Waste Management 37 (2015) 116–136

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Review

Reprint of: Pyrolysis technologies for municipal solid waste: A review q

Dezhen Chen a,⇑, Lijie Yin a, Huan Wang a, Pinjing He b
a
Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092, China
b
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 a b s t r a c t

Article history: Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW)
Received 23 February 2014 disposal that allows energy and resource recovery; however, it has seldom been applied independently
Accepted 1 August 2014 with the output of pyrolysis products as end products. This review addresses the state-of-the-art of
Available online 17 February 2015
MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this
review, first, the influence of important operating parameters such as final temperature, heating rate
Keywords: (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then
Municipal solid waste (MSW)
the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third,
Pyrolysis
Reactor
the yields and main properties of the pyrolytic products from individual MSW components, refuse-
Product derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emis-
Environmental impact sions 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-to-
energy 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.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2. Pyrolysis behaviours of MSW with respect to products and the influential factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.1. Terminology and scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.2. Factors influencing MSW pyrolysis behaviours and products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3. Pyrolysis technologies and the reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.1. Pyrolysis technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.2. Pyrolysis reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
3.2.1. Fixed-bed reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.2.2. Rotary kiln reactors and their systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.2.3. Fluidised-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.2.4. Tubular reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.2.5. Other pyrolysis reactors and technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4. Products from pyrolysis of typical MSW components and MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.1. Pyrolysis products from waste paper. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

Abbreviations: HCs, hydrocarbons; HDPE, high-density polyethylene; HHV, higher heat value, the same meaning as gross calorific 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.
DOI of original article: http://dx.doi.org/10.1016/j.wasman.2014.08.004
q
This article is a reprint of a previously published article. The article is reprinted here for the reader’s convenience and for the continuity of the special issue. For citation
purposes, please use the original publication details; D. Chen et al./Waste Management 34 (2014) 2466–2486 DOI of original item: 10.1016/j.wasman.2014.08.004.
⇑ Corresponding author. Tel.: +86 21 6598 5009.
E-mail address: chendezhen@tongji.edu.cn (D. Chen).

http://dx.doi.org/10.1016/j.wasman.2015.01.022
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
 D. Chen et al. / Waste Management 37 (2015) 116–136 117

4.2. Pyrolysis products from MPW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

4.3. Pyrolysis products from wood and woody mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
4.4. Pyrolysis products from fallen leaves and vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.5. Pyrolysis products from RDF from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.6. Pyrolysis products from MSW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.6.1. Properties of gas products from MSW. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.6.2. Liquid products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.6.3. Solid products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.6.4. Standardized product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.7. Considerations for pyrolysis technology and product choice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5. Environmental effects of MSW pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.1. Emissions and contaminants associated with the MSW pyrolysis process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.2. Pyrolysis-associated emission control technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

1. Introduction Balasubramanian, 2012). These reviews facilitate making the

The treatment, management and disposal of municipal solid
waste (MSW) are common concerns in every country. MSW pyro-
lysis 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 incinera-
tion 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 pyroly-
sis-involved treatment technique for MSW (Saffarzadeh et al.,
2006).
In general, pyrolysis represents a process of thermal degrada-
tion of the waste in the total absence of air that produces recycla-
ble 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
flexible. 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 difficulty in finding
new sites for incinerators and landfills. Generally distributed
MSW treatment facilities are difficult to ensure environmental
safety due to capital cost limitations; while pyrolysis plants of
proper capacity with energy products output are suitable alterna-
tive when the quality of char, oil/wax and combustible gases is
under fine 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 (Martínez et al.,
2013); and the mechanism investigation or kinetics modelling of
the pyrolysis process (Al-Salem et al., 2010; Quek and
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
liquid production, and the state-of-the-art of this technology has
also been addressed in a recent review (Fonts et al., 2012). How-
ever, compared to waste types such as tyres, plastics and sewage
sludge, MSW is more heterogeneous in composition and size. Cur-
rently, for MSW pyrolysis, information on technology develop-
ment, characterization of products and correlated pollution is not
sufficient to support technology application and system design,
especially in regards to environmental impacts, which is funda-
mental 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 pol-
lutants involved with the MSW pyrolysis process and product
applications, and the reported measures to alleviate the associated
environmental impacts. The final aim is to provide essential infor-
mation 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 influential factors
2.1. Terminology and scope
Reactions take place in a recognized pyrolysis process can be
expressed as:
CxHyOz þ Q ! Char þ Liquid þ Gas þ H2 O ð1Þ
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 cal-
culated as:
1
Q 1 ¼ W  2260; kJ kg ð2Þ
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 separated before pyrolysis. In addition, in order to reduce this
portion of energy a drying step is usually adopted in front of pyro-
lysis reactor.
 Caloric requirement of pyrolysis Q2
118 D. Chen et al. / Waste Management 37 (2015) 116–136
The caloric requirement of the pyrolysis is calculated using the
following equation (Raveendran et al., 1996):
Z Z Z From Table 1 it can be seen that the reported pyrolysis temper-
Q 2 ¼ C p;M mM dT þ C p;ch mch dT þ C p;v mv dT þ Q p ; kJ kg
1
ð3Þ
where Cp,M, Cp,ch, Cp,v are the specific 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 pyro-
lysis, J kg1. Q2 can be obtained through differential scanning calo-
rimetry (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 reac-
tor, 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 radi-
ation 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 influencing 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 individ-
ual 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; Atesß 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;
Atesß 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; Sørum 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.
ature varied from 300 to 900 °C, but the typical running tempera-
ture is around 500–550 °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 com-
plex impact of residence time on products can be deduced from Eq.
(1): in a longer residence time, more heat is input into 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 impor-
tant 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 res-
idence 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:
DT  a 
HR ¼ ; C S1 ð4Þ
m  Cp
where DT is the temperature difference between the reactor
wall and the feedstock, °C; a is heat transfer coefficient 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 specific 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 flash
pyrolysis, as shown in Table 1. While in a practical and continu-
ously running reactor HR is decided by the reactor type which is
characterized with its special temperature difference (DT) and heat
transfer coefficient (a) features. The pyrolysis reactors reported in
the literatures are mainly fixed-bed reactors, rotary kilns and fluid-
ised bed reactors, as shown in Table 2; they are of a sequence in
ascending order according to HR. The fluidised bed reactors are
characterized with very high heat transfer coefficient of 112–559
(J/s m2 K) (Garcia et al., 1995a). But very few reports are available
on heat transfer coefficients for MSW pyrolysis in rotary kilns and
fixed-bed reactors, as they are affected by many factors; and they
are also the company’s private know-how for designing and run-
ning pyrolysis reactors. The transport tube thermo-chemical con-
vertor in Table 2 shows a new reactor type, it belongs to a family
of tubular reactor, which will be discussed later.
As for the influence 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
Table 1
Pyrolysis behaviours and products under different reaction conditions.

