Chen Et Al (2014)

Waste Management xxx (2014) xxxxxx
Contents lists available at ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
Review
Pyrolysis technologies for municipal solid waste: A review

Dezhen Chen a,, Lijie Yin a, Huan Wang a, Pinjing He b
a
b
Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092, China
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
a r t i c l e
i n f o
Article history:
Received 23 February 2014
Accepted 1 August 2014
Available online xxxx
Keywords:
Municipal solid waste (MSW)
Pyrolysis
Reactor
Product
Environmental impact
a b s t r a c t
Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW)
disposal that allows energy and resource recovery; however, it has seldom been applied independently
with the output of pyrolysis products as end products. This review addresses the state-of-the-art of
MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this
review, rst, the inuence of important operating parameters such as nal temperature, heating rate
(HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then
the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third,
the yields and main properties of the pyrolytic products from individual MSW components, refusederived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO2 and NH3, contaminants in the products, including PCDD/F
and heavy metals, are also reviewed, and available measures for improving the environmental impacts of
pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-toenergy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information,
the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested.
2014 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pyrolysis behaviours of MSW with respect to products and the influential factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Terminology and scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Factors influencing MSW pyrolysis behaviours and products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pyrolysis technologies and the reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Pyrolysis technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Pyrolysis reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1.
Fixed-bed reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2.
Rotary kiln reactors and their systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3.
Fluidised-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.4.
Tubular reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.5.
Other pyrolysis reactors and technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Products from pyrolysis of typical MSW components and MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Pyrolysis products from waste paper. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Pyrolysis products from MPW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Pyrolysis products from wood and woody mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Pyrolysis products from fallen leaves and vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abbreviations: HCs, hydrocarbons; HDPE, high-density polyethylene; HHV, higher heat value, the same meaning as gross caloric value; LDPE, low-density polyethylene;
LHV, lower heat value; MSW, municipal solid wastes; MPW, mixed plastic waste; PCDD/F, polychlorinated dibenzodioxins/furans; PET, polyethylene terephthalate; PP,
polypropylene; PS, polystyrene; MPW, mixed plastics waste; PVC, polyvinyl chloride; RDF, refused-drive fuel; rpm, revolution per minute; TG-FTIR, thermogravimetric
analysis-Fourier transform infrared spectrometer.
Corresponding author. Tel.: +86 21 6598 5009.
E-mail address: chendezhen@tongji.edu.cn (D. Chen).
http://dx.doi.org/10.1016/j.wasman.2014.08.004
0956-053X/ 2014 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Chen, D., et al. Pyrolysis technologies for municipal solid waste: A review. Waste Management (2014), http://dx.doi.org/
10.1016/j.wasman.2014.08.004
D. Chen et al. / Waste Management xxx (2014) xxxxxx
4.5.
4.6.
5.
6.
Pyrolysis products from RDF from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Pyrolysis products from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.1.
Properties of gas products from MSW. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.2.
Liquid products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.3.
Solid products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.4.
Standardized product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.7.
Considerations for pyrolysis technology and product choice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Environmental effects of MSW pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Emissions and contaminants associated with the MSW pyrolysis process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Pyrolysis-associated emission control technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
The treatment, management and disposal of municipal solid
waste (MSW) are common concerns in every country. MSW pyrolysis is considered as an innovative alternative for treating MSW
that obtains different chemicals and fuels (Schaefer, 1975;
Malkow, 2004). In a pyrolysis-involved process, energy can be
obtained in a cleaner way than from conventional MSW incineration plants as lower amounts of nitrogen oxides (NOx) and sulphur
oxides (SO2) are produced as a consequence of the inert atmosphere in the pyrolysis processes and the opportunity to wash
syngas before its combustion. In addition to reduced gas emissions,
better quality of solid residues can be also expected from pyrolysis-involved treatment technique for MSW (Saffarzadeh et al.,
2006).
In general, pyrolysis represents a process of thermal degradation of the waste in the total absence of air that produces recyclable products, including char, oil/wax and combustible gases.
Pyrolysis has been used to produce charcoal from biomass for
thousands of years. When applied to waste management, MSW
can be turned into fuel and safely disposable substances (char,
metals, etc.), and the pyrolysis process conditions can be optimised
to produce either a solid char, gas or liquid/oil product, namely, a
pyrolysis reactor acts as an effective waste-to-energy convertor.
Compared to the conventional incineration plant which runs in
capacity of kiloton per day; the scale of pyrolysis plant is more
exible. Recently, MSW pyrolysis is receiving increasing attention
in small cities and towns due to the desire to prevent long-distance
transportation; and it is also demanded in big cities as a distributed
MSW treatment method due to the increased difculty in nding
new sites for incinerators and landlls. Generally distributed
MSW treatment facilities are difcult to ensure environmental
safety due to capital cost limitations; while pyrolysis plants of
proper capacity with energy products output are suitable alternative when the quality of char, oil/wax and combustible gases is
under ne control.
A variety of pyrolysis studies have been conducted on industrial
wastes such as tyres and plastics, and several reviews have
reported on the characterization of the development of pyrolysis
technologies in terms of different aspects, for example, reactor
development and product characterization (Sannita et al., 2012;
Williams, 2013; Yang et al., 2013); conditions for oil production,
oil characteristics and upgrading (Quek and Balasubramanian,
2013); the heating rate and other governing variables affecting
pyrolysis process and pyrolysis products of tyres (Martnez et al.,
2013); and the mechanism investigation or kinetics modelling of
the pyrolysis process (Al-Salem et al., 2010; Quek and
Balasubramanian, 2012). These reviews facilitate making the
state-of-the-art of the development of pyrolysis of waste tyres
and industrial plastics well known. As for municipal wastes, the
pyrolysis of sewage sludge has been investigated for decades for
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liquid production, and the state-of-the-art of this technology has

also been addressed in a recent review (Fonts et al., 2012). However, compared to waste types such as tyres, plastics and sewage
sludge, MSW is more heterogeneous in composition and size.
Currently, for MSW pyrolysis, information on technology development, characterization of products and correlated pollution is not
sufcient to support technology application and system design,
especially in regards to environmental impacts, which is fundamental for a single step MSW pyrolysis application.
Therefore, this work reviews pyrolysis technologies for MSW,
with focus on reactors, the products from MSW pyrolysis, the
pollutants involved with the MSW pyrolysis process and product
applications, and the reported measures to alleviate the
associated environmental impacts. The nal aim is to provide
essential information for understanding the pyrolysis process
applied to MSW and to standardize its application as an energy
converter.
2. Pyrolysis behaviours of MSW with respect to products and
the inuential factors
2.1. Terminology and scope
Reactions take place in a recognized pyrolysis process can be
expressed as:
CxHyOz Q ! Char Liquid Gas H2 O
where Q is the heat that needs to be input to the reactor for the
reactions to take place, it includes three portions:
Moisture vaporization Q1
During pyrolysis the feedstock will not undergo thermal
decomposition before its moisture is vaporized, and Q1 can be calculated as:
Q 1 W 2260; kJ kg
1
where W is the water content of the feedstock to the reactor, %;

therefore to reduce this part of energy, MSW components with
high moisture content such as food wastes, biomass are suggested
to be separate before pyrolysis. In addition, in order to reduce this
portion of energy a drying step is usually adopted in front of pyrolysis reactor.
Caloric requirement of pyrolysis Q2
The caloric requirement of the pyrolysis is calculated using the
following equation (Raveendran et al., 1996):
Q 2 C p;M
mM dT C p;ch
mch dT C p;v
mv dT Q p ; kJ kg
1
10.1016/j.wasman.2014.08.004
where Cp,M, Cp,ch, Cp,v are the specic heat capacities of the dry
materials, char and volatile generated, J kg1 C1; mM, mch and
mp,v are the mass ratio of the dry materials, char and volatile to
the feedstock, %; the former three items at the right side of Eq. (3)
are the energy required for heating feedstock and the products to
the pyrolysis temperature; and Qp is the reaction heat of the pyrolysis, J kg1. Q2 can be obtained through differential scanning calorimetry (DSC) or differential thermal analysis (DTA) techniques for
different MSW components (He et al., 2006), and it has been found
that for reactor design purpose Qp can be neglected and the Q2 is
mainly decided by pyrolysis temperature (Boukis et al., 2007;
Wang et al., 2012). The higher pyrolysis temperature does not only
result in a higher energy requirement, but also cause challenge to
the safety of reactors.
The radiation loss from the reactor to the surrounding Q3
As heat is transferred from outside to the inner side of the reactor, Q3 can be ignored for heat transfer surface design; but on the
contrary, when the reactor is heated opposite, the heat transfer
surface should bear this portion of energy to maintain the desired
temperature of the reactor. Better insulation will reduce this radiation loss Q3.
A pyrolysis system consisting of the pyrolysis reactor and other
appurtenances serves the purposes of supplying the heat Q to the
reactor, controlling the proper conditions for the desired products,
namely liquid, gas and char shown in Eq. (1) and preventing side
effects such as pollution. Numerous studies have been performed
based on Eq. (1) to investigate the pyrolysis kinetics, pyrolysis
behaviours vs. the reaction conditions and to characterize the
products. But with the focus on giving instruction in setting up a
proper pyrolysis technology for MSW, only those literatures most
relevant to MSW pyrolysis technologies and products are reviewed
here.
2.2. Factors inuencing MSW pyrolysis behaviours and products
MSW consists mainly of paper, cloth material, yard waste
(including fallen leaves and branches, etc.), food wastes, plastics
and a small amount of leather and rubber, metals, glass, ceramic,
earthen materials and miscellaneous other materials. The fractions
subjected to pyrolysis mainly include paper, cloth, plastics and
yard wastes. Highly wet food wastes should be separated to reduce
Q1. Numerous studies have been performed in laboratories to
determine pyrolysis behaviours and product properties of individual MSW fractions such as paper, plastics, fabric, lignocellulosic
materials and putrescibles (Di Blasi, 1996; Wu et al., 2002, 2003;
Wu et al., 2005; Zhang et al., 2008; Zheng et al., 2009; Luo et al.,
2010a; Ates et al., 2013; Miskolczi et al., 2013), refuse-derived fuel
(RDF) pellets (Cozzani et al., 1995; Garcia et al., 1995a,b; Lin et al.,
1999; Buah et al., 2007; Dou et al., 2007; Grammelis et al., 2009;
Bosmans et al., 2013) and real MSW ( Islam and Beg, 2004; Islam
et al., 2005; He et al., 2010; Luo et al., 2010b; Zhao et al., 2011;
Ates et al., 2013; Miskolczi et al., 2013). The interactions between
the different individual fractions and the pyrolysis products have
also been explored (Williams and Williams, 1997; Williams and
Williams, 1999b; Srum et al., 2001; Grieco and Baldi, 2012;
Ding et al., 2013), but not as extensively. The previous researches
indicated that the important parameters affecting MSW pyrolysis
included temperature, heating rate (HR), residence time in the
reaction zone and materials size, etc.; and their effects on pyrolysis behaviours and the products can be deduced from the summary
in Table 1.
From Table 1 it can be seen that the reported pyrolysis temperature varied from 300 to 900 C, but the typical running temperature is around 500550 C with liquid products as major portion of
products. At temperatures higher than 700 C, syngas is the vital
product. Most of the researches paid more attention to the liquid
and syngas products than the char due to the fact that the oil
and syngas are more valuable; and the yields and composition of
pyrolysis oil and syngas are mainly changing with temperature.
The residence time of the materials in the reaction zone is another
important parameter; which was reported to be in the range of a
few seconds to 2 h as shown in Table 1. It was well recognized that
longer residence time would enhance the tar cracking and result in
higher gas yields; but at the same time longer residence time
reduced water content and waxy material in the liquid products
(Velghe et al., 2011), conduced to the improved quality. The complex impact of residence time on products can be deduced from Eq.
(1): in a longer residence time, more heat is input to the reactor,
the extra heat will evaporate the water produced, crack the tar into
small molecules, and vaporise more organics from the char, all of
this would result in higher gas yield. But longer residence time will
lead to lower treatment capacity of the reactor. The third important factor affecting MSW pyrolysis is heating rate (HR) and it
was reported to vary from about 4 C min1 to 670 C S1 as shown
in Table 1. Higher HR is corresponded to a higher volatile matter
(tar and gas) yield, accordingly less char will be left (Li et al.,
1999a,b; Yi, 2007; Velghe et al., 2011); together with a longer residence time, higher yield of syngas will be obtained due to tar
cracking; while as the volatile matter is extracted immediately
and cooled down, higher yield of liquid products can be obtained
(Font et al., 1995a,b). Theoretically the HR can be calculated as:
HR
DT a
; C S1
m Cp
where DT is the temperature difference between the reactor

