples of technologies currently
terminated for financial reasons. Both processes employed
a hydrocracking reactor above 400  C producing rich oils [66].
The main technology applied in PSW recycling via hydrogena-
tion technology is the Veba process. Based upon the coal liquefac-
tion technology, Veba Oel AGÒ converted coal by this process into
naphtha and gas oil. The current PSW treatment technology
employs a depolymerization section, where the agglomerated
plastic waste is kept between 350 and 400  C to effect depoly-
merization and dechlorination (in the case of PVC rich waste). The
overhead of this product is partially condensed [63]. The conden-
sate, containing 18 % of the chlorine input, is fed into a hydro-
cracker. The HCl is eliminated with the formation water. The
resulting Cl-free condensate and gas are mixed with the depoly-
merisate for treatment in the VCC section. The main outputs of the
process could be summarized as follows: (i) HCl, (ii) Syncrude from
the VCC section (chlorine free), (iii) Hydrogenated solid residue, (iv)
Off gas. The input for the depolymerization section was described
by Sas [111] as follows: (i) particle size < 1.0 cm, (ii) bulk
density  300 kg m3, (iii) water content < 1.0 wt%, (iv) PVC < 4%
(2 wt% chlorine), (v) inert content < 4.5 wt% at 650  C, (vi) metal
content < 1.0 wt%, (vii) content of plastic  90.0 wt%.
2.6. Treatments of chemical nature
In this section, other treatments of either pure chemical nature
or other (non-thermolysis) schemes employing polymer degrada-
tion technologies are stated. Most technologies (on an industrial
scale) operate a reactor in the process, whether being a kiln or
a rotary, etc. One of the main technologies of the eighties is the
degradative extrusion process, where the plastic degrades in an
extruder utilizing the extrusion operation in recovering certain
chemicals. The process employs high operating temperatures and
influences PSW degradation via mechanical and chemical energy
[112]. Degradation promoting additives might be employed. IKV
process is one of the main technologies used in degradative
extrusion. The input to the process is PSW with a maximum PVC
content of 80%. The operating temperature is between 300 and
400  C, employed in a pilot scale twin screw extruder [113]. Other
employed technologies are the Leuna and Stahlwerkke processes,
with 400 and 200 kg h1 capacity, respectively. Both processes
operate in the range of 400  C for PSW with up to 50% PVC content.
Degradative extrusion provides an optimum engineering solu-
tion especially on a small-industrial scale (10 kg h1). Menges and
Lackner [114] stated the advantages of degradative extrusion as (i)
achieving molecular breakdown of thermoplastics and hence low
viscosity polymer melts, (ii) applying a combination of mechanical
and chemical recycling scheme prompts the degradation process by
introducing steam, gas, oxygen or catalysts, if needed. Another
advantageous technology for chemical treatment is catalytic and
steam cracking. The concept for both processes is the employment
of either steam or a catalyst in a unit operation. Table 7 summarizes
the main technologies employed in steam and catalytic cracking of
PSW.
Whilst degradative extrusion, steam and catalytic cracking are
employed worldwide, thermoplastics (mainly polyolefins) are
advantageous for other recovery methods that are present on both
pilot and industrial schemes. These schemes fall into the category
of chemical recycling, and can be subdivided into feedstock
(monomer) recycling and recycling of chemical nature.
Recycling PSW via pure chemical routes could be summarized
by the following technologies: hydrolysis, glycolysis, fractionation,
hydroglycolysis, aminolysis, methanolysis and acid cleavage. Table
8 summarizes chemical recycling schemes, not stated previously
and not classified within the advanced thermo-chemical treatment
category.
First of the chemical recycling schemes is hydrolysis (refers to
the reaction with water) which can produce both polyols and amine
intermediates [42] from post consumer PSW. The most common
single-polymer plastics treated via hydrolysis are PET and PU
foams. Polyols produced from hydrolysis can be used as effective
fuels [24] and the intermediates can be used to produce virgin
single-polymer plastics (i.e. PU). This method uses heated, oxygen
free environment to break down PU and other PSW into gases, oils
and solids [24]. It is believed that superheated steam (200  C)
converts PU foams into a two-phase liquid within around 15 min, at
a volume reduction of factor of 30. The chemistry can be summa-
rized as:
R0  NH  CO  O  R00 þ H2 O/R  NH2 þ HO  R þ CO2
R0  NH  CO  NH  R00 þ H2 O/2R  NH2 þ CO2 ð25Þ
Focusing on the recovery of the polyols showed that super-
heated steam temperature should be around 288  C, producing
a polyol that can be utilized in virgin plastic production when
mixed with 5% pure resins. Other hydrolysis treatments could be
combined with a basic thermolysis scheme. This is demonstrated
by the case of PA 6 treatment, which also follows a monomer or
feedstock recycling scheme. A step description was given by Mas-
tellone [5], for the case of PET glycolysis. At a temperature
exceeding 240  C in a catalytic bed, the addition of Ethylene glycol
to PET (condensation polymer produced by the reversible reaction
of teraphalic acid and ethylene glycol) the formation of bis-
hydroxyethyl teraphthalate will occur. After treatment with water,
teraphalic acid (original monomer) will form giving us the hydro-
lysis step. If instead of water, methanol was used, the dimethyl ester
of teraphalic acid would be formed along with ethylene glycol
(methanolysis) (Table 8).
Another chemical treatment scheme (commonly used for PET
and PU) is glycolysis, which describes a polymer’s reaction with
diols at temperatures above 200  C [24]. The objective of this
process is the recovery of polyols as well (Table 9). The process also
uses fine granules of 6 mm to be heated up for several hours. Unlike
alcoholysis (reaction with alcohol under pressure at elevated
temperatures), the process is widely used for granules recovered
from foam PSW [115]. A different chemical process used in chemical
treatment schemes is fractionation. A description was given by Zia
et al. [36] for the methods applied in PU containing materials. The
principle is based on combining a PU containing material with
a solvent to form a solution. The solvent is usually a polar one
chosen from the dimethylsulfoxide group (DMSO), finally a filtra-
tion process is conducted to remove the solution before the non-
solvent is added to form a suspension.
3. Energy recovery: quaternary treatments of PSW via
combustion processes
3.1. Background information
Economical constrains pose a major dilemma in industry,
especially with recovery methods of processes scrap and hetero-
geneous waste streams. Energy recovery offers a solution to such
problems employing combustion processes to produce heat, steam
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 117

Table 6
Summary of main Gasification technologies reported on PSW.

Technology Summary Reference

WGT process Different types of wastes (PSW, MSW, sludges and) are mechanically pre-treated, sorting out incombustibles [99]
and granulated to optimum sized particles and fed into a cylindrical reactor for gasification at 700–900  C to yield a
HCV gas. Upon discharge and subsequent separation of gas and char, the latter may be utilized via combustion in a
boiler to raise steam.

Texaco process PSW is mildly thermally cracked (depolymerization) into synthetic heavy oil and some condensable and non-condensable [100,101]
gas fractions. The non-condensable gases are reused in the liquefaction as fuel (together with natural gas). The gasification
is carried out with oxygen and steam at a temperature of 1200–1500  C.

SVZ process Input is fed into a reactor (kiln), together with lignite (in the form of briquettes) and waste oil. Oxygen and steam are used as [73]
gasification media, and are supplied in counter flow with the input materials. Liquid hydrocarbons are further processed by
oil pressure. The gas is used mainly for methanol production and around 20% is used for electricity production.