Reaction conditions
MSW was decomposed in the 500–900 °C temperature
range, and the lignin was decomposed in the range of
600–900 °C
Sample mass for the fluidised-bed reactor was 1–3 g (at
temperatures greater than 700 °C) or 0–30 g in the
remaining cases. Particle size of PE was 0.5 cm. Almond
shells was 0.297–0.500 mm in particle size. MSW sample
was 0.8–5 g and ground
No information on residence time and heating rate (HR)
The reactor was running at high nominal temperatures
(700–850 °C) batch by batch
Feedstock Reactor type
MSW, almond shells, An analytical Pyroprobe
lignin and apparatus, and a fluidised
polyethylene sand bed reactor
Dry pellets of MSW A helium fluidised sand-bed
reactor
Main results respect to pyrolysis behaviours and the products Reference
When to investigate kinetics of the primary decomposition and the tar Font et al. (1995a,b)
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 flash pyrolysis in fluidised-bed reactor results in a high gas
yield
For pyrolysis products in the fluidised 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 coefficients in the sand fluidised-bed reactor for MSW Garcia et al. (1995a,b)
pyrolysis was reported to be 112–559 (J/s m2 K)

D. Chen et al. / Waste Management 37 (2015) 116–136

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: 0.8–5 g
Residence time: approximately 20 min
The final temperature in the reactor was 850 °C. For fast
pyrolysis, the reactor was heated to 850 °C first, and then,
the sample was fed. For slow pyrolysis the MSW
components was heated together with the reactor wall
HR: 5–60 °C min1*
Sample mass: 1000 g per batch
Residence time: 7–15 min
The reactor was heated up after materials were fed. The final 9 components in MSW, An electrically heated fixed-
temperature was changed from 300 to 700 °C crushed to less than bed reactor with N2 flush in
HR: not mentioned 10 mm and then mixed the beginning
Sample mass: 600 g per batch
Residence time: 55–180 min depending on the temperature
The bed temperature was varied from 500 to 900 °C
Sample mass: 1000 g per batch
Sample size: less than 5 cm
HR: not mentioned
Residence time: up to 50 min
Around 70–80% 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 (700–850 °C) and to explore the influence 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%
9 components in MSW, An externally heated rotary When investigate the yield and the calorific value of the syngas changing with Li et al. (1999a)
pre-treated kiln running at 3r min1 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 calorific value of the syngas was in
the range of 13000–23000 kJ kg1.
Smaller size did not match the higher syngas yield
When investigate the yields of pyrolysis products varying with final Wang et al. (2005a,b)
temperature, the researchers found that the char yield decreased with the
increase of temperature, especially within the temperature range 300–550 °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
Wood, paper, An electrically heated fixed- When investigate the production distribution, the gas characteristics, the Jiang, 2006
municipal plastic bed reactor pyrolysis gas quality, the characteristics of the pyrolysis liquids and char, the
waste and crushed researchers found that the pyrolysis temperature is the top-drawer parameter
MSW 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 calorific value of pyrolysis gas has a maximum within the
testing range, whereas the calorific value of char displays an increasing trend.
The liquid products are rich in moisture and volatiles, and the gross content of
the fixed carbon and ash in liquid is less than 3%

119
(continued on next page)
 120
Table 1 (continued)

Reaction conditions Feedstock Reactor type Main results respect to pyrolysis behaviours and the products Reference
The pyrolysis temperature was increased from 400 to 700 °C MSW in the form of A fixed-bed reactor It has been found that the yield and composition of the pyrolysis products Buah et al., 2007
HR: 10 K min1 refuse-derived fuel constructed of stainless depended on temperature. The char yield fell as the pyrolysis temperature was
Sample mass: 15 g per batch (RDF) pellets with a steel and it was externally increased from 400 °C to 700 °C, whereas that of oil/wax and gaseous products
Residence time: estimated to be 40–70 min* particle size of heated by an electrical ring rose. The chars recovered were also found to have properties that depended on
approximately 8 mm furnace 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 calorific 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
The reactor bed temperature was varied from 600 to 900 °C. Prepared MSW of A fixed-bed reactor heated When to evaluate the effects of particle size at different bed temperatures on Luo et al., 2010b
When the desired temperatures were achieved in the uniform size in three by an electrical ring furnace product yield and composition during MSW pyrolysis, it was found that higher
reactor, the screw feeder was turned on to feed material groups: smaller than with a screw feeder at top of temperature resulted in higher gas yields with less tar and char, and dry gas
into the reactor with a flow rate of 5 g min1 5 mm, between 5 and the reactor yield increased with a decrease in particle size, and the char and tar yield
No information was available for the residence time and HR 10 mm and between 10 decreased. The differences due to particle sizes in pyrolysis and gasification

D. Chen et al. / Waste Management 37 (2015) 116–136

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 flow rate of 24 g/min or 12 g/min
Pyrolysis was performed up to 550 °C (with HR of 20–25 °C/
min) in a 30 min process
Sample mass: 1000 g per batch
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
and 20 mm
MSW cut in 2 mm A semi-batch reactor filled
pieces and oven dried with hot sand as a heat
at 110 °C before transfer medium under N2
pyrolysis atmosphere; A Archimedes’
screw ensures good mixing
of the samples and the sand
and creates a ‘fluidized bed
effect’
MSW fractions and Three-section reactor, with
mixed waste plastics individual temperature
controls at different
sections, batch run or
continuous operation
PE (representative for A static batch reactor under
plastic materials in a N2 atmosphere
MSW), paper and
bamboo
(representative for
wood & biomass in
MSW)
performance practically disappeared at the highest temperatures tested.
Smaller particle sizes resulted in higher H2 and CO contents for both pyrolysis
and gasification of MSW. Minimising the size of raw materials is an alternative
method to improve the gas quality of MSW pyrolysis and gasification
This research was to investigate the effect of reactor temperature and HR on Velghe et al., 2011
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 findings 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, Zhao et al. (2011)
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 Pan, 2012
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
 D. Chen et al. / Waste Management 37 (2015) 116–136 121

was minimal (Luo et al., 2010b) due to the lower HR effect corre-
lated to coarser particle size was compensated by the increase of