wall and the feedstock, C; a is heat transfer coefcient inside
the reactor, W m2 C1; m is the mass of feedstock heated by
per m2 of heat transfer surface (reactor wall), kg m2; Cp is the is
the specic heat of the feedstock, J kg1 C1.
According to Eq. (4), HR is decided by DT, a and the mass load of
the reactor. In the laboratory researches, the HR was setting by
adjusting DT or mass fed to the reactor to realize slow or ash
pyrolysis, as shown in Table 1. While in a practical and continuously running reactor HR is decided by the reactor type which is
characterized with its special temperature difference (DT) and heat
transfer coefcient (a) features. The pyrolysis reactors reported in
the literatures are mainly xed-bed reactors, rotary kilns and uidised bed reactors, as shown in Table 2; they are of a sequence in
ascending order according to HR. The uidised bed reactors are
characterized with very high heat transfer coefcient of 112559
(J/s m2 K) (Garcia et al., 1995a). But very few reports are available
on heat transfer coefcients for MSW pyrolysis in rotary kilns and
xed-bed reactors, as they are affected by many factors; and they
are also the companys private know-how for designing and running pyrolysis reactors. The transport tube thermo-chemical convertor in Table 2 shows a new reactor type, it belongs to a family
of tubular reactor, which will be discussed later.
As for the inuence of particle size on the MSW pyrolysis, it was
not extensively investigated; but in general smaller particles contributed to a larger surface area and faster HRs (Di Blasi, 1996),
therefore smaller particle size caused higher yields of liquid or
gas products. Coarser particles correspond to the lower HR therefore longer residence time is required. However, once the temperature is high enough, the difference in yields of products was
minimal (Luo et al., 2010b) due to the lower HR effect correlated
to coarser particle size was compensated by the increase of the
radiation contribution to heat transfer. Basically the inuence of
particle size is a combination of HR and the interaction between
the volatile matter and the char, the latter takes place when the
volatile matter diffuses from inner particle to the outside.
Finally, as shown in Table 2, all of the experimental pyrolysis
systems are equipped with products cooling and collection devices,
10.1016/j.wasman.2014.08.004
Reaction conditions
Feedstock
Reactor type
Main results respect to pyrolysis behaviours and the products
Reference
MSW was decomposed in the 500900 C temperature

range, and the lignin was decomposed in the range of
600900 C
Sample mass for the uidised-bed reactor was 13 g (at
temperatures greater than 700 C) or 030 g in the
remaining cases. Particle size of PE was 0.5 cm. Almond
shells was 0.2970.500 mm in particle size. MSW sample
was 0.85 g and ground
No information on residence time and heating rate (HR)
MSW, almond shells,

lignin and
polyethylene
An analytical Pyroprobe
apparatus, and a uidised
sand bed reactor
When to investigate kinetics of the primary decomposition and the tar

cracking, it was found that when there was no tar cracking, the increase in
yields are linear with time; and that tar cracking took place from the top of the
sand bed to the reactor head. In addition, the sample could continue
decomposing during the cooling period if the temperature is not too low, and
this explains why ash pyrolysis in uidised-bed reactor results in a high gas
yield
For pyrolysis products in the uidised bed at 850 C, almond shells
corresponded to 89% of total gas with 8.6% of methane and 4.2% of ethylene;
MSW had 47% of total gas with 4.2% methane and 3.4% of ethylene. At 800 C,
polyethylene had 95% of total conversion with 19% of methane, 4% of ethane,
37% of ethylene, 5% of propylene, 5.5% of butylenes, 5.0% of pentane, 25% of
benzene and 2.1% of toluene. By using the Pyroprobe and a secondary reactor,
the yields for Kraft lignin were 9% of methane, 12% of aromatics and 1.5% of
ethylene
The heat transfer coefcients in the sand uidised-bed reactor for MSW
pyrolysis was reported to be 112559 (J/s m2 K)
Around 7080% of the primary tars can be cracked to low molecular weight gases
When to study the production of gases from MSW pyrolysis at high nominal
temperatures (700850 C) and to explore the inuence of pyrolysis
temperature and residence time of volatiles in the hot zone of reactor on the
yields of pyrolysis compounds, it was found that biomass decomposition
followed by tar cracking reactions took place inside the reactor. The primary
tars evolved cracked at approximately 70% at 800 C, increasing the gas yield
(from 23.8% (primary yields) to 48.0% (secondary yields))
At the highest operating temperature (850 C) and high residence times, when
the cracking of tar was complete, the gas components were CH4 6.1%, C2H6
0.32%, C2H4 4.5%, C3H8 0.001%, C3H6 0.079%, C2H20.19%, C4H80.002%, CO 26.1%,
CO215.7% and H2 2.4%
When investigate the yield and the caloric value of the syngas changing with
individual MSW components, the size of raw materials and the heating modes,
the authors found that the conversion of energy contained in MSW
components into syngas was much higher under the fast heating mode; PE
was corresponded to the highest syngas yield of 720 L kg1 and vegetables had
the lowest syngas yield of 51 L kg1, but the latter corresponded to the highest
tar and water yield of 0.888 kg kg1. The caloric value of the syngas was in
the range of 1300023000 kJ kg1.
Smaller size did not match the higher syngas yield.
When investigate the yields of pyrolysis products varying with nal
temperature, the researchers found that the char yield decreased with the
increase of temperature, especially within the temperature range 300550 C,
and that the pyrolysis liquid yield increased with the increase of temperature
till 550 C, whereas, afterward, it began to decline. The gas yield steadily
increased with the increase of temperature in the whole test temperature
range
When investigate the production distribution, the gas characteristics, the
pyrolysis gas quality, the characteristics of the pyrolysis liquids and char, the
researchers found that the pyrolysis temperature is the top-drawer parameter
affecting the pyrolysis of the MSW. With temperature increases, the gaseous
yield increased, and the yield of pyrolysis liquids and char yield decreased
accordingly. The main components of pyrolysis gas were CO, H2, CH4 and CO2.
The CO and H2content increased in the gaseous component with the increase
in temperature; the caloric value of pyrolysis gas has a maximum within the
testing range, whereas the caloric value of char displays an increasing trend.
The liquid products are rich in moisture and volatiles, and the gross content of
the xed carbon and ash in liquid is less than 3%
Font et al. (1995a,b)
Dry pellets of MSW

The reactor was running at high nominal temperatures
(700850 C) batch by batch
The HR of the sample was evaluated to be approximately
670 C/s when the nominal temperature was 850 C and
approximately 425 C/s if the nominal temperature is 700 C
Sample mass: 0.85 g
Residence time: approximately 20 min
The nal temperature in the reactor was 850 C. For fast

pyrolysis, the reactor was heated to 850 C rst, and then,
the sample was fed. For slow pyrolysis the MSW
components was heated together with the reactor wall
HR: 560 C min1*
Sample mass: 1000 g per batch
Residence time: 715 min
A helium uidised sand-bed

reactor
9 components in MSW, An externally heated rotary

pre-treated
kiln running at 3r min1
The reactor was heated up after materials were fed. The nal 9 components in MSW, An electrically heated xedbed reactor with N2 ush in
crushed to less than
temperature was changed from 300 to 700 C
10 mm and then mixed the beginning
HR: not mentioned
Residence time: 55180 min depending on the temperature
The bed temperature was varied from 500 to 900 C

Sample size: less than 5 cm
HR: not mentioned
Residence time: up to 50 min
Wood, paper,
municipal plastic
waste and crushed
MSW
An electrically heated xedbed reactor
Garcia et al. (1995a,b)
Li et al. (1999a)
Wang et al. (2005a,b)
Jiang, 2006
10.1016/j.wasman.2014.08.004
Table 1
Pyrolysis behaviours and products under different reaction conditions.
Reaction conditions
Feedstock
Reactor type
Reference
The pyrolysis temperature was increased from 400 to 700 C

HR: 10 K min1
Residence time: estimated to be 4070 min*
MSW in the form of

refuse-derived fuel
(RDF) pellets with a
particle size of
approximately 8 mm
A xed-bed reactor
constructed of stainless
steel and it was externally
heated by an electrical ring
furnace
Buah et al., 2007
The reactor bed temperature was varied from 600 to 900 C.

When the desired temperatures were achieved in the
reactor, the screw feeder was turned on to feed material
into the reactor with a ow rate of 5 g min1
No information was available for the residence time and HR
Prepared MSW of
uniform size in three
groups: smaller than
5 mm, between 5 and
10 mm and between 10
and 20 mm
A xed-bed reactor heated

by an electrical ring furnace
with a screw feeder at top of
the reactor
Slow pyrolysis was performed up to 550 C (with HR of 4 C/

min) in a 2 h process
Fast pyrolysis was performed at 450, 480, 510 and 550 C with
few seconds of residence.
Sample mass: 70 g MSW in a ow rate of 24 g/min or 12 g/min
MSW cut in 2 mm
pieces and oven dried
at 110 C before
pyrolysis
A semi-batch reactor lled

with hot sand as a heat
transfer medium under N2
atmosphere; A Archimedes
screw ensures good mixing
of the samples and the sand
and creates a uidized bed
effect
Pyrolysis was performed up to 550 C (with HR of 2025 C/

min) in a 30 min process
MSW fractions and

mixed waste plastics
Three-section reactor, with

individual temperature
controls at different
sections, batch run or
continuous operation
The temperature inside the reactor was electrically heated up

to 700, 800 and 900 C respectively before feeding samples
HR: assumed to be up to 1000 K min1 at 900 C
Sample mass: 4 g
Residence time: 10 min
PE (representative for
plastic materials in
MSW), paper and
bamboo
(representative for
wood & biomass in
MSW)
A static batch reactor under

a N2 atmosphere
It has been found that the yield and composition of the pyrolysis products
depended on temperature. The char yield fell as the pyrolysis temperature was
increased from 400 C to 700 C, whereas that of oil/wax and gaseous products
rose. The chars recovered were also found to have properties that depended on
the size fraction analysed. The gaseous products obtained from the pyrolysis
consisted mainly of CO2, CO, H2, CH4, C2H6 and C3H8 with lower concentrations
of other hydrocarbon gases. Both the caloric value of the gases and the
surface areas of the chars increased with pyrolysis temperature. Carboxylic
acids and their derivatives, alkanes, alkenes, mono- and polycyclic and
substituted aromatic groups were present in the oils, and the oils displayed an
increase in aromatic groups and a decrease in aliphatic groups as the
temperature rose. The surface area, moisture, ash and volatile content of the
chars were dependent on the size range used for analysis
When to evaluate the effects of particle size at different bed temperatures on
product yield and composition during MSW pyrolysis, it was found that higher
temperature resulted in higher gas yields with less tar and char, and dry gas
yield increased with a decrease in particle size, and the char and tar yield
decreased. The differences due to particle sizes in pyrolysis and gasication
performance practically disappeared at the highest temperatures tested.
Smaller particle sizes resulted in higher H2 and CO contents for both pyrolysis
and gasication of MSW. Minimising the size of raw materials is an alternative
method to improve the gas quality of MSW pyrolysis and gasication
This research was to investigate the effect of reactor temperature and HR on
composition and yield/distribution of pyrolysis products; to investigate the
distribution of metals present in MSW towards the pyrolysis products and to
investigate the obtained products for their use as fuel for energy production or
as raw chemical feedstock.
The important ndings included: (1) The volatile matter was degraded
between 200 C and 560 C at a HR of 20 C min1, as revealed by
thermogravimetric analyses. (2) The highest yield of solid products was
obtained by slow pyrolysis up to 550 C, but under this condition the liquid
fractions were low with very low water content, free of waxy material and a
good candidate as chemical feedstock and fuel. (3) The fast pyrolysis process
induces the presence of waxy material in the liquid products; and incomplete
breakdown may happen within very limited residence time. (4) The syngas
gases contain mainly hydrocarbons and have an averaged LHV of around 13
20 MJ N m3 and ever higher at higher feeding rate. (5) The distribution of
metal ions towards oils is negligible
This research was to investigate the impact of impurities such as food wastes,
paper, textile and especially soil on the pyrolysis of waste plastics. Emissions,
gas and liquid products from pyrolysis of waste plastics and impurities were
studied. In addition, the transfer of elemental N, Cl, and S from the substrates
to the pyrolysis products was investigated. It was found that the presence of
food waste reduced the heat value of the pyrolysis oil and increased the
moisture in the liquid products. Therefore, the food residue should be
removed, but the soil enhanced the waste plastic pyrolysis by improving the
quality of gas and oil products. The presence of food residue, textile and paper
led to higher gas emissions
This research was to investigate the effects of CaO additives and heating rates
on tar generation during MSW pyrolysis. It was found that CaO additives can
reduce the content of acids, phenols and hydrocarbons in tar from bamboo and
paper pulp pyrolysis, but there was no obvious effect on PE. A higher heating
rate resulted in more tar formation, consisting of acids, phenols and
hydrocarbons within a wider temperature range
The LHV of syngas from PE pyrolysis varies between 37 and 51 MJ Nm3, more
than twice of that of bamboo or paper
Luo et al., 2010b
Velghe et al., 2011
Zhao et al. (2011)
Pan, 2012
(continued on next page)
10.1016/j.wasman.2014.08.004
Table 1 (continued)
Miskolczi et al., 2013