Akzo Nobel The process consists of two separate circulating fluid bed (CFB) reactors at atmospheric pressure. The first is a gasification reactor [73]
in which waste (usually rich with PVC) is converted at 700–900  C into product gas (fuel and HCl gas) and tars. The second unit is a
combustion reactor that burns the residual tar to provide heat for the gasification process. Circulating sand between the gasifier
and combustor transfers heat between the two reactors.

and/or electricity. PSW posses’ high calorific value when compared
to other materials due to its crude oil origins, as Table 9 illustrates
by comparison to gas oil, heavy oil and other crude oil derivatives.
Since the heating value of plastics is high, they make a convenient
energy source. Producing water and carbon dioxide upon
combustion makes PSW similar to other petroleum based fuels. In
general, it is considered that incineration of PSW results in
a volume reduction of 90–99%, which reduces the reliability on
landfilling. In the process of energy recovery, the destruction of
foams and granules resulting from PSW also destroys CFCs and
other harmful blowing agents present [24]. Yet again, the presence
of FRs complicates the technical aspects of energy recovery
receiving much of the attention nowadays.
Dependency on fossil fuels as an energy source could be reduced
by PSW utilization in energy recovery schemes. It is estimated that
by 2020, 17% of the UK electricity could come from waste compared
to the 0.5% currently observed [116]. The Department of Environ-
ment, Food and Rural Affairs (DEFRA, UK) published in 2006
a review on England’s waste strategy with a set target of 25% MSW
recovered as EfW materials, which corresponds to 700 MWe of
electric capacity. Further to that review, many associated agencies
embraced the idea of direct incineration and recovery of energy by
thermal processing. Three new EfW plants in Hampshire accounted
for 46% and 35% of its MSW and recycling capacities in 2004–2005,
and a new EfW plant to treat 500,000 tonnes/year is under
construction in Kent; in Sheffield, the existing EfW plant with

Table 7
Summary of main steam and catalytic cracking technologies employed in PSW chemical recycling.

Technology name Process conditions Notes References

Fuji process Top ¼ 400  C, Tip ¼ 250  C
Capacity (pilot): 500 tonnes/year
Capacity (input): 5000 tonnes/year
Industrial scale [73,113]
Low-temperature catalytic cracking
Employing pyrolysis technology
Zeolite catalysts are used (ZSM-5)
Input: polyolefin waste
Output: 80% oil, 15% gas & 5% solid rest fraction

Kentucky process Top ¼ 400–450  C, P ¼ 56 atm Developed in the University of Kentucky [73]
Input: PSW Research stage
Output: 90% oil Zeolite catalysts are used

Leuna degradative extrusion þ steam
cracking process
Top (extrusion) ¼ 400–500  C, Top
(extrusion)  800  C
Input: 13 wt% PSW
Output: C2, C3 and C4 monomers
Description: light PSW fraction is treated with degradative [73]
extrusion and then mixed with paraffin from hydrocracking.
This mixture is the input for steam cracker.
Project showed good results but terminated
due to lack of interest.

Amoco Top ¼ 490–580  C Research [63]

Input: PE, PP, PS, PSW mixed with
vacuum gas oil
Input quality: in solution
Output: naphtha, light mineral oil

Mazda Input: shredded PSW from scrap Pilot [63]

car parts.
Output: 60% (oil þ kerosene)

Nikon Top ¼ 200–250  C Pilot [63]

Input: PSW (10 mm in size) Metal catalyst are employed
Output: 80% oil Research

Molten metal technology Top ¼ 1400  C Nickel based catalyst are used 30% HCl has [166]
Input: PSW and organic waste been recovered in lab scale
Output: synthesis gas, HCl, slag