Miskolczi et al., 2013

the radiation contribution to heat transfer. Basically the influence
Atesß et al. (2013)

of particle size is a combination of HR and the interaction between

the volatile matter and the char, the latter takes place when the
Reference

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,
amounts of pyrolysis oils were decreased when using catalysts. Comparing the

MSW. Both the carbon frame and double bond isomerisation occurred during
and most of them have N2 flush to keep inert atmosphere, both of
It has been found that viscosity, average molecular length and contaminant
properties for both thermal pyrolysis and thermo-catalytic pyrolysis. It was

two raw materials, the catalysts displayed higher activity using MPW than
found that gases contained hydrogen and hydrocarbons; CO and CO2 were

thermo-catalytic pyrolysis. The morphology and texture of the chars were

obtained only from MSW; aromatic and cyclic compounds predominantly

them affect the final product yields. Tar would continue cracking
This research was to characterize product yields, gas and pyrolysis oil

formed in the presence of catalysts, and the catalytic effect was more

during the cooling period if the temperature is not too low (Font
et al., 1995a), therefore a slow cooling of volatile from a high tem-
perature reactor would result in higher gas yield; fast and deep
Main results respect to pyrolysis behaviours and the products

cooling of the volatile would gain higher liquid yield and it is also
preferable to obtain cleaner gas. As for N2 flush, it changed the flow
rate and residence time of the volatile in the reactor, and the cool-
modified by catalysts, especially by Ni–Mo catalysts

ing of the volatile was interfered too, so data obtained from those
systems with N2 flush may deviate from practice.

3. Pyrolysis technologies and the reactors

3.1. Pyrolysis technologies

The concept of pyrolysis technology can be represented by

significant using MPW

RWE-ConThermÒ 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 pro-
cesses and technologies available in European market from the
point view of energy efficiency, some of these processes with their
updated information and the presently available commercial, dem-
onstration or pilot technologies are summarized in Table 3 from
A batch fixed reactor, N2

the point view of technologies details and emissions abatement.

It can be seen that the existing commercial pyrolysis technologies
The same as above

are characterized with the following configurations:

Reactor type

 Combined technologies
flushed

The existing commercial pyrolysis technologies seldom run

alone with gas, tar and char output as end products, most of them
(MPW) in particles less

are combined with gasification, combustion and smelting; and the

than 10 mm in main
mixed plastic waste

The same as above

Crushed MSW and

combination with gasification produces moderate-calorific-valued

dimension with &
without catalysts

fuel gas, it still receives extensive attention in waste-to-energy

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

processes in recent studies (Smith et al., 2001; Li et al., 2007; Yi,

Feedstock

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 reactor was heated to 500, 550 and 600 °C for thermal

Fully decomposition of MPW pyrolysis have higher time

Residence time: 5239 s for MSW at 500 °C in absence of
catalyst; in the range of 4331–5110 s using catalysts.

necessity than MSW in absence of catalyst; 6652 s at

 Fed with pre-treated materials

pyrolysis and 500 °C for thermo-catalytic pyrolysis

500 °C, 5299 s at 550 °C and 4187 s at 600 °C

All of those MSW pyrolysis technologies accept pre-treated

MSW instead of raw MSW in its original state, suggesting pre-
treatment is a necessary step for pyrolysis technology. The pre-
treatment 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
Sample mass: 50 g per batch

to the reactor.
The above RWE-ConThermÒ plant (Hamm) is no longer in oper-
No information on HR

ation after the chimney collapse in December 2009. The accident

Reaction conditions

The same as above

was analysed to be caused by the feeding waste material, for the

Table 1 (continued)

feed composition did not match the process as designed, resulting

in process temperatures beyond tolerable limits. However prepara-
tion of input waste stream to match the process could be too
expensive to be beyond profitability. A process flexible to the
waste input is more practical, and combination of pyrolysis and
*
122 D. Chen et al. / Waste Management 37 (2015) 116–136

Table 2
Typical MSW pyrolysis reactors and system in literatures.

Pyrolysis reactor and system in researches Reference

waste collection Atesß et al. (2013), Miskolczi et al. (2013)

waste separation Metals, paper, organic

waste, etc
Shredding

Crushing Gases
3
6

4 5
7 2 Pyrolysis oil

1 4

Char
Water
Fixed-bed reactor and pyrolysis system (1-N2 bottle; 2-reactor; 3-heat exchanger; 4-separation unit,
5-water trap; 6-gas flow meter; 7-rotameter)
7 Wang et al. (2005b)
10
3 11

5 9
8
8
8

4 1
6
2
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-filter; 10-accumulative
flowmeter; 11-computer; 12-gas sampling device; 13-feed and discharge opening; 14-speed
adjustable electrical machinery)
Williams and Williams (1999a)
Feed Hopper

TC Gas sample bag

De-mister
Pyrolysis TC
reactor Cyclone
TC
TC
Glass wool
Fluidised TC Catch trap
bed pot
Distributer
CO2/ acetone
condensers

Gas pre-heater
 D. Chen et al. / Waste Management 37 (2015) 116–136 123

Table 2 (continued)

Pyrolysis reactor and system in researches Reference

Fluidised-bed pyrolysis system

Process gases analysis Marculescu et al. (2007)
Alimentation with Natural gas
towards burner and treatment
divided solid

Heated case

Transport tube

Treatment gas inlet

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

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 Pyrolysis coke to
5.Material sluice 6.Rotary pyrolysis Inerts boiler
7.Burner system Metals
8.Solid residue discharge
9.Fan
10.Cyclone(dedusting)

Fig. 1. Schematic flow sheet of RWE-ConThermÒ process (Tech Trade, 2014).

gasification stage and independent utilization of the pyrolysis

products serve the necessity of process flexibility.
 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
standardized and not ready for the market. In those technologies
with pyrolysis gases exported to gas engine, gasification acts as pri-
mary processing, and gas scrubbing is followed to ensure the qual-
ity 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. Some-
time 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 temper-
ature combustion inside the system is a suitable choice.
 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 flue gas emission control devices
include particulate filters, 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 pro-
duced in the pyrolysis process. The hot flue 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 decomposi-
tion and gasification. The pilot tests were based on an artificially
assembled MSW with the following composition: rubber 8.27%,
PVC 8.51%, PE 8.51%, kitchen waste 24.33%, pericarp14.60%, vegeta-
124 D. Chen et al. / Waste Management 37 (2015) 116–136

Table 3
Main pyrolysis involved units and technologies used in pilot, demonstration and industrial plants.