It has been found that viscosity, average molecular length and contaminant
amounts of pyrolysis oils were decreased when using catalysts. Comparing the
two raw materials, the catalysts displayed higher activity using MPW than
MSW. Both the carbon frame and double bond isomerisation occurred during
thermo-catalytic pyrolysis. The morphology and texture of the chars were
modied by catalysts, especially by NiMo catalysts
The same as above
and most of them have N2 ush to keep inert atmosphere, both of

them affect the nal product yields. Tar would continue cracking
during the cooling period if the temperature is not too low (Font
et al., 1995a), therefore a slow cooling of volatile from a high temperature reactor would result in higher gas yield; fast and deep
cooling of the volatile would gain higher liquid yield and it is also
preferable to obtain cleaner gas. As for N2 ush, it changed the ow
rate and residence time of the volatile in the reactor, and the cooling of the volatile was interfered too, so data obtained from those
systems with N2 ush may deviate from practice.
3. Pyrolysis technologies and the reactors
3.1. Pyrolysis technologies
The concept of pyrolysis technology can be represented by
RWE-ConTherm process (Hauk et al., 2004), as shown in Fig. 1,
which involves a rotary kiln as pyrolysis reactor with a shredder
in front, exports pyrolysis gas and char to a conventional boiler.
Malkow (2004) summarised the typical pyrolysis-involved processes and technologies available in European market from the
point view of energy efciency, some of these processes with their
updated information and the presently available commercial, demonstration or pilot technologies are summarized in Table 3 from
the point view of technologies details and emissions abatement.
It can be seen that the existing commercial pyrolysis technologies
are characterized with the following congurations:
Combined technologies
The existing commercial pyrolysis technologies seldom run
alone with gas, tar and char output as end products, most of them
are combined with gasication, combustion and smelting; and the
combination with gasication produces moderate-caloric-valued
fuel gas, it still receives extensive attention in waste-to-energy
processes in recent studies (Smith et al., 2001; Li et al., 2007; Yi,
2007; Ohmukai et al., 2008) and will be a competitive choice in
the future. But at the same time, all the combined technologies
in Table 3 are expensive and may not be affordable in places where
the pyrolysis technology is needed.
The same as above
Reference
Ates et al. (2013)
This research was to characterize product yields, gas and pyrolysis oil
properties for both thermal pyrolysis and thermo-catalytic pyrolysis. It was
found that gases contained hydrogen and hydrocarbons; CO and CO2 were
obtained only from MSW; aromatic and cyclic compounds predominantly
formed in the presence of catalysts, and the catalytic effect was more
signicant using MPW
A batch xed reactor, N2
Crushed MSW and
mixed plastic waste
ushed
(MPW) in particles less
than 10 mm in main
dimension with &
without catalysts
Estimated by this article author according to the substance in reference text.
Fed with pre-treated materials
Table 1 (continued)
Reactor type
Feedstock
The reactor was heated to 500, 550 and 600 C for thermal
pyrolysis and 500 C for thermo-catalytic pyrolysis
No information on HR
Residence time: 5239 s for MSW at 500 C in absence of
catalyst; in the range of 43315110 s using catalysts.
Fully decomposition of MPW pyrolysis have higher time
necessity than MSW in absence of catalyst; 6652 s at
500 C, 5299 s at 550 C and 4187 s at 600 C
The same as above
Reaction conditions
All of those MSW pyrolysis technologies accept pre-treated

MSW instead of raw MSW in its original state, suggesting pretreatment is a necessary step for pyrolysis technology. The pretreatment generally includes separation of undesirable materials
and size reduction; sometime a drying step in front of pyrolysis
reactor is needed to reduce moisture content of materials feeding
to the reactor.
The above RWE-ConTherm plant (Hamm) is no longer in operation after the chimney collapse in December 2009. The accident
was analysed to be caused by the feeding waste material, for the
feed composition did not match the process as designed, resulting
in process temperatures beyond tolerable limits. However preparation of input waste stream to match the process could be too
expensive to be beyond protability. A process exible to the
waste input is more practical, and combination of pyrolysis and
gasication stage and independent utilization of the pyrolysis
products serve the necessity of process exibility.
Installed with secondary treatment of products
The commercial technologies listed in Table 3 are characterized
with the immediate utilization of their products in a combustion
chamber or a gas engine, suggesting that those products are not
10.1016/j.wasman.2014.08.004
standardized and not ready for the market. In those technologies

with pyrolysis gases exported to gas engine, gasication acts as primary processing, and gas scrubbing is followed to ensure the quality of the syngas. The char should have secondary treatment
measures such as quenching, screening and separation of metals
when sold as carbon-rich material for industrial purposes. Sometime secondary treatment of pyrolysis products could be very rigid
depending on the feeding materials and the way to use products.
To avoid extensive secondary treatment of products, high temperature combustion inside the system is a suitable choice.
Table 2
Typical MSW pyrolysis reactors and system in literatures.
Pyrolysis reactor and system in researches
Reference
waste collection
Ates et al. (2013), Miskolczi et al. (2013)
waste separation
Metals, paper, organic

waste, etc
Shredding
Crushing
Gases
3
6
4
Pyrolysis oil
4
1
Char
Water
Fixed-bed reactor and pyrolysis system (1-N2 bottle; 2-reactor; 3-heat exchanger; 4-separation unit,
5-water trap; 6-gas ow meter; 7-rotameter)
Wang et al. (2005b)
10
8
8
8
4
11
1
6
Fixed bed pyrolysis system (1-furnace; 2-pyrolysis reactor; 3-thermocouple; 4-temperature controller;
5-N2 pipe; 6-liquid gathering tank; 7-thermometer; 8-condenser; 9-pressure gauge; 10-sampling vent)
Li et al. (1999a,b), Li et al. (2000a,b)
Rotary kiln pyrolysis system (1-thermometer; 2-bearing; 3-gear transmission; 4-electrical furnace;
5-rotary kiln; 6-temperature controller; 7-seal; 8-two-steps condenser; 9-lter; 10-accumulative
owmeter; 11-computer; 12-gas sampling device; 13-feed and discharge opening; 14-speed
adjustable electrical machinery)
Williams and Williams (1999a)
Feed Hopper
Gas sample bag
TC
De-mister
Pyrolysis
reactor
Fluidised
bed
TC
TC
TC
Cyclone
TC
Distributer
Glass wool
trap
Catch
pot
CO2/ acetone
condensers
Gas pre-heater
10.1016/j.wasman.2014.08.004
Table 2 (continued)
Pyrolysis reactor and system in researches
Reference
Fluidised-bed pyrolysis system
Alimentation with
divided solid
Natural gas
towards burner
Marculescu et al. (2007)
Process gases analysis

and treatment
Heated case
Transport tube
Treatment gas inlet

(comburant or inert)
Burned gases
Functional scheme of the transport tube thermo-chemical convertor
Solid residue analysis
Integrated Pyrolysis for Power Plants

Pyrolysis of high calorific solid recoverd fuels
Flue gas to boiler
pyrolysis gas to boiler
1.Tipping bunker
2. Shredder
3.Fine material bunker
4.Crane system
5.Material sluice
6.Rotary pyrolysis
7.Burner system
8.Solid residue discharge
9.Fan
10.Cyclone(dedusting)
Inerts
Metals
Pyrolysis coke to
boiler
Fig. 1. Schematic ow sheet of RWE-ConTherm process (Tech Trade, 2014).
Equipped with emission abatement devices

As shown in Table 3, all of the commercial pyrolysis processes
are equipped with emissions abatement devices similar to incineration plant, ensuring the pyrolysis-involved process is a clean one.
Typical exhaust ue gas emission control devices include particulate lters, cooling tower, wet scrubbers, etc., but when compared
to those adopted in incineration plants, they are reduced in
dimension.
In addition to the commercial and semi-commercial pyrolysis
technologies, some pilot or demonstration technologies are newly
developed with purpose to simply the pyrolysis system for MSW
through applying pyrolysis alone.
Fig. 2 shows a pilot MSW pyrolysis facility developed in Tianjin,
China (Li et al., 2007) with a capacity of 5 tons per day. Dealing
with unsorted MSW, it consisted of a main reactor and a subsidiary
reactor. The main pyrolysis reactor was a tubular reactor with a
screw inside to push the MSW forward; the tube was heated from
outside by burning solid fuels such as coal or the charcoal produced in the pyrolysis process. The hot ue gas leaving the main
reactor was then conveyed to the subsidiary reactor, and, after
cooling in a radiation duct, it mixed together with pyrolysis gas
and contacted MSW directly to heat up the latter for decomposition and gasication. The pilot tests were based on an articially
assembled MSW with the following composition: rubber 8.27%,
PVC 8.51%, PE 8.51%, kitchen waste 24.33%, pericarp14.60%, vegetables 7.30%, cloth 5.35%, paper 18.25% and sawdust 4.87%. The
results revealed that as the temperature in the main reactor changed from 500 to 700 C, the gas yield increased from 24.4% to
38.9%, and the oil yields changed from 21% to 16.4%. At around
600 C, the averaged caloric value of the gas was 7.5464 MJ m3.
The H2 content was 15.2%, and the total C2H4, C2H6, C3H6 and CH4
content was 10%. No recommendation was given for the end products; but syngas seemed to be the most valuable product. There
was none sequel to this pilot MSW pyrolysis facility, possibly due
to the fact that tubular reactor with a screw inside cannot deal
with unsorted and unprepared MSW.
The Honghoo technology shown in Fig. 3 is a pure pyrolysis
process with multi-section rotary reactors, which run under the
temperatures from 300 C in section I to 500 C in section III. The
demonstration plant was feeding with unsorted MSW, syngas, oil
and char are output as products. According to a previous testing
operation analysis (Chen et al., 2013), the moisture-free oil yield
and the char yield were approximately 3% (moisture separated)
10.1016/j.wasman.2014.08.004

Table 3
Main pyrolysis involved units and technologies used in pilot, demonstration and industrial plants.
Process name
Reactor & operation conditions
Materials input & products
Technologies
Application
example
Environmental protection
device
PYROPLEQ process
(Bracker et al., 1998;
Modern Power
Systems, 2014)
Rotary drum, pyrolysis at 450