PC: process conditions, Top ( C): operating temperatures, Tip ( C): input temperatures.
118 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Table 8
Summary of chemical and monomer (feedstock) recycling schemes of a non thermo-chemical nature.
Technology name Process conditions
PET hydrolysis Top ¼ 200  C
P ¼ 2–5 MPa
PU hydrolysis (Bayer general motors) – Pilot scale
PA 6 treatment via thermolysis/hydrolysis Top ¼ 300  C
P ¼ 20–100 bar
Methanolysis of PET Top > 200  C
P > 2 MPa
Glycolysis of PET Top > 200  C
PMMA depolymerization Top > 300  C
Acid cleavage of PA 6 Phosphoric acid medium used
a capacity of 135,000 tonnes is being replaced by a new plant with
a capacity of 225,000 tonnes [116–119].
3.2. Co-incineration (direct one stage, two stage and fluidized bed
combustion process of waste)
MSW can be accepted with high fractions of PSW in municipal
solid waste incinerators (MSWIs). However, for such combustion
processes to be dictated to PSW a number of issues arise. First, if
one wants to produce reusable slags, the heavy metal input into the
incinerator should be limited [37,110]. Furthermore, an important
point is the relatively low incineration temperature of MSWIs
(around 850  C). Direct one stage incineration could be used for
many types of waste [37,115].
Fluidized bed combustors (FBCs) are increasing in popularity
amongst many incineration lines due to (i) less complex emissions
control systems, (ii) high combustion efficiency with simple oper-
ation and fast response, (iii) reduction in boiler size and (iv) low
corrosion with easier ash removal. Yasin et al. [116] reviewed FBCs
technologies in Europe, where the revolving fluid bed developed by
Ebara Co. is stated to be emerging very rapidly on the continent.
More than 100 units are installed worldwide including Madrid’s
plant unit which takes 10% of the city’s waste (with 9% commingled
PSW) to produce electricity. The main principle for this technology
is the mechanism of the internal furnace with no moving parts,
equipped with a slanted bed floor to produce a revolving sand
motion.
Germany has the highest number of incinerators in Europe, with
over 53 units exceeding the capacity of 10.7 million tonnes/year
[120]. In the USA, the design capacity (110 tonnes/day) of over 190
incinerators has been exceeded in 2006. In the EU, ISOPA supports
the incineration of MSW with high content of PSW (which make up
on average 7% of MSW), which resulted in a high calorific value fuel
with constant ash content [121]. Many countries within the EU
cover the electrical demand to hundreds of communities by direct
incineration, e.g. Denmark, Sweden, and Germany. In the UK,
DEFRA announced that currently 15 energy from waste (EfW)
plants exist in the UK with a design capacity exceeding 3 million
tonnes of municipal waste [122]. Current technologies can recover
the inherit energy value of PSW and reduce fossil fuel consumption.
A series of experiments conducted by Alliance of the Polyurethane
Industry (API, US), adding flexible PU and other fractions of PSW to
MSW (up to 20 wt%). This resulted in a high calorific value fuel,
whilst ash generation remained constant [121]. Municipal solid
waste incinerators (MSWIs) are usually built to deal with waste of
a calorific value between 9 and 13 MJ kg1. Reference is usually
made to Rittmeyer and Vehlow [123] and Rittmeyer et al. [124] on
the co-firing of PSW (PU filled) in municipal solid waste
Notes References
PET is heated with an excess of water at high temperatures [24,42,113]
[24,42,113]
Depolymerization (monomer) recycling with water at [42]
high temperatures
Metal catalysts are applied in this process [5]
Insensitive to contaminants
Acceleration with catalyst [42]
Molten baths used (tin and lead) [42,43]
Several minutes residence time
Industrial scale [42]
incineration plants (MSWIPs). The TAMARA test incineration used
was equipped with a co-current furnace.
Weigand et al. [125] showed the application of bubbling fluid-
ized beds (BFBs) in the combustion of MSW with high fraction of
PSW. The coal fired BFB was a 39 MW reactor with superheated
steam at 475  C and 64 bars. When used with large fractions of PU
foam, PE and PS, the coal mix resulted in a heating value of 17.6 MJ
kg1. Emissions of pollutants or carbon (in ash) did not increase,
except for the concentration of the ten trace elements grouped as
Sn þ As þ Pb þ Cr þ Co þ Cu þ Mn þ Ni þ V þ Sn which increased by
a factor of 3–4 (0.06–0.09 / 0.22–0.32 mg m3) which is mainly
due to the presence of Sn (tin) used as a catalyst in polymerization
[24]. A two stage incineration was successful in the study con-
ducted by Rogaume et al. [126] aiming at optimizing combustion
conditions that result in minimal NO and CO emissions by com-
busting PU foams from automobile car seats.
Co-incineration could furthermore aid in the energy supply
issue and reduce air pollutants emission control problems. A
number of European nations have adopted the strategy of mixing
high content of PSW residues with coal capitalizing upon the
concept of economies of scale. Yet still, transportation issues rise in
this case. Normally, it has been demonstrated that fuels from
wastes within a distance of 80 km could support, at the maximum,
a 20 MW power plant. This may be sufficient for industrial appli-
cations. However, the optimal sized power plant in today’s world,
however, exceeds 1000 MW in capacity. A previous study by Boa-
vida et al. [127] demonstrated the co-combustion of PSW with coal
using a fluidized bed combustor (FBC) with the aim of achieving
a fuel mixture with little variations in its heating value and
simultaneously upgrading the mixture for energy purposes. Results
obtained indicate that waste feeding plays an important role in
stable combustion. The form in which the fuel is fed to the
combustor makes a significant contribution to achieve desirable
combustion performance and differences were observed in results
regarding the combustion efficiency and emissions when waste
was fed densified or in a fluffy state when it was burned mixed with
coal. Part of the combustion of waste material, contrary to that of
coal, was observed to take place in the freeboard where the
temperature was as much as 150  C above that of the bed. The
addition of waste by 20% in weight was found to cause a little
disturbance in the bed temperature but relatively more enhanced
variations in the freeboard, due to increase in volatiles released.
Co-incineration, namely in FBCs, depends on both the rate of
volatiles release and success of the subsequent mixing between the
volatiles and air, thus giving rise to oscillations in temperature along
the freeboard height. Many previous studies utilize FBCs, especially
in a bubbling mode. However, recirculation of ash to the bed is
always avoided in order to allow collection and verification of various
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Table 9
Calorific value of some major plastics compared with common fuels [5,70].
Item Calorific value (MJ kg1)
Polyethylene 43.3–46.5
Polypropylene 46.50
Polystyrene 41.90
Kerosene 46.50
Gas oil 45.20
Heavy oil 42.50
Petroleum 42.3
Household PSW mixture 31.8
elements distribution. In R&D affiliated work, furnaces are usually
pre-heated to 500  C to establish uniformity during material feeding.
And during combustion in FBCs, water cooling in a number of heat
exchangers is used to maintain the process temperature, as well as,
primary and secondary air supplies (25% of the total air supplied) are
introduced to avoid elutriation from the bed. Another observation
made in co-incineration is that the form in which the waste is fed
appears to have a strong influence on the combustion performance
[127]. Excess air is observed to be an important parameter in
achieving satisfactory combustion, because the minimum amount
required is found to be about 25% [127]. Above this value, greater
emissions of NOx and N2O were observed. Because of the strict
regulations governing the co-incineration of waste (addressed
mainly by EU directive 2000/76/EC), certain economies of scale
aspects (in terms of plants efficiency and operation parameters) are
of major concern on the continent. The directive sets certain regu-
lations regarding the operating conditions, such as gas temperatures
and residence times (850  C/2 s for MSW and 1100  C/2 s for waste
with greater than 1% halogenated organic substance expressed as
chlorine). It also states that all combustion gas temperatures should
be measured near the inner wall or another representative point in
the combustion chamber as authorised by the regulator. The
temperature measurement point should be located after the last
injection of combustion air, including secondary air and re-circulated
flue gases where carried out. The directive also requires that any heat
generated by the incineration or the co-incineration process should
be recovered as far as practicable. It will, therefore, be necessary for
all operators of incineration plants to demonstrate that this condi-
tion has been met or explain why it is not possible to recover energy.
In all cases it will be necessary to consider pollution control aspects
Alternative fuels
Gases
Liquids
Clinkers
Fig. 14. Schematic of cement kiln combustion [168].
119
when assessing options for increasing energy recovery. For example,
boiler designs must also minimise the potential for dioxin reforma-
tion (de novo synthesis) in the 450–200  C range. Maximising elec-
trical energy recovery may not be appropriate where some of that
energy might be better used to improve the dispersion of wet plumes
from wet scrubbers.
3.3. Rotary and cement kiln combustion
Many industrial schemes utilize cement kilns as incinerators.
The energy costs of cement kilns can be up to 25% of the turnover,
and the financial benefits of using waste as a fuel are obvious. The
cement industry is a branch of industry that has been using alter-
native fuels made from PSW for over two decades. Fig. 14 illustrates
schematically the concept of cement kiln processing of waste with
high PSW content. The technological requirements of this industry
make it particularly well suited to the incineration of fuels made
from waste. Cement kiln operators and cement producers have set
their own standards utilizing PSW as a feedstock. For example,
Lafarge plant in Poland set the following requirements: a calorific
value of over 14 MJ kg1 (weekly average), 11.7 MJ kg1, a chlorine
content of less than 2.5%, a PCBs (polychlorinated benzene) content
of less than 5 ppm and a heavy metal content of less than
2500 ppm. Cement kiln operation lines are especially suitable for
the use of PSW as a feedstock [73]. The incineration conditions in
cement kilns make them suitable for using alternatives fuels made
from PSW because of the following factors: a high temperature,
a sizeable kiln length, a long total time of fuel staying in the kiln,
and the alkine environment present within the kiln. Temperatures
in the kiln are very high (the gas temperature in the combustion
zone reaches 2000  C); the gas residence time in temperatures
around 1200  C is about three seconds given a 2–3% oxygen content
in the gases,. These conditions are far above the temperature level
and time necessary for the total combustion of high molecular
hydrocarbons. Currently there are 250 cement plants in the Euro-
pean Union producing 170 million tonnes of cement per year [130].
In Poland there are 12 full-production cycle cement plant. Poland
produced almost 11 million tonnes of cement in 2003. According to
recent estimates, the greatest usage of alternative fuels in European
countries is to be found in Holland (725), Switzerland (34%) and
Belgium (30%) [73,131].
Coal
Alternative fuels
Gases
Liquids
Solids
Kiln
Mineral
components
Cement
Raw materials
120 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Many cement kilns in the UK, Belgium, Holland, Switzerland and
other countries have therefore started to use pre-treated waste
streams as a fuel. A valid example is the cement plant owned and
operated by Lafarge cement S.A. (Poland) using alternative fuels
made from processes waste. Cement kilns produce a clinker by
sintering alkalic raw materials such as lime (CaCO3), clay (SiO2 and
Al2O3) and gypsum (CaSO4) in a kiln at a very high temperature
(1450  C in the solid fraction). The kiln can, in fact, could be seen as
a rotary kiln with a much longer length (200 m). Furthermore, the
solid materials flow in the opposite direction to the incineration
gases. The length of the kiln results in a long residence time of
incineration gases at high temperatures: 4 to 6 seconds at 1800  C
and 15–20 s at 1200  C [63]. Two processes are dominant in this
application, i.e. a dry process and wet combustion. In the dry
process the raw materials are introduced in dry form into the kiln.
In the wet process, these materials are introduced in the form of
slurry. The type of process used depends, amongst others things, on
the source of the kiln’s raw materials. A clear disadvantage of the
wet process is that it needs much more energy than the dry process
(5000 MJ/tonne against 3600 MJ/tonne clinker respectively), since