Process name Reactor & operation conditions
PYROPLEQÒ process Rotary drum, pyrolysis at 450–
(Bracker et al., 1998; 500 °C; syngas was burnt at
Modern Power 1200 °C and the hot gas from the
Systems, 2014) combustion chamber heats the
pyrolysis drum from the outside
ConThermÒ technology Rotary kilns, pyrolysis taking
(Tech Trade, 2014; place at 500–550 °C for about
Hauk et al., 2004) 1 h, gas combustion in a
pulverised coal (PC)-fired boiler,
see Fig. 1
Gibros PEC Process or Rotary kiln, pyrolysis at 500–
PKA technology in 550 °C, for approximately 45–
Germany (IEA 60 min, the kiln was externally
Bioenergy, 2004) heated with part of the gas
produced in the process
The pyrolysis gases containing
tars are subsequently gasified in
a high temperature (1200–
1300 °C) gasifier; char is smelted
(at 1400–1500 °C)
EDDITh process A rotary kiln running at 450–
(Martin et al., 1998; 600 °C for 45 min; gas is
Malkow 2004) combusted at approximately
1100 °C with air coming from
the dryer while the char
undergoes separation and
materials filtering
Noell-KRC conversion A rotary kiln and a gasifier,
process (now Future pyrolysis at approximately
Energy) (Malkow, 550 °C, gasification at 1400–
2004; Jaeger and 2000 °C and 2–50 bars
Mayer, 2000)
Serpac technology Two interconnected chambers of Input: Mixed waste, MSW,
(Malkow, 2004) cylindrical and conical shape,
inclined and rotary. Pyrolysis at Output: steam; ash and
600–700 °C, char gasification
with air at about approximately
800 oC; gas is combusted at
approximately 1100–1200 °C
Siemens Schwel-Brenn A rotating drum and a high
technology temperature furnace coupled
(Malkow, 2004; with a steam boiler, pyrolysis at Output: Energy in form of
Richers and 450 °C for approximately 1 h;
Bergfeldt, 1996) the finer carbon-enriched (30%) and ash
fraction is ground to 0.1 mm and
combusted together with the gas
in the slagging furnace at
1300 °C
Mitsui R21 Process, a Rotary drum running at 450 °C, Input: MSW is shredded into
branch of Siemens gas combustion at 1300 °C
Schwel-Brenn
technology. (IEA
Bioenergy, 2002)
Takuma SBV(Kawai, Rotary kiln and ash-melting
2009) (Derived from system. Pyrolysis at 500–550 °C sewage sludge, etc.
the above Siemens in the rotary kiln; pyrolysis gas is Output: Energy (power &
Schwel-Brenn burnt in a high temperature
process) chamber
Materials input & products
Input: Pre-treated domestic
refuse; MPW
Output: The char with
calorific value of around
10 GJ t1. Power from steam
turbine
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
Output: CO/H2-rich fuel gas,
metals, basalt
Input: Shredded MSW,
industrial waste and sludge
Output: Gas (12 MJ kg1),
coke (16 MJ kg1, CARBORÒ),
metals, salts, mainly CaCl2
and NaCl, APC residues. Gas is
burnt for heat and power
generation
Input: MSW, other feedstocks
(dried sewage sludges) may
be co-gasified
Output: Medium calorific
value gas; a part of the
cleaned gas is used to heat the
kiln. Metals and slag can be
used as construction
materials
industrial and hospital waste
metals
Input: Tyres, MSW, sewage
sludge, industrial wastes
steam or power. Metals, glass
less than 200 mm in length
Output: power generation
from pyrolysis gas
combustion; char, ferrous and
non-ferrous metals;
production of a fused ash
product.
Input: MSW, industry waste,
steam), iron, aluminium
Technologies Application Environmental protection
example device
Pyrolysis & The Ticino Canton Hot-gas filtration by means of
combustion waste treatment ceramic filter cartridges. Lime is
centre in Switzerland added to the reactor for acid gas
removal. Conventional flue gas
clean up with a bag filter for fly
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 landfill
disposal
Pyrolysis & The Hamm power- The pyrolysis gas passed through
combustion plant, Germany, with a cyclone before boiler
capacity of 100 kt/ Flue gas scrubbing system of the
year. Stopped coal-fired power plant
A combination Aalen, Germany, with Gas scrubbing unit to wash out
of pyrolysis, capacity of 25,000 inorganic acid pollutants,
gasification tons per year followed by a bag filter to
(thermal remove the remaining dust; and
cracking), and a basic and a biological washer
smelting to remove H2S. Finally, an active
coal filter to absorb dioxins,
furans, and Hg
Pyrolysis & Arras, France, with The flue gases produced by the
combustion capacity of 50,000 tpa combustion of the thermolysis
gases need a deduster and
rational scrubbing system
Pyrolysis and Freiberg, Germany, Pyrolysis gas is dedusted and
entrained flow with capacity of dewatered before entering the
gasification 12,000 tpa sewage gasifier. There are two scrubbers
sludge + 5760 tpa to clean gas from the gasifier.
MSW. Demonstration The first stage removes H2S and
plant heavy metals, and the second
stage washes all of the other
contaminants
Pyrolysis, Keflavic, Iceland, with Rational scrubbing techniques
gasification & capacity of 45 tons for fuel gas and flue gas
combustion per day
A combination Fürth, Germany, with Dust collection and flue gas
of pyrolysis and capacity of 100.000– scrubber
high 150.000 kt/y, Shut
temperature down August 1998
combustion after accident with
pyrolysis gas
A combination Yame Seibu Plant, Flue Gas cooler followed by two
of pyrolysis Japan, with capacity bag filters in series: No.1 for
gasification & of 220 t/d, etc. particulate collection and
melting process recycling of ashes to the
combustor, and No. 2 with dry
lime injection for acid gas
emission control, with landfill
disposal of the solid residues
A combination Kakegawa Plant, Flue gas quencher followed by
of pyrolysis and Japan, with capacity two scrubber stag
gasification & of 140 t/d MSW
melting process
 D. Chen et al. / Waste Management 37 (2015) 116–136 125