500 C; syngas was burnt at
1200 C and the hot gas from the
combustion chamber heats the
pyrolysis drum from the outside
Input: Pre-treated domestic

refuse; MPW
Output: The char with
caloric value of around
10 GJ t1. Power from steam
turbine
Pyrolysis &
combustion
The Ticino Canton

waste treatment
centre in Switzerland
Input: Shredded MSW,

automotive shredder residues
as well as up to 50% waste
plastics
Output: Power from steam
turbine
Input: MSW, industrial waste,
spent tyres, industrial and
plastic waste as well as
contaminated soil
Pyrolysis &
combustion
The Hamm powerplant, Germany, with

capacity of 100 kt/
year. Stopped
Hot-gas ltration by means of

ceramic lter cartridges. Lime is
added to the reactor for acid gas
removal. Conventional ue gas
clean up with a bag lter for y
ash collection with sodium
bicarbonate injection for acid gas
emission control is used. The ash
and acid gas clean-up solids are
mixed and sent for landll
disposal
The pyrolysis gas passed through
a cyclone before boiler
Flue gas scrubbing system of the
coal-red power plant
A combination
of pyrolysis,
gasication
(thermal
cracking), and
smelting
Aalen, Germany, with Gas scrubbing unit to wash out

inorganic acid pollutants,
capacity of 25,000
followed by a bag lter to
tons per year
remove the remaining dust; and
a basic and a biological washer
to remove H2S. Finally, an active
coal lter to absorb dioxins,
furans, and Hg
Pyrolysis &
combustion
Arras, France, with

The ue gases produced by the
capacity of 50,000 tpa combustion of the thermolysis
gases need a deduster and
rational scrubbing system
Pyrolysis and
entrained ow
gasication
Freiberg, Germany,
with capacity of
12,000 tpa sewage
sludge + 5760 tpa
MSW. Demonstration
plant
Pyrolysis,
gasication &
combustion
Keavic, Iceland, with Rational scrubbing techniques

for fuel gas and ue gas
capacity of 45 tons
per day
A combination
of pyrolysis and
high
temperature
combustion
Frth, Germany, with

capacity of 100.000
150.000 kt/y, Shut
down August 1998
after accident with
pyrolysis gas
ConTherm technology Rotary kilns, pyrolysis taking

place at 500550 C for about
(Tech Trade, 2014;
1 h, gas combustion in a
Hauk et al., 2004)
pulverised coal (PC)-red boiler,
see Fig. 1
Rotary kiln, pyrolysis at 500
550 C, for approximately 45
60 min, the kiln was externally
heated with part of the gas
produced in the process
The pyrolysis gases containing
tars are subsequently gasied in
a high temperature (1200
1300 C) gasier; char is smelted
(at 14001500 C)
A rotary kiln running at 450
EDDITh process
(Martin et al., 1998; 600 C for 45 min; gas is
combusted at approximately
Malkow 2004)
1100 C with air coming from
the dryer while the char
undergoes separation and
materials ltering
Gibros PEC Process or

PKA technology in
Germany (IEA
Bioenergy, 2004)
Output: CO/H2-rich fuel gas,

metals, basalt
Input: Shredded MSW,

industrial waste and sludge
Output: Gas (12 MJ kg1),
coke (16 MJ kg1, CARBOR),
metals, salts, mainly CaCl2
and NaCl, APC residues. Gas is
burnt for heat and power
generation
Input: MSW, other feedstocks
A rotary kiln and a gasier,
Noell-KRC conversion
(dried sewage sludges) may
process (now Future pyrolysis at approximately
be co-gasied
550 C, gasication at 1400
Energy) (Malkow,
2000 C and 250 bars
2004; Jaeger and
Output: Medium caloric
Mayer, 2000)
value gas; a part of the
cleaned gas is used to heat the
kiln. Metals and slag can be
used as construction
materials
Serpac technology
Two interconnected chambers of Input: Mixed waste, MSW,
(Malkow, 2004)
cylindrical and conical shape,
industrial and hospital waste
inclined and rotary. Pyrolysis at Output: steam; ash and
600700 C, char gasication
metals
with air at about approximately
800 oC; gas is combusted at
approximately 11001200 C
Input: Tyres, MSW, sewage
Siemens Schwel-Brenn A rotating drum and a high
sludge, industrial wastes
temperature furnace coupled
technology
with a steam boiler, pyrolysis at Output: Energy in form of
(Malkow, 2004;
steam or power. Metals, glass
450 C for approximately 1 h;
Richers and
the ner carbon-enriched (30%) and ash
Bergfeldt, 1996)
fraction is ground to 0.1 mm and
combusted together with the gas
in the slagging furnace at
1300 C
Rotary drum running at 450 C, Input: MSW is shredded into
Mitsui R21 Process, a
gas combustion at 1300 C
less than 200 mm in length
branch of Siemens
Output: power generation
Schwel-Brenn
from pyrolysis gas
technology. (IEA
combustion; char, ferrous and
Bioenergy, 2002)
non-ferrous metals;
production of a fused ash
product.
Input: MSW, industry waste,
Rotary kiln and ash-melting
Takuma SBV(Kawai,
2009) (Derived from system. Pyrolysis at 500550 C sewage sludge, etc.
in the rotary kiln; pyrolysis gas is Output: Energy (power &
the above Siemens
steam), iron, aluminium
burnt in a high temperature
Schwel-Brenn
chamber
process)
A combination Yame Seibu Plant,

Japan, with capacity
of pyrolysis
of 220 t/d, etc.
gasication &
melting process
A combination Kakegawa Plant,

of pyrolysis and Japan, with capacity
of 140 t/d MSW
gasication &
melting process
Pyrolysis gas is dedusted and

dewatered before entering the
gasier. There are two scrubbers
to clean gas from the gasier.
The rst stage removes H2S and
heavy metals, and the second
stage washes all of the other
contaminants
Dust collection and ue gas

scrubber
Flue Gas cooler followed by two

bag lters in series: No.1 for
particulate collection and
recycling of ashes to the
combustor, and No. 2 with dry
lime injection for acid gas
emission control, with landll
disposal of the solid residues
Flue gas quencher followed by
two scrubber stag
10.1016/j.wasman.2014.08.004
10
Table 3 (continued)
Process name
Reactor & operation conditions
Materials input & products
Thermoselect process
(Malkow, 2004;
Thermoselect S.A.,
2000)
Moving channel bed. The process

consists of shredding, in the
channel MSW is heated from 50
to 600 C and pyrolyses,
followed by gasication at 1200
2000 C
Input: Unsorted domestic

waste, shredded
Output: Medium caloric
value gas, a part of cleaned
gas is used to heat the
channel. Mineral and metals
from the smelt slag
A combination Mutsu, Japan, with

of pyrolysis and capacity of 50,000 tpa
gasication &
melting process
Von Roll RCP

technology
(Malkow, 2004;
Hesseling, 2002)
A forward reciprocating grate

furnace as a pyrolysis
(degassing) chamber; the
pyrolysis temperature in the
chamber is heated by partial
combustion of the gas with
oxygen to approximately 500
900 C; product gas and char are
sent to a smelting reactor at
1400 C and then to a circulating
uidised-bed furnace
Pyrolysis in the two tubular
reactors at 800 C; the char is
reacted with steam and air in a
xed bed gasier, and gas
combustion is in a cyclone
chamber at 12001250 C
Input: Dewatered sewage

sludges, pre-treated MSW,
clinical wastes, scrap tire
crumbs;
Output: Energy in form of
steam or power; Char/ash
material from the gasication
unit
Input: pre-treated MSW
Output: syngas with
moderate to low caloric
value, char, metals and ash
Pyrolysis,
gasication and
high
temperature
combustion
Avonmouth, UK, with

capacity of 8000 tpa.
(Mainly clinical waste
now)
Pyrolysis &
partial
gasication
Tianjin, China, with

Gas cooler and lter
capacity of 200 kg h1
Compact Power
process (now Ethos
Renewables
Avonmouth (ERA)
Limited) (Malkow,
2004)
A gasication-coupled pyrolysis
process. The main reactor is a
screw-bed reactor, and
gasication takes place in the
subsidiary reactor. No
information on pyrolysis
temperature. See Fig. 2
Honghoo technology
Multi-sectional rotary kilns,
(Chen et al., 2013)
pyrolysis at lower temperature
of approximately 400450 C,
none-catalytic pyrolysis, indirect
heat transfer; the gas is burnt
online to supply the heat. See
Fig. 3
CNRS thermo-chemical A tubular rectilinear reactor
heated by circulation of hot ueconvertor
gases (natural gas burner) within
(Marculescu et al.,
an external double envelope. The
2007)
solid continuously advances by
vibro-uidised transport
Flow rate up to 50 kg/h
Running from pyrolysis to
combustion with temperature
changing from 400 to 1000 C.
See Table 2
Pilot pyrolysis process

in Tianjin, China (Li
et al., 2007)
Technologies
Application
example
Environmental protection
device
A water jet quenching section is

used to avoid the formation of
dioxins, and an acid gas scrubber
unit is used to remove the HCl
and HF; an alkaline scrubber unit
with an aqueous sodium
hydroxide solution at higher pH
is used to remove residual traces
of CO2 and SO2, and the
desulphurisation stage removes
H2S from the gas; an activated
carbon lter is installed to act as
a nal polishing unit for the
synthesis gas
Particulate emission control
A combination Bremerhaven,
Input: Pre-treated MSW,
systems and acid gas scrubbing
residual waste from recycling, of pyrolysis and Germany, a pilot
plant with capacity of equipment used in a common
melting &
industrial waste
Output: Metal, slag; energy in combustion
power generation system
6 t/h MSW
form of steam or power
Dry scrubber with sodium

bicarbonate and Selective
Catalytic NOx Reduction (SCR).
The solid residues from the dry
scrubbing unit are sent for
landll disposal
Input: Raw MSW with bottles, Pyrolysis alone

stones, bricks and glass
separated
Output: Oil, char, cleaned gas
(for power generation)
Shanghai, China, with Pyrolysis gas was scrubbed

capacity of 100 ton/d, before burning. Char was
quenched and separated from
demonstration plant
metals
Input: Ground MSW

Output: Syngas or ue gas
depending on whether
comburant or inert gas is
supplied; accordingly char or
ash output
Pilot test facility
and 20% of the feedstock, respectively, whereas the moisture and

syngas gases accounted for approximately 77% of the feedstock.
However, as the input wastes were raw MSW with a moisture content of approximately 60%, the moisture condensate in the liquid
products was more than 50% of its income in the feedstock, and
the vaporisation heat of the moisture in the reactor consumed
most of the reaction heat, reducing the treatment capacity from
the designed 100 tons per day to the actual value of less than
30 tons per day. The end products are syngas and the char; the syngas was cleaned and used for power generation. Oil was planned to
replace the cleaned gas for heating the system after being
upgraded with distillation, the heavy residue would be sent back
to the reactor. Presently Honghoo technology is on the way to be
Pyrolysis alone
Not mentioned
commercialized, yet its char product needs to be standardized

and it should be equipped with MSW pre-treatment devices to
ensure the stable operation and improve the quality of products.
3.2. Pyrolysis reactor
The reported reactors for MSW pyrolysis include xed-bed
reactors, rotary kilns, uidised bed reactors and some innovative
reactors, the concepts of these reactors are shown in Table 2. In
regards to the reaction conditions, most pyrolysis processes have
been conducted at atmospheric pressure. Vacuum pyrolysis has
only been reported in studies of special wastes such as printed
circuit board disposal (Peng et al., 2006; Li et al., 2009). Although
10.1016/j.wasman.2014.08.004
11
Fig. 2. Schematic of the pilot MSW pyrolysis plant in Tianjin, China (Li et al., 2007).
Drying section
Collecting and seperating systems for

gas,oil and water
Purified Gas
Oil
Wastes
Gas engine
Gas
Chartank
Char discharge
Automatic
Control System
Fig. 3. Honghoo technology schematic (Chen et al., 2013) (I, II and III are the rst, second and third section of the pyrolysis reactor, respectively, and IV is the char cooling
drum).
vacuum pyrolysis is reported to shorten the residence time of

volatile products in the high-temperature zone, reducing the
secondary decomposition and increasing the heat value of the
gas products, achieving vacuum pyrolysis is difcult in practice.
Therefore, all of the following discussions in this review are based
on atmospheric pressure. The reactors used in studies and at industrial scale are summarised.
uniform inside the sample (Wang et al., 2006), and the feedstock
is decomposed at different temperatures simultaneously. Fixedbed reactors have mainly been used to identify governing parameters affecting pyrolysis products, as discussed previously and
shown in Table 1, but few comparisons have been reported with
changed sample masses. Due to its inefciency this reactor is seldom adopted in scale-up facilities.
3.2.1. Fixed-bed reactor

The xed-bed reactor is characterized by a low HR, as the result
of its low heat transfer coefcient, as shown by Eq. (4). Therefore,
when a greater sample mass is tested, the temperature is not
3.2.2. Rotary kiln reactors and their systems