no water has to be evaporated in the dry process. In the canton of
Zug (Switzerland) more than 30 fractions of waste are collected and
sent for incineration outside the canton [128]. In the period
between 1995 till 2000, all commingled PSW was send to the
cement kiln of Untervaz. In 2001, the efficiency of the kiln was
increased by 10% by altering the feed and recycling plastic bottles
and containers from collection points. By 2001, 50% of all plastic
waste was collected separately for cement production.
A Finnish study [129] considered the behaviour of nitrogen from
polymers and plastics in waste-derived fuels during rotary kiln
combustion. It was found that the emissions of NO þ NO2 during
rotary kiln combustion in an entrained gas quartz tube reactor (at
750–950  C, in 7% O2/93% N2) depended strongly on the amount of
char produced from high-nitrogen fuels (PU foam, nylon, RDF,
MSW, urea/formaldehyde glue, sewage sludge) and the nitrogen
content of the fuels. At nitrogen content of 6.6 wt%, less than 10% of
the PU nitrogen was emitted as NO þ NO2.
One of the main technologies used in incineration via rotary
kilns is the BSL technology. The rotary kiln is able to process solid,
fluid, and gaseous waste streams into useful feedstocks and energy.
If necessary, natural gas or liquid energy carriers can be added in
order to reach the necessary high temperatures. The waste is
incinerated in the rotary kiln and a post-combustion chamber,
directly after the rotary kiln, at temperatures of 900 to 1200  C. The
flue gas from the post-combustion is cooled from 1200  C to the
range of 230–300  C. The process can deal with a mixture of high-
chlorinated wastes (solvents, chlorinated tars, plastics). The
accepted particle size for the incineration process is
10  10  10 cm. When larger parts are offered, a shredder is
needed [73]. No information about accepted moisture content,
amount of dirt, etc. has been obtained.
3.4. Blast furnace application
Out of the different recycling technologies, recovery of energy
and fuel from plastic waste is a very important and effective option.
For the smelting of iron ore for pig iron production, traditionally
coke is used in a blast furnace to generate CO and heat. PSW have
replaced part of the coke or pulverized coal for pig iron production.
Energy and chemical recycling processes have been developed
worldwide to treat PSW via blast furnaces as a reducing agent to
coal or coke implementing pyrolysis, gasification, a combination of
both in a step wise fashion or combustion. It should also be stated
that PSW as a feedstock has two main objectives within concerned
industry: (i) acting as fuel to supply energy in it is subsequent
combustion phase, (ii) acting as a reducing agent in pyrolysis and
gasification processes to replace coke [78]. Over the past decade,
enviro-friendly chemical recycling processes became of interest,
and among them, in the steel making industry the use of waste
plastics as a supplemental fuel with coal [130,131]. Occurring
reactions are shown in Table 10 and illustrates the existence of
reducing and oxidizing reactions. This thermal application has
multiple merits (i) one large furnace can consume over 150,000
tonnes of waste plastics per year [132], (ii) it has higher energy
efficiency up to 80% [133,134], and lastly environmentally less
hazardous due to the lack of dioxin generation [134,135].
This technology has been dominant in a number of markets and
industries worldwide and has been reported by a number of steel
manufacturers. Bremen Steel Company in Germany successfully
substituted heavy oil that was used as a supplemental fuel with
recycled plastics up to 50,000 tonnes [136,137], whilst in Japan
numerous efforts have been made on bench and industrial scales
[138–140]. In Korea, Pohang Iron and Steel Making Company
(POSCO) has shown the possibility of using waste plastic for
a similar purpose in 1996; however the higher cost and relatively
low combustibility (i.e. above higher energy efficiency) of waste
plastics compared with pulverized coal hinder the application
[138]. A programme sponsored by the Ministry of Environment and
Forests (India) has announced back in 2006 the establishment of an
800 kcal NM3 (on the tonne) blast furnace unit for the treatment
of PSW [141]. The PSW fed is injected to form a broken down
reducer gas (CO and H2). The reducer gas raises through the raw
material layers in the blast furnace and reacts with iron ore. Whilst
the reducer gas reacts with the iron ore to produce pig iron, the gas
after the reduction reaction is recovered at the top of the blast
furnace.
Generally, PSW (namely polyolefins) decomposes thermally into
gases and oily liquid (tars) phase [24,30]. Thermogravimetric
results on commercial low-density polyethylene (LDPE) and waste
PE have demonstrated that weight loss could occur at temperatures
as low as 300  C followed by fast thermal decomposition that ends
around 400  C [142–144].
3.4.1. Simplified design approach for pulverized particle injection
Previous reports have been focused on hot models representing
blast furnaces for a number of applications [141–145]. Regular
injection of the pulverized particles (plastics, coal, etc.) is coupled
with N2 gas from an upstream tuyere tip. The combustion of
pulverized particles is modelled as three phase flow consisting of gas,
coke bed and dispersed particle phase. Summarized and simplified
below is the mathematical breakdown of the modelling sequence of
blast furnace in a hot model [145,146]. A schematic drawing of the
hot model used for the simulation is given in Fig.15. Properties of the
pulverized coal and plastic (PE) are given in Table 10.
Equations for the gas and coke bed phases are solved with
Eulerian methods. However, the dispersed particle phase is tracked
in a Lagrangian fashion. First, calculations of fluid flow, heat and
Table 10
Injection fuel analysis determined by Goto et al. [145].
Component (wt%) Coal Polyethylene
Volatile 33.32 99.87
Ash 7.40 0.13
Fixed carbon 59.28 –
C 76.76 84.83
H 4.70 14.08
O 8.65 –
Calorific value (MJ kg1) 27.28 41.85
Density (kg m3) 1300 920
Heat capacity (J kg1 K1) 1300 2400
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Plastic
feed Coke bed
Raceway
Blowpipe
Blast
Fig. 15. Schematic diagram of the hot model of a blast furnace [145].
mass transfer in the blowpipe are done in a three-dimensional
cylindrical system. Table 11 illustrates the design algorithm and
main equations used.
In the coke bed, a volume fraction (ag) distribution is taken from
a three plane distribution Goto et al. [145]. As for the effectiveness
of the diffusion of the gas in the coke bed (D), Lingy’s method
[144,149] was used to model the parameter (Eq. (32)). Furthermore,
the effective thermal conductivity of the gas in the coke bed is
modelled by replacing the Schmidt number with the Prandtl
number in Eq. (32). It should also be noted that the particle Rey-
nolds number (Rep) is defined on the basis of the Alsip velocity
dpjug  up jr=m and the drag force coefficient (CD) are adapted from
Clift et al. [147]. The chemical reactions are modelled according to
the reaction scheme presented in Table 12.
In reaction C1, a first order devolatilization of plastic particles to
volatile matter (V.M.) is assumed and reaction rate is defined in an
Arrhenius form. Shoji et al. [148] and Goto et al. [145] have assumed
the products to be hydrocarbon mixtures containing C, H and O.
Combustion reactions for coal char particles (C2, C3 and C4) are
assumed to follow a limiting kinetic/diffusion rate (Eq. (21)). It
should be noted that the Lagrangian equations for the particle
motion and heat transfer are solved using a Runga–Kutta–Gill
method. Results demonstrated by Goto et al. [145] show that plastic
particles (>4 mm) were more dispersed in the radial direction than
particles between 2 and 4 mm. It was also witnessed that the
average particle temperature in the blowpipe was very slow (300–
550 K in 0.1 m) compared to the pulverized coal (300–550 K in
0.1 m).
3.4.2. Blast furnace combustion characteristics
PSW fed to the blast furnaces are usually crushed after removing
foreign substances. The plastic is then gasified in the high-
temperature region of the blast furnace. CO2 generation at the
expense of O2 will lead to the characteristics of combustion reac-
tions. Plastic treated (virgin or waste) in blast furnaces experience
50% weight loss at around 390  C, similar to the behaviour wit-
nessed in thermogravimetric chambers [22]. A number of reasons
cause the diversity in the reports previously published with regards
to blast furnace treatment, mainly differences in molecular weight,
microscopic density and type and length of branching.
A major issue in plastic blast furnace operation is imperfect
combustion due to insufficient supply of oxygen (i.e. sub-stoichio-
metric combustion conditions) or oxygen limited access due to
diffusion controlled processes (i.e. mass transfer). Plastic particle
size and O2 content were reported to have influenced the
combustion efficiency. A study by Kim et al. [146] demonstrated the
combustion of PE particles in a blast furnace hot model. The PE
particles were injected through the blowpipe at 1100  C and gas
concentrations (CO, CO2 and O2) were determined by using GC-MS.
121
A downshift of the position of the maximum raceway temperature
to the direction of the tuyere with the increase of O2 enrichment
and blast temperature was observed. Another observation was
made regarding the distance window of maximum raceway
temperature on the model used: O2 enrichment expands the
window by a factor of almost two.
Blast furnace operation in industry occurs with PSW and
a mixture of secondary fuel (i.e. pulverized coal or heavy oil). To
that extent, it is desired to simulate the co-combustion of PSW and
other materials in experiments and models. Kim et al. [146] pub-
lished the results of a study of PE and coal mixture combustion
compared with previous studies on direct combustion PSW and
coal combustion. Two types of mixture both having 10 wt% of
recycled PE but with different particle sizes were used. Combustion
behaviour from 100 wt% pulverized coal was compared with that of
the mixture as a reference line. As anticipated, the increase of
distance from the tuyere enhances the combustion efficiency, for
instance, 100% pulverized coal shows an increasing efficiency from
68 to 81% along the raceway.
3.5. Environmental concerns and management issues of PSW
incineration
Several definitions of sustainable development have been put
forth, including the following one: development that meets the
needs of the present without compromising the ability and needs of
future generations [152]. Increasing awareness of the environ-
mental impact of certain emissions associated with combustion
processes (i.e. CO2, NOx and SOx) triggered a renewed interest in
enviro-friendly integrated systems. NOx and particulate emissions
are a major topic in combustion science. It has to be considered
even in the total absence of nitrogen filled fuels or operation under
high temperatures for release of thermal NOx, as in the case for
many industrial applications.
PSW combustion generates volatile organic compounds (VOCs),
smoke (particulate matter), particulate-bound heavy metals, poly-
cyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzofu-
rans (PCDFs) and dioxins. Carcinogenic substances (PAHs, nitro-
PAHs, dioxins, etc.) have been identified in airborne particles from
incineration or combustion of synthetic polymers such as PVC, PET,
PS and PE. These particulates have been found to be highly
mutagenic.
The thermal resistance of many polymeric articles is enhanced
by the addition of flame retardants (FRs), which interfere with the
thermal decomposition of the material resulting in enhanced car-
bonisation and/or interfere with the flame chemistry (i.e. the gas
phase radical pool). FRs are often chlorine or bromine based
compounds, which upon sufficient heat-up produce Cl and Br
radicals in the gas phase [36]. Presence of certain FRs is also
problematic (in terms of unit operation) when it comes to
combustion, namely chlorine and bromine based [73]. They can
reduce the efficiency of the process by forming products (from side
reactions) and increase corrosivity and fly ash generation [73,155].
Better performance is found when also antimony oxide Sb2O3, is
added. In the case of many polymer based expanded grades and
foams, typical values of 18–20 wt% Cl or 12–20 wt% Br, which
change to 4% þ 4% Cl þ Sb2O3, or 1.5% þ 2.5% Br þ Sb2O3, are cited
[36,151]. Due to environmental concerns (e.g. formation of poly-
brominated toxic gases whilst incinerating the plastic) and health
reasons associated with brominated FRs, flame retardants based on
phosphorus or nitrogen; are used nowadays. Work on the synthesis
and characterisation of a phosphorus containing PU showed that
the starting temperature for thermal degradation shifts to a some-
what higher temperature (270–288  C) and char yields at 700  C
increase as well (35–48%), for 2 wt% phosphorus PU, based on
122 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

