Waste Management: Dezhen Chen, Lijie Yin, Huan Wang, Pinjing He

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

state-of-the-art of the development of pyrolysis of waste tyres
The treatment, management and disposal of municipal solid and industrial plastics well known. As for municipal wastes, the
waste (MSW) are common concerns in every country. MSW pyro- pyrolysis of sewage sludge has been investigated for decades for
lysis is considered as an innovative alternative for treating MSW liquid production, and the state-of-the-art of this technology has
that obtains different chemicals and fuels (Schaefer, 1975; also been addressed in a recent review (Fonts et al., 2012). How-
Malkow, 2004). In a pyrolysis-involved process, energy can be ever, compared to waste types such as tyres, plastics and sewage
obtained in a cleaner way than from conventional MSW incinera- sludge, MSW is more heterogeneous in composition and size. Cur-
tion plants as lower amounts of nitrogen oxides (NOx) and sulphur rently, for MSW pyrolysis, information on technology develop-
oxides (SO2) are produced as a consequence of the inert ment, characterization of products and correlated pollution is not
atmosphere in the pyrolysis processes and the opportunity to wash sufficient to support technology application and system design,
syngas before its combustion. In addition to reduced gas emissions, especially in regards to environmental impacts, which is funda-
better quality of solid residues can be also expected from pyroly- mental for a single step MSW pyrolysis application.
sis-involved treatment technique for MSW (Saffarzadeh et al., Therefore, this work reviews pyrolysis technologies for MSW,
2006). with focus on reactors, the products from MSW pyrolysis, the pol-
In general, pyrolysis represents a process of thermal degrada- lutants involved with the MSW pyrolysis process and product
tion of the waste in the total absence of air that produces recycla- applications, and the reported measures to alleviate the associated
ble products, including char, oil/wax and combustible gases. environmental impacts. The final aim is to provide essential infor-
Pyrolysis has been used to produce charcoal from biomass for mation for understanding the pyrolysis process applied to MSW
thousands of years. When applied to waste management, MSW and to standardize its application as an energy converter.
can be turned into fuel and safely disposable substances (char,
metals, etc.), and the pyrolysis process conditions can be optimised
2. Pyrolysis behaviours of MSW with respect to products and
to produce either a solid char, gas or liquid/oil product, namely, a
the influential factors
pyrolysis reactor acts as an effective waste-to-energy convertor.
Compared to the conventional incineration plant which runs in
2.1. Terminology and scope
capacity of kiloton per day; the scale of pyrolysis plant is more
flexible. Recently, MSW pyrolysis is receiving increasing attention
Reactions take place in a recognized pyrolysis process can be
in small cities and towns due to the desire to prevent long-distance
expressed as:
transportation; and it is also demanded in big cities as a distributed
MSW treatment method due to the increased difficulty in finding CxHyOz þ Q ! Char þ Liquid þ Gas þ H2 O ð1Þ
new sites for incinerators and landfills. Generally distributed
MSW treatment facilities are difficult to ensure environmental where Q is the heat that needs to be input to the reactor for the
safety due to capital cost limitations; while pyrolysis plants of reactions to take place, it includes three portions:
proper capacity with energy products output are suitable alterna- Moisture vaporization Q1
tive when the quality of char, oil/wax and combustible gases is During pyrolysis the feedstock will not undergo thermal
under fine control. decomposition before its moisture is vaporized, and Q1 can be cal-
A variety of pyrolysis studies have been conducted on industrial culated as:
wastes such as tyres and plastics, and several reviews have 1
Q 1 ¼ W 2260; kJ kg ð2Þ
reported on the characterization of the development of pyrolysis
technologies in terms of different aspects, for example, reactor where W is the water content of the feedstock to the reactor, %;
development and product characterization (Sannita et al., 2012; therefore to reduce this part of energy, MSW components with
Williams, 2013; Yang et al., 2013); conditions for oil production, high moisture content such as food wastes, biomass are suggested
oil characteristics and upgrading (Quek and Balasubramanian, to be separated before pyrolysis. In addition, in order to reduce this
2013); the heating rate and other governing variables affecting portion of energy a drying step is usually adopted in front of pyro-
pyrolysis process and pyrolysis products of tyres (Martínez et al., lysis reactor.
2013); and the mechanism investigation or kinetics modelling of
the pyrolysis process (Al-Salem et al., 2010; Quek and 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 pyrolysis behaviours and the products can be deduced from the
following equation (Raveendran et al., 1996): summary in Table 1.