The rotary kiln is more efcient than the xed-bed reactor in
heating up the feedstock. The slow rotation of an inclined kiln
enables good mixing of wastes. The rotary kiln reactors are widely
10.1016/j.wasman.2014.08.004
12
used, but they are typical reactors used for conventional pyrolysis
(slow pyrolysis), which proceeds under a slow HR with signicant
product portions of char, liquid and gas. The reported HRs are not
higher than 100 C min1 as shown in Table 1 and the residence
time is up to 1 h, as shown in Table 3. This is because during pyrolysis, only the reactor wall serves to transport heat from outside to
the particles; the small wall surface distributed to the unit mass of
feedstock and coarse size of the particles result in a low HR. However, most reported MSW pyrolysis technologies are based on
rotary kiln pyrolysers, as shown in Table 3, because the rotary kiln
reactor has many unique advantages over other types of reactors.
In addition to the good mixing of wastes, the exible adjustment
of residence time and larger channel for the waste stream allow
feeding of heterogeneous materials, and thus, extensive pre-treatment of wastes is not required, and its maintenance is also simple.
Rotary kilns for pyrolysis are externally heated using combusted
pyrolysis gas. The calculation of heat and mass transfer and design
of the kiln have been extensively investigated for homogeneous
materials (Donald and Rosseman, 1962; Rutgers, 1965;
Bridgewater, 1985; Boateng and Barr, 1996; Li et al., 2005). For
MSW pyrolysis, Li et al. (2002) performed comparative studies of
homogeneous sand and irregular MSW in a rotary kiln in a cold
state; examined the impacts of material characteristics, kiln geometry characteristics (i.e., roughness of kiln wall, exit end dam and
internal structures) and operational parameters (i.e., kiln inclination and rotational speed) on both material residence time (MRT)
and material volumetric ow (MVF); and then proposed a set of
simplied formulas for the proper prediction of the MRT and MVF
of MSW during pyrolysis (Li et al., 2002). But there is not much
information in the literature on their heat transfer coefcients for
heterogeneous MSW with changing particle size and composition.
3.2.3. Fluidised-bed reactors
Fluidised-bed reactors are characterized by a high HR and good
blending of the feedstock. Therefore, such reactors are more
frequently used to describe the inuence of temperature and
residence time on pyrolysis behaviour and products (Williams
and Williams, 1999a; Mastral et al., 2002, 2003; Dai et al.,
2001a,b).Typically, uidised-bed reactors are used to investigate
the behaviours of fast pyrolysis (or ash pyrolysis) and to explore
the secondary cracking of tar at longer residence times.
Although uidised-bed reactors have been extensively adopted
in laboratory studies, their industrial application is not common
for MSW pyrolysis. The reason is that the separation of bed material from coke, along with its external heating and recirculation, is
complicated. However, providing uniform products is usually
expected for a polymer cracking process, and polymer pyrolysis
in a uidised-bed reactor can provide remarkable advantages over
other reactors wherein heat is not as properly transferred for the
cracking of polymers because polymers have a very low thermal
conductivity and high viscosity. Therefore, uidised-bed reactors
are widely adopted as pyrolysis reactors for MPW, such as in, for
example, the Hamburg process developed by Kaminsky (1992,
2006) and BP polymer cracking process (Botom, 1993; Al-Salem
et al., 2010). Arena and Mastellone (2006) summarised all of those
processes for MPW pyrolysis and their commercial states, concluding that the uidised-bed technology appears mature and particularly attractive for plastic waste pyrolysis. As for its application to
MSW pyrolysis, in addition to the problems of bed material separation, external heating and recirculation, uidising agent (gas)
choice and MSW pretreatment should be dealt with thoroughly,
as they are expensive steps.
3.2.4. Tubular reactors
Tubular reactors include a family of reactors with xed walls in
a tube shape, but for which, the materials move inside via various
driving modes. Tubular reactors are generally heated externally,

and they studies featuring them reported different forms, such as
a screw pyrolyser (Aguado et al., 2002), a tubular rectilinear reactor
with solid driven forward by a vibro-uidised transport
(Marculescu et al., 2007), as shown in Fig. 4; and a tube with an
inner mixer (Walendziewski, 2002). In Table 3, the pyrolysis reactors in the Thermoselect process, the Compact Power process and
CNRS thermo-chemical convertor are all tubular reactors. The
advantages of these systems include continuous coke and gas
removal from the reactor tubes free from leakage, larger heat
transfer surface in a unit volume and convenience for syngas
reforming. It is easy to design and run a tubular reactor if the heat
transfer coefcient is known because of its simplicity and safety. As
a typical tubular reactor, the screw tube, with its lower construction and operation costs, has great future prospects. For this design,
the screw speed can be varied within 0.525 rpm, thereby changing the residence time of the materials; this reactor system has
been found to be useful for both the thermal and catalytic cracking
of waste plastics (Aguado et al., 2002). However, tubular reactors
have the same rigid requirements for MSW pretreatment as the
uidised-bed reactors due to the small channel for passage of
MSW. In addition, erosion caused by sand and other hard solids
contained in the MSW can be a risk for this reactor, and heat transfer coefcients are not well dened for different waste types.
In a conclusion, adaptability of different reactors to MSW pyrolysis can be summarised in Table 4, from Table 4 it can be predicted
that rotary kiln will still serve as the main reactor type for MSW
pyrolysis. However, for small and moderate scale, tubular reactor
can be competitive. The operation temperatures are dependent
on product choice.
3.2.5. Other pyrolysis reactors and technologies
In addition to the above single-stage reactor types, whose products must be post-treated outside the reactors, some multi-stage
reactor types have also been adopted, and they are mainly for
reforming or improving products. For example, a two-stage tube
reactor was used to investigate the effect of steam reforming on
the tar produced in the rst reactor stage (Ohmukai et al., 2008),
as the two stages can be controlled under different conditions.
For a similar purpose, Zhao et al. (2011) proposed a three-stage
reactor, in the rst stage, HCl can be extracted immediately,
whereas the volatiles generated in the second stage can be
extracted out or passed through the third stage and vice versa
for product reforming. Those multi-stage reactors give hope for
the independent running of pyrolysis technology.
In a traditional thermal pyrolysis, in which process the heat Q in
Eq. (1) is supplied externally by hot ue gas, alternatively Q can be
supplied through volumetric heating as performed in the new
technologies such as plasma pyrolysis (George, 1994; Hrabovsky
et al., 2006) and microwave pyrolysis (Cho et al., 2009;
Macquarrie et al., 2012) .
Plasma pyrolysis is the process of heating waste to a very high
temperature over 1000 C using plasma torches without an air supply, which converts waste into a synthetic gas (mainly CO and H2)
and other end-products, such as a vitried matrix. The highly
efcient delivery of heat for simultaneous rapid promotion of both
physical and chemical changes in waste materials results in better
control of process temperature, higher process rates, lower
reaction volume and especially optimum composition of produced
syngas. The properties of plasma pyrolysis products are predictable, suitable for energy and material recycling, and harmless in
terms of public health and the environment (Huang and Tang,
2007), but plasma pyrolysis requires a large amount of secondary
energy, for example,1 kW h kg1 for arc plasma technology
(George, 1994; Wang and Huang, 2008). Presently, plasma pyrolysis is being tested mainly for hazardous waste disposal. For its
10.1016/j.wasman.2014.08.004
13

Table 4
Adaptability of different reactors to MSW pyrolysis.
Reactor type
Running experiences
Requirements on
material
preparation
Capacity
Maintenance
requirement
Flexibility to
operation parameters
change
Application recommendation
Fixed-bed reactor
Running in batch, only

in laboratory
researches
Small, may not

exceed several
tons per day
Not recommended for

industrial application
Most common
Low, but batch by

batch operation
demanding manual
labour
Low to moderate
Excellent exibility
Rotary kiln
Almost no
requirements
except for energysaving purpose
Not rigid
Good exibility
Fluidised-bed
reactor
Only for laboratory

researches, no
practical experiences
for MSW
A few
Very rigid
Large
theoretically
Highest
Rigid
Moderate, up
to 50,000 tpa
Moderate to high
Very limited to size

change; good
exibility to
temperature, etc.
Limited to size and
temperature change
Recommended but efciency

should be improved; multisectional reactor suggested
Heating system should be
improved before application
to MSW pyrolysis
Tubular reactor
Large, up to
150,000 tpa
MSW application, a life cycle assessment comparison of the whole

process with a thermal cracking system is suggested, even a facility
is available.
Microwave pyrolysis is being investigated mainly for homogenous wastes such as sludge, shredded plastics and tyres. It is a type
of microwave dielectric heating method, and its main advantages
include rapid, efcient in-core volumetric heating for direct
coupling of microwave energy with the molecules that are present
in the reactants, easily controlled and maintained desired temperature of pyrolysis for desired product raising, lower temperatures
for the reaction vessel (or material surface) and higher temperatures for the reaction mixture (or material interior), etc.
(Baghurst and Mingos, 1992). However, to achieve the required
rapid heating rate, the feedstock particles have to be very ne to
full the requirements, and achieving accurate temperature control in a microwave reactor is dependent on accurate dielectric
data in the microwave frequency range as a function of temperature, which is not available for most of waste components. In addition, solid-laden vapour has to be swept out of a microwave reactor
very rapidly to reduce secondary cracking of organic vapour in the
freeboard and to drive water vapour and water-soluble small polar
molecules out of the reactor (Yin, 2012). Together with its relatively small treatment capacity, the application of microwave
pyrolysis to heterogeneous MSW is not practical in the near future.
In addition pyrolysis with various catalysts was adopted to
improve products. Process catalysts have been widely used in
MPW pyrolysis in literatures. Pure polymer thermal degradation
in the absence of catalyst produces a high boiling point wax-like
mixture that requires further upgrading via conventional renery
processes. The use of catalysts in pyrolysis presents some advantages compared with simple thermal processes: i.e., lower energy
consumption, shorter reaction time and good selectivity to
higher-valued products. In addition, the liquid products formed
are in the boiling point range of commercial motor engine fuel,
eliminating the necessity for an upgrade process as well as the
necessity for the whole process to be installed near existing reneries (Gulab et al., 2010). For MSW pyrolysis, the summary listed in
Table 1 shows that catalysts improved oil quality and enhanced gas
generation, but only cheap catalysts such as calcined dolomite (Yi,
2007; He et al., 2010) and CaO (Pan, 2012) can be used, as the catalysts cannot be subsequently recycled. In addition, the catalytic
effects are usually not sufcient; more signicant effects can be
achieved for MPW than for MSW under the same conditions
(Miskolczi et al., 2013) because of the poor contact between the
MSW and the catalysts. To improve the MSW pyrolysis process,
cheap catalysts that can absorb acidic gases at the same time are
more preferred than highly effective and expensive catalysts.
Recommended, especially
the multi-sectional tubular
reactor
4. Products from pyrolysis of typical MSW components and