a thermogravimetric analysis in air [155]. Emissions concerned
with polymeric materials combustions can be reduced by
increasing the cross-linking of the material, using cyanurate
structures (increasing its charring tendency instead), or introduce
smoke suppressants into the polymer structure, for example alco-
hols such as furfuryl alcohol [150–152].
The quality of the flue gas could be improved by two methods,
manipulating the combustion system itself (i.e. recalculation of
burnt gas) or end of pipe techniques (i.e. scrubbing, dust and
particulate removal and filtration, etc.). Burnt gas from flames is
commonly circulated in two ways in many industrial processes: (i)
internally, by baffling and restricting flow of the burnt gas away
from the burner, resulting in flame re-entry, (ii) externally, by
diverting up to 10% of the flue gas back into the flame. Table 13
summarizes the most common methods of controlling particulates
from combustion processes. It is also paramount to improve the
efficiency of combustion processes (in general) and thermal treat-
ments (in particular) to environmentally benefit from them.

Table 11
Design equations algorithm for blast furnace combustion [145].

Classification Design equations Nomenclature/subscripts

Governing equations of gas
and coke bed phase in
blast furnace simulation
ug  ub
 
a: volume fraction, r: density (kg m3), i: stands for phase
V$ðai ri ui qi Þ ¼ V$ðGqi Vðai qi ÞÞ þ Sqi þ SP qi þ Sbqi (26) i, q: generalized variable, S: is a source term, b: coke bed
phase, p: particle, g: gas phase, Fgb: drag force of coke bed
  rg
acting on gas phase (N m3), CD: drag coefficient of a single
Fgb ¼ ð3=4Þ$CDo $a2g $ 1  ag $ $f ag ; Regb (27)
dcoke coke particle, f (ag,Regb) is a function of the void fraction and
 3:45 Reynolds number of the interface between gas and coke
0:06
CDo ¼ 2:25Re0:31
gb þ 0:36Regb (28) bed, Regb: reynolds number (Eq. (29)), j: is shape factor,
m: viscosity in (Pa s), d: diameter (m), hbg: heat transfer

ag jcoke dcoke rg
ug  ub
coefficient, T: temperature (K), lg: thermal conductivity
Regb ¼ (29) (KW.m1.K1), Nu: nusselt number, Pr: Prandtl number.
mg
 
6 1  ag  
Ebg ¼ $ T  Tb (30)
j$dcoke gb g
$h

lg lg  
hbg ¼ $Nu ¼ 2 þ 1:1Pr 1=3 Re0:6
gb (31)
j$dcoke j$dcoke
Coke bed and pulverized a1, a2 & a3: constants, Sc: schmidt number, Pe:
particle phase models 1 a1 a2 Peclet number for diffusion defined as ug$dcoke/D,
¼ þ a3 (32)
Pe Re$Sc 1 þ Re$Sc Rep: particle renoylds number defined as dp jug  up j:r=m,
CD: drag force coefficient (Eq. (34)), Tp: particle temperature
m$CD $Rep   (K), rad: radiation, conv: convection, react: reaction,
dup =dt ¼ ð3=4Þ$ $ ug  up þ g (33)
rp $d2p mp: mass of particle (kg), Cpp: specific heat (kJ K1 m1),
Q: heat exchange rate (kW kg1), hp: heat transfer
8 24  0:8920:05$logðRep Þ
 9
< Rep 1 þ 0:132$Rep
> ; 0:01 < Rep < 20 >
= coefficient, l: thermal conductivity (kW m1 K1), 3p:
 emissivity of a particle, G: incident radiation (kW sr1),
CD ¼ 24
1 þ 0:1935$Rep 0:6305 ; 20 < Rep < 737 (34)
>
: Rep >
; sst: Stefan–Boltzman constant (kW m2 K4).
0:44; 737 < Rep
 
mp Cpp dTp =dt ¼ Qconv þ Qrad þ Qreact (35)