Table 3 (continued)

Process name Reactor & operation conditions
Thermoselect process Moving channel bed. The process
(Malkow, 2004; consists of shredding, in the
Thermoselect S.A., ‘channel’ MSW is heated from 50
2000) to 600 °C and pyrolyses,
followed by gasification at 1200–
2000 °C
Von Roll RCP A forward reciprocating grate
technology furnace as a pyrolysis
(Malkow, 2004; (degassing) chamber; the
Hesseling, 2002) 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
fluidised-bed furnace
Compact Power Pyrolysis in the two tubular
process (now Ethos reactors at 800 °C; the char is
Renewables reacted with steam and air in a
Avonmouth (ERA) fixed bed gasifier, and gas
Limited) (Malkow, combustion is in a cyclone
2004) chamber at 1200–1250 °C
A gasification-coupled pyrolysis
Pilot pyrolysis process
process. The main reactor is a
in Tianjin, China (Li
et al., 2007) screw-bed reactor, and
gasification 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 400–450 °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
convertor heated by circulation of hot flue-
(Marculescu et al., gases (natural gas burner) within
2007) an external double envelope. The
solid continuously advances by
vibro-fluidised transport
Flow rate up to 50 kg/h
Running from pyrolysis to
combustion with temperature
changing from 400 to 1000 °C.
See Table 2
Materials input & products
Input: Unsorted domestic
waste, shredded
Output: Medium calorific
value gas, a part of cleaned
gas is used to heat the
channel. Mineral and metals
from the smelt slag
Input: Pre-treated MSW,
residual waste from recycling, of pyrolysis and Germany, a pilot
industrial waste
Output: Metal, slag; energy in combustion
form of steam or power
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 gasification
unit
Input: pre-treated MSW
Output: syngas with
moderate to low calorific
value, char, metals and ash
Input: Raw MSW with bottles, Pyrolysis alone
stones, bricks and glass
separated
Output: Oil, char, cleaned gas
(for power generation)
Input: Ground MSW
Output: Syngas or flue gas
depending on whether
comburant or inert gas is
supplied; accordingly char or
ash output
Technologies Application Environmental protection
example device
A combination Mutsu, Japan, with A water jet quenching section is
of pyrolysis and capacity of 50,000 tpaused to avoid the formation of
gasification & dioxins, and an acid gas scrubber
melting process 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 filter is installed to act as
a final polishing unit for the
synthesis gas
A combination Bremerhaven, Particulate emission control
systems and acid gas scrubbing
melting & plant with capacity of equipment used in a common
6 t/h MSW power generation system
Pyrolysis, Avonmouth, UK, with Dry scrubber with sodium
gasification and capacity of 8000 tpa. bicarbonate and Selective
high (Mainly clinical waste Catalytic NOx Reduction (SCR).
temperature now) The solid residues from the dry
combustion scrubbing unit are sent for
landfill disposal
Pyrolysis & Tianjin, China, with Gas cooler and filter
partial capacity of 200 kg h1
gasification
Shanghai, China, with Pyrolysis gas was scrubbed
capacity of 100 ton/d, before burning. Char was
demonstration plant quenched and separated from
metals
Pyrolysis alone Pilot test facility Not mentioned

bles 7.30%, cloth 5.35%, paper 18.25% and sawdust 4.87%. The
results revealed that as the temperature in the main reactor chan-
ged 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 calorific 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 prod-
ucts; 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)
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 con-
tent 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
126 D. Chen et al. / Waste Management 37 (2015) 116–136

Fig. 2. Schematic of the pilot MSW pyrolysis plant in Tianjin, China (Li et al., 2007).

Drying section

Collecting and seperating systems for

T gas,oil and water

Purified Gas
Oil
Wastes
Gas engine
Chartank Gas
Char discharge P

Automatic
Control System

Fig. 3. Honghoo technology schematic (Chen et al., 2013) (I, II and III are the first, second and third section of the pyrolysis reactor, respectively, and IV is the char cooling
drum).