MSW
A great advantage of pyrolysis technology over incineration is to
export high quality products of oil or gas instead of heat, especially
for the small-scaled systems. As the information on MSW pyrolysis
products is very limited, and composition of MSW changed from
place to place, a brief survey of products of principal MSW components will help to elucidate the products from practical MSW pyrolysis process.
4.1. Pyrolysis products from waste paper
Paper represents a mainstream combustible in MSW. As its
principal components are semicellulose and cellulose, waste paper
is an important representative of biomass in MSW. Wu et al. (2002,
2003) investigated newspaper, uncoated printing and writing
paper in MSW and found that paper begins to decompose around
488 K with the HR of 5 K min1, and at 583 K essential matrix
decomposition takes place already. The major pyrolysis in their
studies included non-hydrocarbons (HCs) (H2, CO, CO2, and H2O)
and hydrocarbons (C13, C4, C5, C6, 1-ring, C1012, levoglucosan,
C1315, and C1618), and the concentrations of both non-HC and
HC products increased with temperature. The percentage of volatiles increased from 4.75% to 90.56% when the temperature
increased from 310 C (583 K) to 665 C (938 K) at a low heating
rate of 5 min K1. Tar formation occurred within the moderate
temperature range of 290540 C (563813 K). The tar yield was
approximately 47.03% at 450 C and a heating rate of 10 C min1.
There were four main different compounds they identied in the
tar: anhydrosugars, carboxyl compounds, carbonyl compounds
and aromatic compounds. As temperature increased to 665 C
(938 K), the char was reduced to less than 10% for the newspaper.
Ahmed and Gupta (2009) founded that waste paper pyrolysis had a
considerable overlap with its gasication, especially at higher
temperature, but pyrolysis was more exible compared with
gasication regarding the temperature. In a relatively large-scale
laboratory study based on a xed-bed reactor, Jiang (2006) found
the LHV of syngas from waste paper pyrolysis reached a maximum
of 17.5 MJ N m3 at approximately 600 C with a yield of
301.4 L kg1, and the gas yield increased from 25.12% to 47.14%
as the pyrolysis temperature increased from 600 to 900 C. The
liquid product yield decreased from 44.47% to 32.08% at the same
time, but 67.4% of liquid product was moisture at 600 C. As
the temperature increased, the moisture fraction also increased.
The LHV of the syngas was between 10 and 17.5 MJ N m3 within
the temperature range of 400850 C, which is much higher than
10.1016/j.wasman.2014.08.004
14
the LHV of syngas from gasication, the latter was reported to vary
from 1.8 to 2.5 MJ N m3 within the temperature range of 400
700 C (Xiao et al., 2007). All of these results indicate that syngas
will be an important product from MSW pyrolysis when waste
paper is a principal component, and the reaction temperature
should not be lower than 600 C.
4.2. Pyrolysis products from MPW
MPW is the most important energy contributor to MSW. A
number of important studies on polymers and MPW pyrolysis
were summarised by Al-Salem et al. (2010). The main purpose of
MPW pyrolysis is to recover liquid products in many processes.
For example, the famous BP polymer cracking process, Fuji process
(Fuji Electric, 2001) and Hamburg process are all designed to
recover oil products. To obtain high-quality, market-ready oil, the
pyrolysis recycling of MPW usually consists of two processes.
The rst is the degradation of MPW for the production of heavy
oils, and the second is a catalytic cracking process that converts
the heavy oils into useful hydrocarbons. Many catalytic cracking
processes have been tested and were summarised by Masuda
and Tago (2006). According to their recommendation, catalytic
hydrolysis reactors with steam as a carrier gas and FeOOH as a
catalyst followed by a catalytic cracking reactor with zeolite as a
catalyst could be a promising solution for fuel oil upgrading.
In regards to components, there are six main plastics in MSW:
high-density polyethylene (HDPE), low-density polyethylene
(LDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride
(PVC) and polyethylene terephthalate (PET). PE (including LDPE
and HDPE) and PP account for 70 wt% of the waste plastics stream
in MSW in China (Wang et al., 2013), most important plastic components in UK (Waste watch, 2008) and also worldwide (APME,
2004). Table 5 gives the product yield from the pyrolysis of PE
and PP plastics, as summarised by Williams (2006). It can be seen
that single PE and PP pyrolysis results in a yield of liquid products
varying from 5% to 95%. In vacuum reactor or a uidised-bed reactor running at moderate temperature (approximately 500 C), the
volatiles can be extracted immediately before the secondary cracking takes place, and a higher yield of liquid products can be
expected. Whereas in a high-temperature uidised bed (for example higher than 800 C) or a fast pyrolysis reactor, the volatiles will
be subjected to secondary cracking before leaving the hot zone,
resulting in high gas yields. Grieco and Baldi (2012) showed that
the oil yield of PE pyrolysis performed in a xed-bed reactor

decreased from 90.9% to 86.2% as the HR increased from
0.1 C s1 to 1 C s1, while the gas yield increased from 9.1% to
13.7%. However, a very slow HR would result in a higher char
product, as shown in Table 5 for the two lower temperature cases
(430 C for HDPE and 380 C for PP). The major gaseous products
were H2, methane, ethane, ethylene, propylene, butadiene,
benzene and toluene without CO, CO2 or HCl appearance for PE,
PP and PS. Therefore, gas products are of high caloric value. PVC
is regarded as a harmful component in the MPW, as HCl evolves
during pyrolysis, contaminating the products and causing apparatus corrosion, its separation is desired. All of the reported polymer
cracking processes include an HCl abatement step to separate
chlorine from HCs.
In contrast to biomass, MPW in MSW requires a higher temperature to nish its pyrolysis. Within the conventional pyrolysis
temperature range of 500550 C for rotary kilns oil is the main
product of MPW; and MSW rich in MPW components would inevitably have oil/liquid products generated.
4.3. Pyrolysis products from wood and woody mass
Yard wastes, chopsticks, used furniture, etc. contribute wood
and woody mass in MSW. In terms of components, wood and
woody mass contain cellulose, hemicelluloses and lignin. Yang
et al., 2007a,b studied the pyrolysis of biomass hemicelluloses, cellulose and lignin, and they demonstrated that hemicelluloses, with
higher carboxyl content, accounted for a higher CO2 yield; cellulose
provided higher CO yields, which were mainly attributed to the
thermal cracking of carboxyl and carbonyl, whereas lignin released
more H2 and CH4. The components of gas products from wood pyrolysis are mainly H2, CO, CO2, CH4, C2H4, C2H6, C3H8 and water
(Kinata et al., 2013). In addition, C4H10 also appeared in the gas
products (Xiao et al., 2007). The pyrolysis products from wood chips
or sawdust are summarised in Table 6, in most cases, the density of
the syngas was not reported, so that the yields were either given in
% or m3 kg1; but Li et al. (2000b) reported the density of syngas
from wood pyrolysis decreased from 1.40 to 1.21 kg N m3 when
the temperature changed from 550 to 850 C. From Table 6 it can
be seen that wood and woody mass are suitable contributors for
syngas with moderate LHVs, and higher temperature benets the
gas production. Ni et al. (2006) compared the wood pyrolysis and
its gasication in a uidised-bed reactor and found that the
Table 5
Product yield from the pyrolysis of polyalkene plastics (Williams, 2006).
Feedstock
Reactor type
Temperature (C)
Gas (wt%)
Oil/wax (wt%)
Char (wt%)
PE
PE
LDPE
LDPE
LDPE
LDPE
HDPE
LDPE
LDPE
HDPE
HDPE
HDPE
LDPE
LLDPE
LLDPE
PP
PP
PP
PP
PP
Fluidised-bed
Fluidised-bed
Fluidised-bed
Fluidised-bed
Fluidised-bed
Fixed-bed(batch)
Fixed-bed(batch)
Fixed-bed(batch)
Ultra-fast pyrolysis
Fixed-bed(batch)
Fixed-bed(batch)
Vacuum
Vacuum
Fluidised-bed
Fluidised-bed
Fixed-bed(batch)
Fixed-bed(batch)
Fluidised-bed
Vacuum
Fixed-bed(batch)
760
530
700
600
500
700a
700a
500a
825
450
430
500
500
730
515
380
700a
740
500
500a
55.8
7.6
71.4
24.2
10.8
15.1
18.0
37.0
92.9
13.0
9.6
0.9
2.7
58.4
0.0
24.7
15.3
49.6
3.5
55.0
42.4
92.3
28.6
75.8
89.2
84.3
79.7
67.0
5
84
69.3
97.7
96.0
31.2
89.8
64.9
84.4
48.8
95
45.0
1.8
0.1
0.0
0.0
0.0
0.0
0.0
0.0
2
3
21.1
0.8
1.0
2.1
5.9
10.4
0.2
1.6
<0.1
0.0
Final temperature.
10.1016/j.wasman.2014.08.004
15
pyrolysis gas yield at 600 C was 0.26 m3 kg1 with an LHV of

17.5 kJ m3; under the same temperature, syngas from gasication
was 2.01 m3 kg1 with a LHV of 5.8 MJ N m3; showing pyrolysis
gas has much higher LHV and small volume than that of syngas
from gasication, which is benet for its utilization. High-quality
chars with satisfactory LHVs in Table 6 are natural for the wood,
which are the target products for thousands of years. But wood
and woody mass are not a good feedstock for liquid product
increases. In addition, considerable amount of moisture appeared
in the liquid products, which would lead to very expensive post
treatment of these liquid products. So the recommended products
from wood & woody waste pyrolysis are syngas and char.
4.4. Pyrolysis products from fallen leaves and vegetables
Fallen leaves and vegetables are putrescibles in MSW. There are
a very limited number of studies examining their pyrolysis
behaviours, and the products of fallen leaves and vegetables are
similar to paper if they are dried. Li et al. (1999a) reported that
the gas yield of vegetables in a rotary kiln pyrolyser was only
0.05 N m3 kg1 at 850 C (0.380 N m3 kg1on a dry basis) when
the moisture content was 86.86%, and the char yield was 4.5%;
the residues were water and tar. At the same rotary kiln, Li et al.
(2000a) reported that gas yield of vegetables was 0.388 N m3 kg1
(dry basis) at 850 C, when the initial moisture content was
17.86%; the tar production was 17.6%, and the char production
was 32%. Li et al. (2000a) also reported that for the fallen leaves,
the gas yield was 0.353 N m3 kg1 (dry basis; initial moisture content: 11.49%) at 850 C; the tar yield was 21.5%, and char production was 35.4%, comparable to waste paper. In general, fallen
leaves and vegetables are biomass with little lignin content,
although the dry matter is suitable pyrolyser feedstock for syngas
production, the high moisture content is their main thermal treatment limitation and they are suggested to be separated from MSW
before pyrolysis.
4.5. Pyrolysis products from RDF from MSW
Pyrolysis of MSW in the form of RDF has been extensively investigated. Buah et al. (2007) studied pyrolysis of RDF with a gross
caloric value of 18.9 MJ kg1 in a x-bed reactor and found that

the main weight loss within the lower temperature zone (240
380 C) was due to the degradation of the cellulosic fraction in the
RDF, whereas the second peak of weight loss, occurring between
410 and 500 C was due mainly to degradation of plastic components. Chen et al. (2008) adopted thermogravimetric analysis
Fourier transform infrared spectrometer (TGFTIR) to investigate
the pyrolysis of two different RDFs, and they found similar weight
loss-temperature behaviours. The temperature zones were 220
430 C for biomass degradation, 430520 C for plastics decomposition and higher than 650 C for carbonates. Buah et al. (2007) also
found that the pyrolysis gases from RDF were H2O, CO2, CO, CH4
and other HCs. The yield of char fell as the pyrolysis temperature
rose from 400 to 700 C, and the oil/wax and gas products increased.
The chars recovered were also found to have BET surface areas that
increased with temperature, but this effect was also dependent on
their size distribution. At 400, 500, 600 and 700 C, the caloric values of the chars were 20.4, 16.7, 16.4 and 11.2 MJ kg1, respectively,
with a yield decrease from 50% to approximately 31%, which suggests those chars can be used as a solid fuel, charoil or charwater
slurry for fuel. Alternatively, the char with the proper particle size
can be improved for purposes such as activated carbon production.
The gross caloric values of the syngas from 400, 500, 600 and
700 C were 5.1, 13.7, 16.2, and 16.7 MJ m3, respectively; and their
yields were all approximately 20%. The yield of oil products
increased from 30% to 50% as the temperature increased, and there
was an increase in the aromatic groups and a decrease in aliphatic
groups at the same time. The most recent research of Hwang et al.
(2014) demonstrated that the char from RDF pyrolysis had a similar
BET surface area to the results of Buah et al. (2007), and the RDF used
by Hwang et al. (2014) had a higher heat value (HHV) of
17.9 MJ kg1. Its pyrolysis produced chars with a specic surface
area, changing from 24.6 to 30.4 m2 g1 as the temperature
increased from 500 to 900 C. The values were much lower than that
of chars from wood, waste paper or plastics. The HHVs of the pyrolysis gas from this RDF were 10.4, 17.0 and 19.1 MJ kg1 for temperatures of 500, 700 and 900 C, respectively. These values were also
very close to the results of Buah et al. (2007).
The available results on RDF have proven that during pyrolysis
interactions between different components did not change the
Table 6
Pyrolysis products from wood chips or sawdust in laboratory researches.
Ref.
Product yields
Gas (yield/LHV in MJ N m3)
Li et al., 1999a
Xiao et al., 2006
Jiang, 2006
Yi, 2007
Hwang et al., 2014
Temperature
(C)
Reactor type/feedstock
18.6%
750
850
Approximately 25%, 11.7382
400