 
Qconv ¼ p$d2p $hp Tg  Tp (36)
( )
hp dp 2:0 þ 0:6Re0:5
p Pr
1=3 ; Rep < 776:06
Nu ¼ ¼ (37)
lg 2:0 þ 0:27Re0:62
p Pr 1=3 ; 776:06  Rep

G
Qrad ¼ 3p p$d2p  sst Tp4 (38)
4
Radiative heat I: radiative intensity (kW m2 sr1), s: coordinate along
   
transfer model dIðs; UÞ=ds ¼  kg þ kp þ ks þ kb þ sp Iðs; UÞ þ kg þ ks Ib;g ðsÞ direction s, U: direction of radiation, ks: absorption
Z coefficient, s: scattering coefficient, Np,j: Particle number
sp  00   00  00 density of group j.
þkp Ib;b ðsÞ þ I s; U F U; U $dU (39)
4p

X p$d2p;j
kp ¼ Np;j 3p (40)
j
4

X  p$d2p;j
sp ¼ Np;j 1  3p (41)
j
4

ð3:72C0 Ts Þ
ks ¼ fv (42)
C2
 
pd2coke 1:5$3b 1  ag
kb ¼ 3b Nb ¼ (43)
4 dcoke
2 3
Z
V$qr;g ¼ kg 4 I$dU  4sst Tg4 5 (44)
4p
2 3
Z
V$qr;b ¼ kb 4 I$dU  4sst Tb4 5 (45)
4p
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129 123

Table 11 (continued ).

Classification Design equations Nomenclature/subscripts

Chemical reaction kr;C2 : reaction rate coefficient for reaction C2 (Table 12)
model pd2p defined as Field’s expression in Eq. (47) [145,150],
RC2 ¼ (46) R: reaction rate (s1), Ci: mole concentration (kmol m3),
1 1
þ D: diffusion coefficient (m2 s1), h: effectiveness factor,
kr;C2 PO2 kd;C2
Agb: specific surface area of coke particles defined as
8   9
< 0:8596$exp 17980=Tp ; Tp  1273 K = 6ab/jdcoke, fv: soot volume fraction that could be
kr;C2 ¼ 6 8
8:882x10  1:2435x10 Tp þ 1:559x10 11 2
Tp ; (47) determined using Adams and Smith [151] expression
: ;
Tp > 1237 K (Eq. (26)). Mc: molecular weight of carbon, rs: soot
density (kg m3), bc: mass of carbon atom per mass of
 0:75
DO2 ;0 T   reactant mixture, B1: constant expressing mass fraction
kd;C2 ¼ 1:5 r p log 1 þ YO2 (48)
dp Tstd of volatile carbon which forms soot. B2: fraction of soot
which survives to radiate (Eq. (52)).
pd2p
RCn ¼ Ci (49)
1 1
þ
kr;Cn kd;Cn

Agb
RCn ¼ Ci (50)
1 1
þ
hkr;Cn kd;Cn

B1 B2 bc Mc
fv ¼ (51)
rs
h  i
max 0:0; min Eeq  Eeq;cr ; Eeq;inf  Eeq;cr
B2 ¼   (52)
Eeq;inf  Eeq;cr

Modifying the heat cycle will almost certainly result in better PAHs and toxic metals. A previous study by Valavanidis et al. [1]
processes in many cases. As a direct result, operation energy input illustrated the emissions of common co-mingled PSW in open fire
is reduced per unit output. Also, pollutants generated corre- combustion between 600 and 700  C. PSW batch used contained
spondingly reduce. Heat has a lower exergy, or quality of energy, PS, PVC, LDPE, PP and PET, resulting from a number of sources,
compared with work. Therefore, heat cannot be converted into namely insulating material, bottles, bags and food containers. All
work by 100% efficiency. Consideration of the entire life cycle for plastics demonstrated a difficulty in burning except for PET and
energy resources and technologies suggests that improved effi- PVC, which unlike PS didn’t produce black smoke in burning.
ciency reduces environmental impact during most stages of the life Results focused particulate soot analysis and the residue solid ash,
cycle, namely in combusting processes of PSW. Capture and after combustion. The presence of persistent free radicals which are
removal of flue gases in thermal (in general) and combustion formed have obvious toxicological implications for inhalation of
processes (in particular) is a major issue dealt with by (i) ammonia emissions during open-air burning of plastic PSW. Another
addition to combustion chamber, (ii) flue gas cooling, (iii) acid important toxicological factor in the particulate soot emissions and
neutralization, (iv) activated carbon addition and/or (v) filtration residue ash are the toxic metals, such as Pb, Cd, Cr, Cu, Ni, although
[117]. Yan et al. [153] stated that the removal of acidic pollutants their concentrations were found to be very low. PAHs have been
(e.g. HCl, HF and SO2) can occur by adding a neutralizing sorbent detected in the particulate soot at relatively high concentrations.
(e.g. hydrate lime (Ca(OH)2) or sodium bicarbonate (NaHCO3)). In incineration processes, temperature is an essential parameter
Nevertheless, usage of sorbents increases corrosivity and fly ash that leads to a reduction in CO and N2O accompanied with an
generation. increase in NOx. The addition of waste material is found to reduce
Yet still, pollutants (namely airborne) are also an issue in N2O but enhanced NOx formation and this is believed to be due to
combustion that needs to be dealt with in a firm manner, avoiding the release of fuel-N from waste materials being mostly NH3 groups.
conflict with environmentally concerned parties. The results of The conversion of fuel-N to NOx varied from 4 to 6% and this is below
most studies showed that the controlled combustion of various what is usually observed in fluidized beds. This was demonstrated in
plastic materials, simulating open-air burning, produces a series of a study by Boavida et al. [127], where the conversion of fuel-S to SO2
toxic compounds including volatile, semivolatiles, organics and was almost complete during co-incineration of PSW with coal.
However, the addition of waste was observed to reduce SO2 due to
Table 12 the presence of greater Ca in the waste ash. Emissions of heavy
Chemical reactions used in the design simulation of the blast furnace [145]. metals are in the same order of magnitude in coal or coal/PSW
No. Type Reactions blends, and are lower than the limits imposed by the EU directives
C1 Devolatilization Pulverized particle / V.M.
[127]. Hence, PSW could be considered as a renewable energy
C2 Char reaction Char þ ½O2 / CO source under certain constrains of feed preparations. Desulphuri-
C3 Char þ H2O / CO þ H2 zation techniques (on an industrial scale) could be divided into two
C4 Char þ CO2 / 2CO categories, throwaway and regenerative process, the latter being
C5 Coke reaction Coke þ ½O2 / CO
more preferable [154]. Throwaway processes are described as
C6 Coke þ ½H2O / CO þ H2O
C7 Coke þ CO2 / 2CO a process that results in a by-product that will be dealt with offsite.
C8 Gas phase reaction V.M. þ aO2 / bCO þ gH2 Regenerative processes are ones that result in a closed-loop system
C9 CO þ ½O2 / CO2 of products. Another classification is based on the active removal
C10 H2 þ ½O2 / CO2 agent containment in a liquid solution, described as either dry or
C11 CO þ H2O 4 CO2 þ H2
wet. The two most common desulphurization techniques are the
124 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129

Table 13
Particle control methods resulting from combustion processes [150–152, 169–173].