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 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 fixed-bed
reactors, rotary kilns, fluidised 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 cir-
cuit board disposal (Peng et al., 2006; Li et al., 2009). Although vac-
uum 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,
 D. Chen et al. / Waste Management 37 (2015) 116–136
achieving vacuum pyrolysis is difficult 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.
3.2.1. Fixed-bed reactor
The fixed-bed reactor is characterized by a low HR, as the result
of its low heat transfer coefficient, as shown by Eq. (4). Therefore,
when a greater sample mass is tested, the temperature is not uni-
form inside the sample (Wang et al., 2006), and the feedstock is
decomposed at different temperatures simultaneously. Fixed-bed
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 inefficiency this reactor is seldom
adopted in scale-up facilities.
3.2.2. Rotary kiln reactors and their systems
The rotary kiln is more efficient than the fixed-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
used, but they are typical reactors used for conventional pyrolysis
(slow pyrolysis), which proceeds under a slow HR with significant
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 pyro-
lysis, 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. How-
ever, 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 flexible adjustment
of residence time and larger channel for the waste stream allow
feeding of heterogeneous materials, and thus, extensive pre-treat-
ment of wastes is not required, and its maintenance is also simple.
Rotary kilns for pyrolysis are externally heated using com-
busted 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 geom-
etry characteristics (i.e., roughness of kiln wall, exit end dam and
internal structures) and operational parameters (i.e., kiln inclina-
tion and rotational speed) on both material residence time (MRT)
and material volumetric flow (MVF); and then proposed a set of
simplified 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 coeffi-
cients 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 fre-
quently used to describe the influence of temperature and resi-
dence time on pyrolysis behaviour and products (Williams and
Williams, 1999a; Mastral et al., 2002, 2003; Dai et al., 2001a,b).
Typically, fluidised-bed reactors are used to investigate the behav-
iours of fast pyrolysis (or flash pyrolysis) and to explore the sec-
ondary cracking of tar at longer residence times.
Although fluidised-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 mate-
127
rial 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 fluidised-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, fluidised-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, conclud-
ing that the fluidised-bed technology appears mature and particu-
larly attractive for plastic waste pyrolysis. As for its application to
MSW pyrolysis, in addition to the problems of bed material separa-
tion, external heating and recirculation, fluidising 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 fixed 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-fluidised transport
(Marculescu et al., 2007), as shown in Fig. 4; and a tube with an
inner mixer (Walendziewski, 2002). In Table 3, the pyrolysis reac-
tors 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 coefficient is known because of its simplicity and safety. As
a typical tubular reactor, the screw tube, with its lower construc-
tion and operation costs, has great future prospects. For this design,
the screw speed can be varied within 0.5–25 rpm, thereby chang-
ing 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
fluidised-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 trans-
fer coefficients are not well defined for different waste types.
In a conclusion, adaptability of different reactors to MSW pyro-
lysis 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 prod-
ucts 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 first 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 first 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
128 D. Chen et al. / Waste Management 37 (2015) 116–136
Table 4
Adaptability of different reactors to MSW pyrolysis.
Reactor type Running experiences Requirements on Capacity
material
preparation
Fixed-bed reactor Running in batch, only Almost no Small, may not
in laboratory requirements exceed several
researches except for energy- tons per day
saving purpose
Rotary kiln Most common Not rigid Large, up to
150,000 tpa
Fluidised-bed Only for laboratory Very rigid Large
reactor researches, no theoretically
practical experiences
for MSW
Tubular reactor A few Rigid Moderate, up
to 50,000 tpa
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 flue 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 sup-
ply, which converts waste into a synthetic gas (mainly CO and H2)
and other end-products, such as a vitrified matrix. The highly effi-
cient 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 reac-
tion volume and especially optimum composition of produced syn-
gas. 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 MSW applica-
tion, 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 homoge-
nous wastes such as sludge, shredded plastics and tyres. It is a type
of microwave dielectric heating method, and its main advantages
include rapid, efficient in-core volumetric heating for direct cou-
pling of microwave energy with the molecules that are present
in the reactants, easily controlled and maintained desired temper-
ature of pyrolysis for desired product raising, lower temperatures
for the reaction vessel (or material surface) and higher tempera-
tures 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 fine to
fulfil the requirements, and achieving accurate temperature con-
trol in a microwave reactor is dependent on accurate dielectric
data in the microwave frequency range as a function of tempera-
ture, which is not available for most of waste components. In addi-
tion, 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 rela-
tively small treatment capacity, the application of microwave
pyrolysis to heterogeneous MSW is not practical in the near future.
Maintenance Flexibility to Application recommendation
requirement operation parameters’
change
Low, but batch by Excellent flexibility Not recommended for
batch operation industrial application
demanding manual
labour
Low to moderate Good flexibility Recommended but efficiency
should be improved; multi-
sectional reactor suggested
Highest Very limited to size Heating system should be
change; good improved before application
flexibility to to MSW pyrolysis
temperature, etc.
Moderate to high Limited to size and Recommended, especially
temperature change the multi-sectional tubular
reactor
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 refinery
processes. The use of catalysts in pyrolysis presents some advanta-
ges 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 refin-
eries (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 cat-
alysts cannot be subsequently recycled. In addition, the catalytic
effects are usually not sufficient; more significant 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.
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 compo-
nents will help to elucidate the products from practical MSW pyro-
lysis 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 (C1–3, C4, C5, C6, 1-ring, C10–12, levoglucosan,
 D. Chen et al. / Waste Management 37 (2015) 116–136 129

C13–15, and C16–18), 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 tempera-
ture range of 290–540 °C (563–813 K). The tar yield was approxi-
mately 47.03% at 450 °C and a heating rate of 10 °C min1. There
were four main different compounds they identified 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 gasification, especially at higher tem-
perature, but pyrolysis was more flexible compared with gasifica-
tion regarding the temperature. In a relatively large-scale
laboratory study based on a fixed-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 400–850 °C, which is much higher than
the LHV of syngas from gasification, 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 waste paper pyrolysis 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 first 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 com-
ponents 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 fluidised-bed reac-
tor running at moderate temperature (approximately 500 °C), the
volatiles can be extracted immediately before the secondary crack-
ing takes place, and a higher yield of liquid products can be
expected. Whereas in a high-temperature fluidised bed (for exam-
ple 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 fixed-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 prod-
uct, 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, ben-
zene and toluene without CO, CO2 or HCl appearance for PE, PP
and PS. Therefore, gas products are of high calorific value. PVC is
regarded as a harmful component in the MPW, as HCl evolves dur-
ing 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 chlo-
rine from HCs.
In contrast to biomass, MPW in MSW requires a higher
temperature to finish its pyrolysis. Within the conventional pyroly-
sis temperature range of 500–550 °C for rotary kilns oil is the main
product of MPW; and MSW rich in MPW components would inev-
itably have oil/liquid products generated.

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 Fluidised-bed 760 55.8 42.4 1.8
PE Fluidised-bed 530 7.6 92.3 0.1
LDPE Fluidised-bed 700 71.4 28.6 0.0
LDPE Fluidised-bed 600 24.2 75.8 0.0
LDPE Fluidised-bed 500 10.8 89.2 0.0
LDPE Fixed-bed(batch) 700a 15.1 84.3 0.0
HDPE Fixed-bed(batch) 700a 18.0 79.7 0.0
LDPE Fixed-bed(batch) 500a 37.0 67.0 0.0
LDPE Ultra-fast pyrolysis 825 92.9 5 2
HDPE Fixed-bed(batch) 450 13.0 84 3
HDPE Fixed-bed(batch) 430 9.6 69.3 21.1
HDPE Vacuum 500 0.9 97.7 0.8
LDPE Vacuum 500 2.7 96.0 1.0
LLDPE Fluidised-bed 730 58.4 31.2 2.1
LLDPE Fluidised-bed 515 0.0 89.8 5.9
PP Fixed-bed(batch) 380 24.7 64.9 10.4
PP Fixed-bed(batch) 700a 15.3 84.4 0.2
PP Fluidised-bed 740 49.6 48.8 1.6
PP Vacuum 500 3.5 95 <0.1
PP Fixed-bed(batch) 500a 55.0 45.0 0.0
a
Final temperature.
130 D. Chen et al. / Waste Management 37 (2015) 116–136