45.11%
43.54% M3: 69.3%
30.75%, M:71.6%
34.72%, M: 75.3%
36.53%
8.0% 4
8.1%4
7.5%4
14.9%4
4041%
3031%
20%

39.57%, 16.326
31.83%, 20.482
23.41%, 23.852
15.76%, 26.115
12.31%, 29.322
22.8%,
13.6%
9.3%
9.6%
8788%
6570%
55%
500
600
700
500
600
700
800
900
600
700
800
900
500
700
900
Rotary kiln, wood chips

L d: 22 40 mm, 4.5 L
in volume
Fluidised bed Woodchip
in 5 mm 5 mm
Sample mass: not mentioned
Liquid (yield/LHV
in MJ kg1)
Char (yield/LHV
in MJ kg1)
LHV: approximately 19.5

0.376 N m3 kg1, 15.0
37.9%

Approximately 35%wt, 1.61
15.32%, approximately 14.5
0.23 Nm3 kg1
0.40 N m3 kg1
0.66 N m3 kg1
0.84 N m3 kg1
0.12 N m3 kg1, 12.2
0.3 N m3 kg1, 16.5
0.52 N m3 kg1, 16.9
Fixed bed, sawdust of 1000 g
Fixed bed, sawdust of about

1000 g mixed with calcined
dolomite
Fixed bed reactor, woody biomass
chip of 7 g
1: Fluidising gas may be included; 2: moisture included; 3: moisture content in liquid products; 4: tar yield.
10.1016/j.wasman.2014.08.004
16
essential pyrolysis behaviours of individual components, and the

target pyrolysis products can be expected by controlling the
MSW components when producing RDF. But because of the energy
consumption involved in the segregation process for making RDF,
MSW in the form of RDF may greatly reduce the energy generation
potential according to Chakraborty et al. (2013). When disposed of
through pyrolysis, the benets of RDF may include its adaptability
to all types of reactors, steady operation and production of uniform
gas, oil and char products. To obtain the valuable syngas the pyrolysis temperature should be 600 C or higher.
4.6. Pyrolysis products from MSW
Roughly pretreated MSW or MSW with source separation collection have been adopted in pyrolysis processes in practice, as
seen in Table 3. In most processes, a gasication or combustion
process is followed because of the fact that energy in the form of
heat and power is a market-ready product. To help standardize
gas, liquid and char products from MSW pyrolysis, these products
are characterized here.
4.6.1. Properties of gas products from MSW
The properties of pyrolysis products from some trials with
unsorted MSW are summarised in Table 7. As MSW varies largely
in components, the pyrolysis yields also vary signicantly. In general, a higher temperature and catalyst addition will increase the
gas yield and reduce the char yield. Combining the data in Tables
1 and 7, it can be seen that the gas yield is usually lower than 1
Nm kg1, and its averaged LHV is approximately 15 MJ N m1
when the pyrolysis temperature is not lower than 600 C, which
is quite different from gasication, where the gas yield can be
higher than 1 N m kg1 but with a lower caloric value (Hwang
et al., 2014).
4.6.2. Liquid products
Liquid products often contain a high moisture fraction, which
makes them difcult to apply. To improve liquid product quality,
the research of Velghe et al.(2011), based on an MSW with an average caloric value of 27 MJ kg1, found that to produce oil, the
optimal pyrolysis conditions are fast pyrolysis at approximately
510 C with a proper feeding rate. Under such conditions, the
associated liquid product contains the highest yield of waxy
material and oil and the lowest water content, the lowest O/C value
and a high heat value, which makes it a promising fuel. In regards
to the composition, the oil fraction is rich in C8C28 aliphatic carbons (63.5% with 44.1% alkenes) in addition to 23.5% aromatic
compounds. They also found that no waxy material existed in
the liquid fractions of the slow pyrolysis products up to 550 C.

Under the slow pyrolysis conditions, the oil yield was low, with
70.2% of the composition being C8C28 aliphatic carbons.
Miskolczi et al. (2013) compared pyrolysis oil from MSW and
MPW at 500 C with a commercial oil (a so-called standard
product) and found that pyrolysis oil from MPW with or without
catalysts meets most of the requirements in commercial oil,
whereas pyrolysis oil from MSW has a much higher water content
and cannot meet the requirements in terms of the cetane index and
corrosion test, in addition to the issue of its unqualied distillation
data. Water in liquid products mainly comes from biomass pyrolysis, so if oil production is desired, it is suggested that MPW instead
of whole MSW be pyrolysed.
4.6.3. Solid products
The data in Table 7 show that char from MSW pyrolysis could be
a valuable fuel due to its relatively high LHV. However, few processes listed in Table 3 (other than the EDDITh process) output
energy in the form of char. In most cases, char is gasied in a later
step or combusted and melted because solid fuel is not as attractive as gas and oil. In addition, before outputting char as a fuel
product, a pretreatment step, such as sorting out metals and pebbles, is needed; this increases the cost and weakens its competition
with rational fuel.
Zhang (2012) explored the potential of adopting char from
MSW pyrolysis as biochar and found that the properties of the char
from MSW pyrolysis are similar to those of normal biochar from
biomass: the char from MSW pyrolysis was rich in hydroxy-OH,
fatty C-H, carboxyl group-COOH, aromatic rings CAH and C@C
bonds on its surface, and the application of the char to the soil
could increase the cation exchange capacity and pH of the soil
and improve soil fertility. However, the accumulation of heavy
metals in the char and their mobility to the soil may hinder this
application.
4.6.4. Standardized product
Presently, there is no standardized product from the MSW
pyrolysis process that is ready for the market, with the exception
of the electricity or heat produced by burning syngas, oil or char
in the facilities. Syngas, oil and char converted from MSW in the
pyrolysis process cannot meet any standards for conventional fuels
and materials. However, the existing commercial pyrolysis processes coupled with gasication or combustion facilities (see
Table 3) are too complicated and expensive, limiting the application of pyrolysis to the places where it is highly demanded due
to the desire to prevent long-distance transport and the increased
difculty in nding new sites for incinerators and landlls. As an
Table 7
Pyrolysis products from MSW.
Ref.
Product yields
Gas (yield/LHV in MJ Nm3)
Liquid (yield/LHV
in MJ kg1) (%)
Char (yield/LHV
in MJ kg1)
Wang et al., 2005b
Approximately 0.15 N m3 kg1
Approximately 40%1
34.83%
Jiang, 2006
8.92%
13.41%
19.85%
31.16%
34.84%
0.33 N m3 kg1,
0.52 N m3 kg1,
0.81 N m3 kg1,
0.96 N m3 kg1,
61.261
59.98
58.73
52.61
50.59
5.12
4.82
4.22
3.62
29.82%,
26.61%,
21.42%,
16.23%,
14.57%,
15%
10.4%
8.1%
7.8%
Yi, 2007
14.6
15.3
15.1
14.1
18.317
21.471
28.154
29.915
30.362
Temperature
(C)
Reactor type/feedstock
550
Fixed bed Rubber, PVC, PE, rice, fruit husks,

vegetables, cloth, paper, wood chips. Sample
mass: 600 g LHV: 19.9 MJ kg1
Fixed bed, mixture of kitchen waste, paper,
cloth, bamboo, plastics and glass, air-dried, size
less than 5 cm, 1000 g
500
600
700
800
900
600
700
800
900
Fixed bed, mixture as above with addition of

calcined dolomite, air-dried to moisture
content of 8.8%, 1237 g
1: moisture included; 2: tar yield.
10.1016/j.wasman.2014.08.004
effective waste-to-energy convertor, MSW pyrolysis is receiving

increased attention in many counties and towns in China because
gas, oil and even char are needed in small cities and towns where
scarcity of commercial fuels is common. Dening standardized
products from MSW pyrolysis will help to normalize the pyrolysis
technology and enhance its application. Syngas, with a moderate
LHV and huge market, is a potential standardized product, especially in the places where fuel gas is needed for utility boilers
and domestic gas, a denition of syngas standard for its market
is necessary. Accordingly, the MSW pyrolysis process should be
formulated to provide high-quality gas and avoid oil output. In this
case, the multi-sectional reactor has the advantage of providing a
chance for product reforming, as indicated by Ohmukai et al.
(2008) and Zhao et al. (2011), and hot char can be used in one of
the reactor section to modify oil and promote gas yield (Wang
et al., 2014).
At the same time quality normalization for the char is also necessary if the pyrolysis alone is adopted.
4.7. Considerations for pyrolysis technology and product choice
Based on the above discussions, considerations for pyrolysis
technology and product choice for MSW pyrolysis can be summarised in Table 8:
From Table 8, it can be seen that the combined pyrolysis & gasication technology is a good choice for taking advantage of fuel
output other than heat from the pyrolysis system; however, the
single pyrolysis stage is cheaper in general, the qualities of the
products should be stipulated to facilitate its application. It is recommended that the combined pyrolysis & gasication technology
be used as the distributed MSW treatment method in cities that
can afford it. Pyrolysis alone may be adapted to the undeveloped
places, and measures such as raising the operation temperature,
separation of inappropriate components in the feedstock and adoption of efcient reactor should be taken to improve the product
qualities. To set up standards for the gas and/or the char is important to make those technologies practical.
5. Environmental effects of MSW pyrolysis
Traditional charcoal production kilns typically vent volatiles to
the atmosphere during operation, which gave this industry a bad
environmental reputation (Laird et al., 2009). In the modern pyrolysis process, all of the products are collected or recycled. Compared to incineration, the use of the MSW pyrolysis process
makes it markedly easier to reduce or avoid corrosion and emissions by retaining alkali and heavy metals (except mercury and
cadmium), sulphur and chlorine within the process residues, prevent large PCDD/F formation and reduce thermal NOx formation
due to the lower temperatures and reducing conditions used in
the process. Advantageously, the smaller fuel gas volume associated with pyrolysis requires lower-dimensioned gas cleanup
devices, which reduces investment and operation costs. However,
Cl and S species such as HCl and SO2 (or H2S) may still occur in
the fuel gas yielded, and other contaminants may exist in the liquid
and solid products. In this section, the emissions from the pyrolysis
process and the potential environmental impact related to pyrolysis product utilization are reviewed.
17
emission is completed at the low temperature stage (230

400 C), while the release of NH3 begins at 260 C and goes through
a much wider temperature range. In the temperature range of 300
to 600 C, a large amount of SO2 was detected. Therefore, not only
gas but also liquid products can be contaminated with NH3 and
SO2. Miskolczi et al. (2013) investigated contaminants in pyrolysis
products from MSW and MPW and found that pyrolysis oils had K,
S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; in the gas phase, S,
Cl and Br occurred. K, S, P Cl, Ca, Zn, Fe, Cr, Br, Sb and Pb were also
found in water scrubbing the gas. Compared with MSW oil, MPW
oil had much less S, Cl, Ca, Zn, Br and Sb. One of the most important
research studies conducted by Mohr et al. (1997) regarding the
behaviour of PCDD/F during the pyrolysis process compared the
PCDD/F input/output in a rotary kiln operating as a disposal facility
with that obtained with a laboratory-scale batch reactor and determined that approximately half of the input amount was found in
the pyrolysis products in both cases. More importantly, the formation of PCDD/F did occur even under the full-scale operating conditions, and due to the high levels of less chlorinated dioxins and
furans appearing in the process products of the rotary kiln, the toxicity equivalent (TE) of the output was approximately threefold
higher than that of the input, and 57% (by mass) of the total input
PCDD/F was in the oily condensate; for a batch-run laboratoryscale reactor, the TE of the output was almost 11-fold higher than
that of the input. Although the effects of temperature, residence
time and other conditions on the fate of PCDD/F during pyrolysis
need to be further investigated, the results of Mohr et al. (1997)
demonstrate that pyrolysis cannot be safely believed to be a
PCDD/F-inhibiting process. However, oil products should be used
with care because they can be contaminated with PCDD/F, and
the output of oil from MSW pyrolysis should either be avoided or
its destination stipulated beforehand.
PVC is an inevitably harmful component in MSW, which emits
HCl during pyrolysis, would cause corrosion to the facility and contaminate the gas and liquid products. Yuan et al. (2014) found that
HCl emission begins as soon as the melting of PVC occurs. However, HCl emission behaviour would be signicantly changed by
other components in the MSW, depending on whether these components enhanced or hindered heat transfer to PVC. In addition,
during MSW pyrolysis, HCl can be formed through the reaction
NaCl + H2O ? HCl + NaOH at higher temperatures, which is why a
diversity of HCl emission behaviours has been reported during
MSW pyrolysis (Bockhorn et al., 1998; Slapak et al., 2000; Kim,
2001; Ma et al., 2002; Zhu et al., 2008; Ren et al., 2009).
The char from MSW pyrolysis is accepted as a low grade fuel
instead of a waste stream. However the char from certain waste
pyrolysis processes can be toxic. Bernardo et al. (2010) reported
that char residues produced in the co-pyrolysis of different wastes
(plastics, pine biomass and used tyres) contained inorganic contaminants (Cd, Pb, Zn, Cu, Hg and As) and organic contaminants
(volatile aromatic hydrocarbons, alkyl phenols, etc.) and were classied as hazardous and ecotoxic wastes. Therefore industrial waste
streams are not suggested to mix with MSW in pyrolysis facilities
where char is output.
Due to contaminants appearing in the pyrolysis products, a single pyrolysis process should be equipped with products improving
facilities, thats why for commercial pyrolysis plants, combined
pyrolysis and gasication or/and combustion technologies were
adopted; in addition emission control devices were installed for
syngas or ue gas scrubbing.
5.1. Emissions and contaminants associated with the MSW pyrolysis