Technique Principle Application

Gravity settlement Natural deposition by gravity of particles from
a horizontally flowing gas, collection in hoppers
Cyclone separator Tangential entry of a particle-laden gas into
a cylindrical or conical enclosure, movement
of the particles to the enclosure wall and
from there to a receiver
Fabric filters Retention of solids by a filter, filter materials
include woven cloth, felt and porous membranes.
The filtration through a fabric filter mainly relies
on the dust layer which is formed on the
fabric during operation
Electrostatic precipitation Passage of particle-laden gas between electrodes,
application of an electric field to the gas, resulting
in acquisition of charge by the particles and attraction
to an electrode where coalescence occurs, electrical
resistivity of the dust an important factor in performance
Ceramic filters Typically made from aluminium oxide and silicon carbide.
The porous ceramic structure has 40–50% open porosity
with pore sizes ranging from 0.25 to 90 mm
Sintered metal filters (SMFs) Suitable for gases and liquids filtration
Cartridge filters Cylindrical tubes hung in multiple rows, providing
larger surface area
Removal of coarse particles (450 mm) from a gas stream,
smaller particles removable in principle but require
excessive flow distances
Numerous applications, wide range of particles sizes
removable, from 5 to 200 mm, poorer efficiencies of
collection for the smaller particles
Used in dust (>1 mm) removal for over a century
Particles down to 0.01 mm removable, extensive application
to the removal of fly ash from pulverized fuel (PF) combustion
Used for solid particulate removal in gas as the filter
media in chemical processes and petrochemicals industry
Typical filtration degree is from 10 up to 150 mm
99% efficiency with particulates loadings ranging between
0.23 and 23 g m3, with as size range of 0.01–0.5 mm

limestone and lime based wet scrubbing systems [154]. In such
processes, the gas is scrubbed with a 5–15% slurry of calcium
sulphate/sulphate salts, which also contains an added amount of
calcium hydroxide (Ca(OH)2) or limestone (CaCO3). The calcium
hydroxide is generally formed by slaking lime in water according to
the following reaction [153,154]:
Thresholds and limits might have changed with time but the CAA
still addresses the issue of the three classes of emissions: (i)
organics (including dioxins), (ii) combustion particulates (including
lead) and (iii) acid gases. The US and EU regulations do still cover
the main three types of MSWIs which can be classified as follows
(depending on airborne emissions and feed processed):