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., 2007 studied the pyrolysis of biomass hemicelluloses,
cellulose and lignin, and they demonstrated that hemicelluloses,
with higher carboxyl content, accounted for a higher CO2 yield; cel-
lulose 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 den-
sity 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 benefits the gas production. Ni et al. (2006)
compared the wood pyrolysis and its gasification in a fluidised-
bed reactor and found that the pyrolysis gas yield at 600 °C was
0.26 m3 kg1 with an LHV of 17.5 kJ m3; under the same temper-
ature, syngas from gasification 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 gasification, which is bene-
fit 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 behav-
iours, 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 pro-
duction 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 mois-
ture 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 inves-
tigated. Buah et al. (2007) studied pyrolysis of RDF with a gross cal-
orific value of 18.9 MJ kg1 in a fix-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 (TG–FTIR) 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, 430–520 °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 calorific 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, char–oil or char–water slurry for fuel. Alternatively,

Table 6
Pyrolysis products from wood chips or sawdust in laboratory researches.

Ref. Product yields Temperature (°C) Reactor type/feedstock

Gas (yield/LHV in MJ N m3) Liquid (yield/LHV in MJ kg1) Char (yield/LHV in MJ kg1)
Li et al., 1999a LHV: approximately 19.5 750 Rotary kiln, wood chips
0.376 N m3 kg1, 15.0 37.9% 18.6% 850 L  d: 22  40 mm, 4.5 L
in volume
Xiao et al., 2006 Approximately 10%, 1.031 Approximately 25%, 11.7382 Approximately 28%, 21.742 400 Fluidised bed Woodchip
in 5 mm  5 mm Sample
Approximately 19%, 0.81 Approximately 38%, 12.015 Approximately 25%, 22.035 500 mass: not mentioned
Approximately 25%, 1.75 Approximately 31%, 8.606 Approximately 23%, 23.744 600
Approximately 35%wt, 1.61 Approximately 25%, 7.361 Approximately 20%, 27.968 700
Jiang, 2006 15.32%, approximately 14.5 45.11% 39.57%, 16.326 500 Fixed bed, sawdust of 1000 g
24.63%, approximately 16.0 43.54% M3: 69.3% 31.83%, 20.482 600
45.84%, approximately 17.0 30.75%, M:71.6% 23.41%, 23.852 700
49.52%, approximately 16.5 34.72%, M: 75.3% 15.76%, 26.115 800
51.16%, approximately 13.8 36.53% 12.31%, 29.322 900
Yi, 2007 0.23 Nm3 kg1 8.0% 4 22.8%, 600 Fixed bed, sawdust of
0.40 N m3 kg1 8.1%4 13.6% 700 about 1000 g mixed
0.66 N m3 kg1 7.5%4 9.3% 800 with calcined dolomite
0.84 N m3 kg1 14.9%4 9.6% 900
Hwang et al., 2014 0.12 N m3 kg1, 12.2 40–41% 87–88% 500 Fixed bed reactor, woody
0.3 N m3 kg1, 16.5 30–31% 65–70% 700 biomass chip of 7 g
0.52 N m3 kg1, 16.9 20% 55% 900

1: Fluidising gas may be included; 2: moisture included; 3: moisture content in liquid products; 4: tar yield.
 D. Chen et al. / Waste Management 37 (2015) 116–136
the char with the proper particle size can be improved for purposes
such as activated carbon production. The gross calorific 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 approxi-
mately 20%. The yield of oil products increased from 30% to 50%
as the temperature increased, and there was an increase in the aro-
matic 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 specific 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
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 benefits 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 pyro-
lysis temperature should be 600 °C or higher.
4.6. Pyrolysis products from MSW
Roughly pretreated MSW or MSW with source separation col-
lection have been adopted in pyrolysis processes in practice, as
seen in Table 3. In most processes, a gasification 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 significantly. In gen-
eral, a higher temperature and catalyst addition will increase the
gas yield and reduce the char yield. Combining the data in Tables
Table 7
Pyrolysis products from MSW.
Ref. Product yields
Gas (yield/LHV in MJ Nm3) Liquid (yield/LHV
in MJ kg1)
Wang et al., 2005b Approximately Approximately 40%1
0.15 N m3 kg1
Jiang, 2006 8.92% 61.261
13.41% 59.98
19.85% 58.73
31.16% 52.61
34.84% 50.59
Yi, 2007 0.33 N m3 kg1, 14.6 5.12
0.52 N m3 kg1, 15.3 4.82
0.81 N m3 kg1, 15.1 4.22
0.96 N m3 kg1, 14.1 3.62
1: moisture included; 2: tar yield.
131
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 gasification, where the gas yield can be
higher than 1 N m kg1 but with a lower calorific value (Hwang
et al., 2014).
4.6.2. Liquid products
Liquid products often contain a high moisture fraction, which
makes them difficult to apply. To improve liquid product quality,
the research of Velghe et al.(2011), based on an MSW with an aver-
age calorific 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 asso-
ciated 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 C8–C28 aliphatic carbons
(63.5% with 44.1% alkenes) in addition to 23.5% aromatic com-
pounds. 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 C8–C28 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 unqualified distillation
data. Water in liquid products mainly comes from biomass pyroly-
sis, 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 pro-
cesses listed in Table 3 (other than the EDDITh process) output
energy in the form of char. In most cases, char is gasified in a later
step or combusted and melted because solid fuel is not as attrac-
tive as gas and oil. In addition, before outputting char as a fuel
product, a pretreatment step, such as sorting out metals and peb-
bles, 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
Temperature Reactor type/feedstock
(°C)
Char (yield/LHV in
MJ kg1)
34.83% 550 Fixed bed Rubber, PVC, PE, rice, fruit husks,
vegetables, cloth, paper, wood chips. Sample
mass: 600 g LHV: 19.9 MJ kg1
29.82%, 18.317 500 Fixed bed, mixture of kitchen waste, paper,
26.61%, 21.471 600 cloth, bamboo, plastics and glass, air-dried, size
21.42%, 28.154 700 less than 5 cm, 1000 g
16.23%, 29.915 800
14.57%, 30.362 900
15% 600 Fixed bed, mixture as above with addition of
10.4% 700 calcined dolomite, air-dried to moisture
8.1% 800 content of 8.8%, 1237 g
7.8% 900
132 D. Chen et al. / Waste Management 37 (2015) 116–136