process
5.2. Pyrolysis-associated emission control technologies
MSW pyrolysis is combined with Cl, S and N emissions due to

the volatility of those elements. With the help of TG-FTIR, Chen
et al. (2008) found that, during the pyrolysis process of RDF, HCl
Numerous measures have been reported to alleviate the environmental effects associated with pyrolysis, including the interception of HCl, SO2, and NH3 from the gaseous phase, the use of
10.1016/j.wasman.2014.08.004
18
Table 8
MSW pyrolysis technology and product choice considerations.
Technology
Oil/wax
Gas
Char
Heat & power
Capacitya
Combined
pyrolysis &
gasication
Combined
pyrolysis &
combustion
(melting)
Not applicable
A suitable product; its quality standard

should be dened
Not applicable
Gas sent to boiler

or gas engine
Not applicable
Not applicable
Not applicable
Not applicable
Not applicable
Not applicable
The only choice,

but power
output is not
suitable for small
scale
Power is
generated by
steam turbine
Small,
moderate
and large
Small,
moderate
and large
If there is no centralized oil/wax renery near

the pyrolysis plant; try to consume it inside
the system. Its output is not recommended.
The operation temperature is suggested to be
600 C or higher
Recommended
A heavier, smaller volume of syngas with a
higher LHV has many advantages in the
energy markets. For example, using the
syngas in gas engines is practical
Quality should be standardized
To export char as
product,
standards of the
char should be
dened
Combined
pyrolysis,
gasication &
combustion
Pyrolysis alone
Applicable if
there is adjacent
boiler or
consumer
Moderate
to large
Small,
moderate
and large
Evaluated mainly with respect to capital cost.
catalysts to upgrade the quality of the products and the avoidance

of certain special components in the feedstock.
As shown in Table 3, industrial pyrolysis apparatuses adopting
gas engines are always installed with gas improving & scrubbing
devices because gas turbine or gas engine has more rigid requirements for syngas cleaning than boiler combustion (Arena, 2012).
An example of a gas improving & scrubbing system is the Thermoselect process list in Table 3; the Thermoselect process uses gasication for tar cracking and reforming. After completion of the
gasication stage, the synthesis gas exits the gasier at approximately 1200 C and ows into a water jet quench where it is
instantaneously cooled to below 95 C The rapid cooling prevents
the formation of dioxins and furans. Entrained particles, heavy
metals, chlorine (in the form of gaseous HC1) and uorine (in the
form of gaseous HF) are also abated in the quench. The pH value
of quench water is maintained at around 2 to ensure that heavy
metals are dissolved as chlorinated and uorinated species, so that
they are washed out of the crude synthesis gas. Following the
quench process, the synthesis gas ows into a demister and then
into alkaline scrubbers, where the remaining particulates and
HC1/HF are removed. Then the gas passes through a desulfurization scrubber for the removal of hydrogen sulde by direct conversion into elemental sulphur (H2S). The H2S scrubber is a packed
bed that is sprayed with scrubbing liquor consisting of water and
a dissolved Fe (3+) chelate that oxidizes the H2S to elemental S0
and water. In the last step the syngas is dried in a countercurrent
packed bed scrubber using tri-ethylene glycol liquor. The fully
cleaned syngas has very low concentrations of impurities; it can
then be conveyed to engines or turbines for electricity production.
Alternatively, the cleaned syngas can be converted to higher
molecular weight fuels in liquid state (Thermoselect, 2014). Not
all of the gas cleaning system is as comprehensive as that of Thermoselect process, if a conventional power plant is situated in the
near, the possibility to use the syngas in existing steam boilers
makes the cleaning step much simpler and cheaper.
To improve oil quality, Miskolczi et al. (2013) reported that the
concentrations of K, S, P, Cl and Br in the oil products could be
decreased by using catalysts. Bhaskar et al. (2002) investigated
the effect of catalysts on HCl removal from PVC pyrolysis and found
that CaC composite had a very strong absorbing effect on HCl,
reaching 63% of the theoretical value. Brebu et al. (2005) investigated the effect of catalysts on the pyrolysis of a plastics mixture
containing PE, PP, PS, a acrylonitrilebutadienestyrene copolymer
with a brominated ame retardant and antimony oxide synergist
(ABSBr) and PVC and reported that iron (FeOOH and FeC
composite) gave best results for the removal of bromine from the
decomposition oil, whereas catalysts based on calcium (CaCO3
and CaC composite) exhibited high efciency for chlorine
removal; however, both Fe- and Ca-catalysts were found to have
a low effect in nitrogen removal.
Dehalogenation prior to the decomposition of plastics is an
effective and simple procedure. The method of dehalogenating rst
and then decomposing plastics is essentially a two-stage pyrolysis
method characterized by the release of halogen hydrides at the low
pyrolysis temperature region and the decomposition of polymer
matrixes at the relatively high temperature region. Many dehalogenating reactors are screw melting devices. To remove HCl more
efciently at the lowest possible temperature and to prevent the
appearance of HCl in gas or oil products, Yuan et al. (2014) developed a uidized bed dehalogenation reactor prior to the main
pyrolysis reactor, and more than 99% of HCl can be removed at
temperatures not higher than 300 C within just a few minutes.
In addition, the separation of certain key components from
MSW would upgrade the pyrolysis quality. Zhao et al. (2011) investigated the transfer of Cl, S and N from food waste, paper and bre
to the oil products in a MPW pyrolysis process and found that the
presence of food waste would result in higher contents of Cl and S
in the oil and reduce the heat value of the pyrolysis oil at the same
time; therefore, the separation of food wastes was suggested.
As for char quality improvement, higher pyrolysis temperature
will help to reduce its volatile organic matter, increase its specic
surface area and LHV (Wang et al., 2012; Rajarao et al., 2014); and
streams with high heavy metal contents should be avoided feeding
to the pyrolyser.
Although many measures are reported, only syngas scrubbing
before combustion and the preparation of char for gasier are
available in practice. To improve the environmental prot by
applying MSW pyrolysis technologies to waste disposal, the char
and oil products need further characterization regarding their
environmental aspects, especially before permitting a single pyrolysis process.
6. Conclusion
As an effective waste-to-energy convertor, the MSW pyrolysis
system is increasing in demand recently as a distributed MSW
treatment method. A review of the literatures and technologies
related to the pyrolysis of MSW has shown that most the industrial
pyrolysis facilities are coupled with gasication or combustion
stage and they all equipped with gas scrubbing devices. The
10.1016/j.wasman.2014.08.004
reported pyrolysis reactors include xed-bed, rotary kiln, uidizedbed and tubular reactors, but only rotary kilns and tubular reactors
are applied to the scale-up facilities. The output products from the
commercial system are mainly power or heat; reformed syngas
and /or char is exported only in rare cases, but technologies for
exporting gas and /or char are more exible and desired. The yield
and composition of the products produced from the pyrolysis of
MSW and the individual components, in particular the oils and
gases, are largely affected by the feedstock, the pyrolysis temperature, the heating rate and the type of reactor adopted. The gas
yields from different feedstock are different and are known to
increase with increasing pyrolysis temperature but are generally
below 1 N m3 kg1 and have an averaged caloric value near
15 MJ N m3 in most cases when the pyrolysis temperature is
about 600 C or higher; thus, the gas is potential end product and
its standards should be stipulated. The liquid products from
MSW pyrolysis are chemically very complex, containing a remarkable fraction of water. Therefore, their output as the end product
should be avoided. To produce oil, MPW instead of MSW should
be used. The char from the pyrolysis of MSW is of high caloric
value and thus a potential solid fuel resource, but it could be contaminated with heavy metals and organic pollutants, standardizing
its LHV, heavy metal concentrations and pyrolysis temperature is
necessary. Since gaseous emissions of HCl, H2S, SO2 and NH3 are
related to MSW pyrolysis, and the products have potential contamination problems, emission control devices are always equipped
with pyrolysis facilities, and measures for improving the quality
of the gas, liquid and char products should be developed to make
MSW pyrolysis a more environmentally benecial process. To formulate the development and application of single stage pyrolysis
technology, standardized products other than heat or power
should be dened.
Acknowledgements
National Basic Research Program of China (No. 2011CB201500)
and Shanghai Municipal Science & Technology Commission Fund
for improving economy in the Yangtze River Delta region (Granted
No. 12195811100).
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Pyrolysis technologies for municipal solid waste: A review

D. Chen et al. / Waste Management xxx (2014) xxxxxx

Pyrolysis products from RDF from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

liquid production, and the state-of-the-art of this technology has

CxHyOz Q ! Char Liquid Gas H2 O

where W is the water content of the feedstock to the reactor, %;

D. Chen et al. / Waste Management xxx (2014) xxxxxx

where DT is the temperature difference between the reactor

Main results respect to pyrolysis behaviours and the products

MSW was decomposed in the 500900 C temperature

MSW, almond shells,

When to investigate kinetics of the primary decomposition and the tar

Font et al. (1995a,b)

Dry pellets of MSW

The nal temperature in the reactor was 850 C. For fast

A helium uidised sand-bed

9 components in MSW, An externally heated rotary

The bed temperature was varied from 500 to 900 C

An electrically heated xedbed reactor

Garcia et al. (1995a,b)

Wang et al. (2005a,b)

D. Chen et al. / Waste Management xxx (2014) xxxxxx

Main results respect to pyrolysis behaviours and the products

The pyrolysis temperature was increased from 400 to 700 C

MSW in the form of

Buah et al., 2007

The reactor bed temperature was varied from 600 to 900 C.

A xed-bed reactor heated

Slow pyrolysis was performed up to 550 C (with HR of 4 C/

A semi-batch reactor lled

Pyrolysis was performed up to 550 C (with HR of 2025 C/

MSW fractions and

Three-section reactor, with

The temperature inside the reactor was electrically heated up

A static batch reactor under

Luo et al., 2010b

Velghe et al., 2011

D. Chen et al. / Waste Management xxx (2014) xxxxxx

Zhao et al. (2011)

(continued on next page)

Miskolczi et al., 2013

and most of them have N2 ush to keep inert atmosphere, both of

The same as above

Ates et al. (2013)

Main results respect to pyrolysis behaviours and the products

Estimated by this article author according to the substance in reference text.

Fed with pre-treated materials

D. Chen et al. / Waste Management xxx (2014) xxxxxx

All of those MSW pyrolysis technologies accept pre-treated

D. Chen et al. / Waste Management xxx (2014) xxxxxx

standardized and not ready for the market. In those technologies

Ates et al. (2013), Miskolczi et al. (2013)

Metals, paper, organic

Gas sample bag

(continued on next page)

D. Chen et al. / Waste Management xxx (2014) xxxxxx

Fluidised-bed pyrolysis system

Marculescu et al. (2007)

Process gases analysis

Treatment gas inlet

Solid residue analysis