CaO þ H2 O/CaðOHÞ2 þHeat
Limestone and lime scrubbers are based on the materials used in
the initial alkaline input. The overall reactions of the limestone and
lime based scrubbers can be summarized by the following
reactions:
1 1
SO2 ðgÞ þ CaCO3 ðsÞ þ H O/CaSO3 $ H2 O þ CO2 ðgÞ
2 2 2 the waste to be processed prior to combustion. Processing
1 3
SO2 ðgÞ þ CaðOHÞ2 ðsÞ þ H2 O/CaSO3 $ H2 O þ H2 OðlÞ
2 2
Further oxidation of the calcium sulphate hemihydrate
(CaSO3$(1/2)H2O), either within the reactor or by forced oxidation
in a secondary reactor, results in the formation of calcium sulphate
dihydrate. In both the limestone and lime wet scrubbers, the liquid
containing the sulphate/sulphate salts and the newly added lime-
stone or calcium hydroxide is conveyed to a spray tower absorber
where the slurry is sprayed into the absorber. Since the solubility of
SO2 in water is relatively low, it is essential to have a reactive
species in the slurry like Ca. The subsequent reactions between the
calcium and the absorbed sulphur dioxide create the compounds
calcium sulphate hemihydrates and calcium sulphate dihydrate
(CaSO3$2H2O). Both reaction products have low solubility in water,
thereby enhancing the absorbtion of SO2 and further dissolution of
CaCO3 or Ca(OH)2.
Current regulation in the EU and North America require 25% of
the waste stream to be separated for recovery prior to incineration.
However, this percentage varies from one country to another
depending on the materials and amount of it in the final MSW line
[155]. The USEPA still follows the engineering guidelines (although
minor amendments took place) from the 1989 sections a, b and d of
the Clean Air Act (CAA) to control emissions from MSWIs.
(53) 1. Mass burn combustors (MBCs): these incineration units
process over 55% on average of the MSW in the EU and US.
MBCs accept all MSW except items that won’t go through the
feed line. Unsegregated refuse is placed on the grate that moves
through the combustion chamber. Air is used in excess and is
forced below and above the grate.
2. Refuse-derived fuel combustors (RDFCs): these units require
(54)
typically include shredding and removal of non-combustibles.
RDFCs maybe co-fired with coal.
(55) 3. Modular combustors: these combustors are the smallest in size.
Types of such vary in operation mode and %excess air.
Despite the relatively low contribution of PSW by weight to the
MSW final stream, plastics contribute by 25% to the total calorific
value of the MSW content [156]. Plastics (commercial grades, resin,
masterbatches and pure polymers) all combust in two phases,
a pyrolysis and a combustion phase (Fig. 16). In the first phase, the
plastics decompose chemically by heat into gases. The composition
of which strongly dependant on the polymers types, contents [157],
and on the incineration process condition (temperature, pressure,
etc.). The mixture of the gases then enters the flame, where the
combustion occurs. Regardless of the type of plastic materials
combusting, gases from combustion processes are typically small
and stable (2–3 atoms) [158]. These gases include H2O, CO2, NO, CO
and SO2.
Composition of the majority of combustion gases are deter-
mined by the ratios of elements C, N, O and H when entering the
flame and the temperature and pressure of it. Other elements
present in plastics (e.g. chlorine, lead, cadmium, tin) experience
a variety of fates. Some are released as gaseous emissions, whilst
others are entrained in fly ash or bottom ash. Incomplete
combustion caused either by insufficient amount of oxygen or low
 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
Smoke
Flame direction
Flame direction
Hea
t f lo
w e at
Flame direction
Hea
t f lo
w at
Pyrolysis gases
Combustible material
Fig. 16. Flame dynamics showing separation of pyrolysis and oxidation [154].
flame temperature may lead to the emission to more complex
compounds. Generally, the most concern in MSW incineration
processes is given for compounds resulting from incomplete
combustion, e.g. chlorobenzene, chlorophenols, PCDDs, PCDFs.
Incomplete combustion also lead to the release of certain amounts
of particulates (soot), which also may disrupt the operation of the
particulate collection devices.
Proven collection control technologies are available to effect
greater than 99% capture of MSWIs particulate emissions and 90%
capture of acid gas emissions (HCl, HF and SO2). Most effective
identified particulate/acid gas controller system consists of a dry
alkaline scrubber coupled with a fabric filter or an electrostatic
precipitator.
Many issues exist with PSW (as a part of MSW) incineration
management and operation. In addition to the formation of
incomplete combustion products (CO, soot, undesired pyrolysis
gases, etc.), combustion of some halogen-containing plastics may
reduce the flame temperature of the incinerator. Also, high calorific
value plastics (in large quantities) will overwhelm the local air
supply in the combustion chamber. This will result in formation of
PICs pockets that may emit from the incinerator if insufficient
secondary air is available to complete the combustion process.
Another issue facing incinerators of high PSW content feed is
excessive flame temperature. Normally, excessive flame tempera-
ture damages the construction material of the incinerator and lead
to high concentration of CO emitted. In the past, PSW contribution
to the overall calorific value of the waste stream outweighs
concerns related to possible occurrence of excessive flame
temperature (due to the formation of excess oxygen). However,
since PSW is increasing in percentage this issue may rise in many
parts of the world. The formation of slag is another issue when it
comes to PSW incineration. Slag is formed when substances melt
under elevated temperatures and pressures, and travel as liquid to
relatively cool zones of the incinerator where they resolidify. These
substances become an operational concern when they start to clog
air inlets or interfere with grates or stroking devices operation.
When it comes to slag formation, the concern with PSW incinera-
tion is minimal to the extent of contribution to MSW slag formation
due to the high calorific value and heat released during PSW
combustion.
125
H2O, CO2, etc.
Flame Oxygen
Reactions
w
flo
H
w
flo
He
Pyrolysis zone Char zone
4. Towards a more sustainable practice through recognizing
PSW as a feedstock
4.1. Life cycle assessment (LCA) implementation
Energy from waste (EFW) has been accepted as a sustainable
practice for waste management systems, certainly when compared
with landfilling. With the development of waste management
assessment methods (e.g. life cycle assessment) it is now easier to
compare material recovery (namely recycling) with energy
recovery case-by-case. LCA is best defined as an objective process to
evaluate the environmental burdens associated with a product,
process or activity, by identifying and quantifying energy and
materials used and waste released to the environment. LCA eval-
uates and implements opportunities to allow environmental
improvements [159]. LCA is also a method for assessing environ-
mental burdens associated with processes or products in a ‘cradle to
grave’ fashion, i.e. from production of the raw materials to ultimate
disposal of waste. The reason behind the development of LCA was
taking into account issues not addressed by other environmental
management tools such as statutory impact assessment, in terms of
assessing environmental burdens associated with products or
processes and choosing the least burdensome option [160]. LCA has
been used in many studies as an environmental tool for compara-
tive assessments of waste disposal options or management
scenarios. Mechanical recycling was compared with incineration in
the context of LCA by Dodbiba et al. [161]. It was concluded that
mechanical recycling of plastics resulting from discarded TV sets in
Japan is a more attractive option than incineration, which has
a larger environmental burden. LCA validated the waste hierarchy
for solid waste management systems in Sweden [162,163], deter-
mined the environmental load of food product consumption and
processing [164,165], and assured the feasibility of recycling rather
than landfilling wasted materials in small urban communities
[166]. Energy resources and their sustainable development require
a supply of energy resources that are available at a reasonable cost
and can cause no negative societal impacts. Thus, it is elementary to
recognize high calorific value waste, namely PSW, as a valuable
feedstock and an energy resource. Various parameters are essential
to achieving sustainable development in a society, i.e. awareness,
126 S.M. Al-Salem et al. / Progress in Energy and Combustion Science 36 (2010) 103–129
environmental education and innovative energy strategies. A field
demonstration of LCA as an impact assessment tool was demon-
strated by Edelmann et al. [128], when LCA was used on the kiln
combustion process in the canton of Zug (Switzerland) in order to
ass environmental burdens. It has provided the solution of the toxic
organic substances and inorganic toxic compounds (e.g. heavy
metals), which are now fixed in the non critical concentration range
in the kiln and retained by the exhaust gas scrubbing devices.
Implementing LCA in PSW assessment could not only increase
the awareness of the concerned parties and public, but it can also
ease the assessment of environmental burdens associated with
certain activities in the polymer life cycle. Using a number of
developed weighing techniques and assessment methodologies,
one can estimate a number of environmental burdens based on
case analysis and scenario development. These methods include
the Ecotax 98 (based on environmental taxes and fees) and Eco-
Indicator 99 (based on the endpoint modelling of burdens) meth-
odologies of weighing [160].
4.2. Integrated solid waste management (ISWM) in PSW
management systems
The main objective of an Integrated Solid Waste Management
(ISWM) system is to combine waste streams, waste collection,
treatment and disposal methods, with the objective of achieving
environmental benefits, economic optimization and social accept-
ability [168]. In the case of PSW, the integration requirements are
very similar (in terms of management systems integration) with
MSW. These requirements could be summarized as optimizing an
effective system of waste still being produced and reducing in the
process the waste generated. To affectively achieve a MSW inte-
grated system, all types and sources of solid waste materials should
be controlled. Managing all types of solid waste is a very hard
concept. In theory, a landfill is the only option that can manage all
types of waste. That is due to the fact that all recycling, composting
and thermal treatments leave a residual behind that needs to be
dealt with, and in many cases landfilled [168]. Nevertheless,
utilizing the proper treatment option will reduce the volume of the
landfilled waste and divert a significant part of the waste stream
from landfills.
Implementing ISWM systems has been proven to be very
successful in many societies. The management scenario that is
being currently undertaken by the municipality of Prato (Italy) is
one of many examples [167,168]. After introducing a collection
scheme for plastic containers (in 1992) and separating the waste at
source (kerbside), the municipality diverted 8% of its MSW from
landfills (closest is 85 km away) by being able to contribute to
composting and recycling schemes around the country. It also
receives 20% revenue from regional taxes of the Italian government.
Therefore, decision making based on organizational positions and
regulatory compliance is essential in an integrated system. The use
of national resources and proper eco-design are also very important
to the success of an integrated system.
5. Conclusions and recommendations
Plastics are derived from crude oil, therefore can be very
advantageous for energy recovery and in many cases can be
compared to coal or other fuels. The various recovery options for
Plastic Solid Waste (PSW) have been presented as part of this
review, which could be categorized into: (i) re-extrusion, (ii)
mechanical, (iii) chemical, and (iv) energy recovery. Re-extrusion
(primary recycling) is considered a very efficient solution to onsite
process scrap, re-introduced into the production loop by various
heat cycles to produce a number of plastic products. Mechanical
recycling also represents itself as a candidate for PSW utilization
when primary treatment fail, due to high contamination and
heterogeneity issue with the plastics. One of the main concerns in
mechanical recycling of plastics is the quality of the resulting
product. Since it is being performed on a single-polymer plastic, the
grade (type of resin or masterbatch) and degree of degradation are
major concepts. Energy recovery (through incineration) and
thermo-chemical methods can reduce the volume of the waste, as
well as the dependency on fossil fuels. This will lead to conserva-
tion of natural resources and establishment of better waste
management systems. Applications of such are vast, in cement and
lime kilns and circulating and bubbling beds. In terms of improving
the image of plastics, chemical recycling methods have contributed
to that and proven very successful in recent years. Advanced
thermo-chemical treatment (pyrolysis, gasification and hydroge-
nation) methods have also proven very successful, especially when
considering the range of valuable petrochemicals they produce.
Advanced thermo-chemical treatments of PSW in the presence of
heat under controlled temperatures (thermolysis) provide a viable
and an optimum engineering solution. Not only have they recov-
ered healthy monomer fractions up to 60% in past reports, but they
produce valuable petrochemicals that could be summarized as
gases (rich with low cut refinery products and hydrocarbons), tars
(waxes and liquids very high in aromatic content) and char (carbon
black and/or activated carbon). Thermolysis and catalytic degra-
dation, have been receiving much attention lately as a route of
producing various fuel and petrochemical fractions. Thermal
decomposition schemes on the end-product (employing lumped
product analysis) are an essential step to be developed and vali-
dated. Advances in that area will aid in the improvement of
pyrolysis and gasification reactors. Designing such units still lack
appropriate scales and end-product achievement with a flexibility
of covering the demands of the fluctuating market. It is critical that
in the future, recycling of PSW is taken into consideration during
the product design phase. This will make it more probable for the
PSW to be recycled at the end of its product life cycle.
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