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 pro-
cesses coupled with gasification or combustion facilities (see
Table 3) are too complicated and expensive, limiting the applica-
tion of pyrolysis to the places where it is highly demanded due
to the desire to prevent long-distance transport and the increased
difficulty in finding new sites for incinerators and landfills. As an
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. Defining 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, espe-
cially in the places where fuel gas is needed for utility boilers
and domestic gas, a definition 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 nec-
essary 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 summa-
rised in Table 8:
From Table 8, it can be seen that the combined pyrolysis & gas-
ification 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 rec-
ommended that the combined pyrolysis & gasification 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 adop-
tion of efficient reactor should be taken to improve the product
qualities. To set up standards for the gas and/or the char is impor-
tant 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 pyro-
lysis process, all of the products are collected or recycled. Com-
pared to incineration, the use of the MSW pyrolysis process
makes it markedly easier to reduce or avoid corrosion and emis-
sions by retaining alkali and heavy metals (except mercury and
cadmium), sulphur and chlorine within the process residues, pre-
vent 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 associ-
ated 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 pyroly-
sis product utilization are reviewed.
5.1. Emissions and contaminants associated with the MSW pyrolysis
process
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
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

Table 8
MSW pyrolysis technology and product choice considerations.

Technology Oil/wax Gas Char Heat & power Capacitya

Combined Not applicable A suitable product; its quality standard Not applicable Gas sent to boiler Small,
pyrolysis & should be defined or gas engine moderate
gasification and large
Combined Not applicable Not applicable Not applicable The only choice, Small,
pyrolysis & but power moderate
combustion output is not and large
(melting) suitable for small
scale
Combined Not applicable Not applicable Not applicable Power is Moderate
pyrolysis, generated by to large
gasification & steam turbine
combustion
Pyrolysis alone If there is no centralized oil/wax refinery near Recommended To export char as Applicable if Small,
the pyrolysis plant; try to consume it inside A heavier, smaller volume of syngas with a product, there is adjacent moderate
the system. Its output is not recommended. higher LHV has many advantages in the standards of the boiler or and large
The operation temperature is suggested to be energy markets. For example, using the char should be consumer
600 °C or higher syngas in gas engines is practical defined
Quality should be standardized
a
Evaluated mainly with respect to capital cost.
 D. Chen et al. / Waste Management 37 (2015) 116–136
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 deter-
mined that approximately half of the input amount was found in
the pyrolysis products in both cases. More importantly, the forma-
tion of PCDD/F did occur even under the full-scale operating condi-
tions, and due to the high levels of less chlorinated dioxins and
furans appearing in the process products of the rotary kiln, the tox-
icity 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 laboratory-
scale 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 con-
taminate the gas and liquid products. Yuan et al. (2014) found that
HCl emission begins as soon as the melting of PVC occurs. How-
ever, HCl emission behaviour would be significantly changed by
other components in the MSW, depending on whether these com-
ponents 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 con-
taminants (Cd, Pb, Zn, Cu, Hg and As) and organic contaminants
(volatile aromatic hydrocarbons, alkyl phenols, etc.) and were clas-
sified 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 sin-
gle pyrolysis process should be equipped with products improving
facilities, that’s why for commercial pyrolysis plants, combined
pyrolysis and gasification or/and combustion technologies were
adopted; in addition emission control devices were installed for
syngas or flue gas scrubbing.
5.2. Pyrolysis-associated emission control technologies
Numerous measures have been reported to alleviate the envi-
ronmental effects associated with pyrolysis, including the inter-
ception of HCl, SO2, and NH3 from the gaseous phase, the use of
catalysts to upgrade the quality of the products and the avoidance
of certain special components in the feedstock.
133
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 require-
ments for syngas cleaning than boiler combustion (Arena, 2012).
An example of a gas improving & scrubbing system is the Thermo-
select process list in Table 3; the Thermoselect process uses gasifi-
cation for tar cracking and reforming. After completion of the
gasification stage, the synthesis gas exits the gasifier at approxi-
mately 1200 °C and flows 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 fluorine (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 fluorinated species, so that
they are washed out of the crude synthesis gas. Following the
quench process, the synthesis gas flows into a demister and then
into alkaline scrubbers, where the remaining particulates and
HC1/HF are removed. Then the gas passes through a desulfuriza-
tion scrubber for the removal of hydrogen sulfide by direct conver-
sion 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 Ther-
moselect 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 Ca–C composite had a very strong absorbing effect on HCl,
reaching 63% of the theoretical value. Brebu et al. (2005) investi-
gated the effect of catalysts on the pyrolysis of a plastics mixture
containing PE, PP, PS, a acrylonitrile–butadiene–styrene copolymer
with a brominated flame retardant and antimony oxide synergist
(ABS–Br) and PVC and reported that iron (FeOOH and Fe–C com-
posite) gave best results for the removal of bromine from the
decomposition oil, whereas catalysts based on calcium (CaCO3
and Ca–C composite) exhibited high efficiency 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
first 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 tem-
perature region. Many dehalogenating reactors are screw melting
devices. To remove HCl more efficiently at the lowest possible
temperature and to prevent the appearance of HCl in gas or oil
products, Yuan et al. (2014) developed a fluidized bed dehalo-
genation 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) inves-
tigated the transfer of Cl, S and N from food waste, paper and fibre
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
134 D. Chen et al. / Waste Management 37 (2015) 116–136
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 specific
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 gasifier are
available in practice. To improve the environmental profit 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 gasification or combustion
stage and they all equipped with gas scrubbing devices. The
reported pyrolysis reactors include fixed-bed, rotary kiln, fluid-
ized-bed 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 flexible 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 tempera-
ture, 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 calorific 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 remark-
able 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 calorific
value and thus a potential solid fuel resource, but it could be con-
taminated 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 contam-
ination 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 beneficial process. To for-
mulate the development and application of single stage pyrolysis
technology, standardized products other than heat or power
should be defined.
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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