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 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
ð3Þ products. At temperatures higher than 700 °C, syngas is the vital
product. Most of the researches paid more attention to the liquid
where Cp,M, Cp,ch, Cp,v are the specific heat capacities of the dry and syngas products than the char due to the fact that the oil
materials, char and volatile generated, J kg1 °C1; mM, mch and and syngas are more valuable; and the yields and composition of
mp,v are the mass ratio of the dry materials, char and volatile to pyrolysis oil and syngas are mainly changing with temperature.
the feedstock, %; the former three items at the right side of Eq. (3) The residence time of the materials in the reaction zone is another
are the energy required for heating feedstock and the products to important parameter; which was reported to be in the range of a
the pyrolysis temperature; and Qp is the reaction heat of the pyro- few seconds to 2 h as shown in Table 1. It was well recognized that
lysis, J kg1. Q2 can be obtained through differential scanning calo- longer residence time would enhance the tar cracking and result in
rimetry (DSC) or differential thermal analysis (DTA) techniques for higher gas yields; but at the same time longer residence time
different MSW components (He et al., 2006), and it has been found reduced water content and waxy material in the liquid products
that for reactor design purpose Qp can be neglected and the Q2 is (Velghe et al., 2011), conduced to the improved quality. The com-
mainly decided by pyrolysis temperature (Boukis et al., 2007; plex impact of residence time on products can be deduced from Eq.
Wang et al., 2012). The higher pyrolysis temperature does not only (1): in a longer residence time, more heat is input into the reactor,
result in a higher energy requirement, but also cause challenge to the extra heat will evaporate the water produced, crack the tar into
the safety of reactors. small molecules, and vaporise more organics from the char, all of
The radiation loss from the reactor to the surrounding Q3 this would result in higher gas yield. But longer residence time will
As heat is transferred from outside to the inner side of the reac- lead to lower treatment capacity of the reactor. The third impor-
tor, Q3 can be ignored for heat transfer surface design; but on the tant factor affecting MSW pyrolysis is heating rate (HR) and it
contrary, when the reactor is heated opposite, the heat transfer was reported to vary from about 4 °C min1 to 670 °C S1 as shown
surface should bear this portion of energy to maintain the desired in Table 1. Higher HR is corresponded to a higher volatile matter
temperature of the reactor. Better insulation will reduce this radi- (tar and gas) yield, accordingly less char will be left (Li et al.,
ation loss Q3. 1999a,b; Yi, 2007; Velghe et al., 2011); together with a longer res-
A pyrolysis system consisting of the pyrolysis reactor and other idence time, higher yield of syngas will be obtained due to tar
appurtenances serves the purposes of supplying the heat Q to the cracking; while as the volatile matter is extracted immediately
reactor, controlling the proper conditions for the desired products, and cooled down, higher yield of liquid products can be obtained
namely liquid, gas and char shown in Eq. (1) and preventing side (Font et al., 1995a,b). Theoretically the HR can be calculated as:
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 DT a
HR ¼ ; C S1 ð4Þ
products. But with the focus on giving instruction in setting up a m Cp
proper pyrolysis technology for MSW, only those literatures most where DT is the temperature difference between the reactor
relevant to MSW pyrolysis technologies and products are reviewed wall and the feedstock, °C; a is heat transfer coefficient inside
here. 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
2.2. Factors influencing MSW pyrolysis behaviours and products the specific heat of the feedstock, J kg1 °C1.
According to Eq. (4), HR is decided by DT, a and the mass load of
MSW consists mainly of paper, cloth material, yard waste the reactor. In the laboratory researches, the HR was setting by
(including fallen leaves and branches, etc.), food wastes, plastics adjusting DT or mass fed to the reactor to realize slow or flash
and a small amount of leather and rubber, metals, glass, ceramic, pyrolysis, as shown in Table 1. While in a practical and continu-
earthen materials and miscellaneous other materials. The fractions ously running reactor HR is decided by the reactor type which is
subjected to pyrolysis mainly include paper, cloth, plastics and characterized with its special temperature difference (DT) and heat
yard wastes. Highly wet food wastes should be separated to reduce transfer coefficient (a) features. The pyrolysis reactors reported in
Q1. Numerous studies have been performed in laboratories to the literatures are mainly fixed-bed reactors, rotary kilns and fluid-
determine pyrolysis behaviours and product properties of individ- ised bed reactors, as shown in Table 2; they are of a sequence in
ual MSW fractions such as paper, plastics, fabric, lignocellulosic ascending order according to HR. The fluidised bed reactors are
materials and putrescibles (Di Blasi, 1996; Wu et al., 2002, 2003; characterized with very high heat transfer coefficient of 112–559
Wu et al., 2005; Zhang et al., 2008; Zheng et al., 2009; Luo et al., (J/s m2 K) (Garcia et al., 1995a). But very few reports are available
2010a; Atesß et al., 2013; Miskolczi et al., 2013), refuse-derived fuel on heat transfer coefficients for MSW pyrolysis in rotary kilns and
(RDF) pellets (Cozzani et al., 1995; Garcia et al., 1995a,b; Lin et al., fixed-bed reactors, as they are affected by many factors; and they
1999; Buah et al., 2007; Dou et al., 2007; Grammelis et al., 2009; are also the company’s private know-how for designing and run-
Bosmans et al., 2013) and real MSW ( Islam and Beg, 2004; Islam ning pyrolysis reactors. The transport tube thermo-chemical con-
et al., 2005; He et al., 2010; Luo et al., 2010b; Zhao et al., 2011; vertor in Table 2 shows a new reactor type, it belongs to a family
Atesß et al., 2013; Miskolczi et al., 2013). The interactions between of tubular reactor, which will be discussed later.
the different individual fractions and the pyrolysis products have As for the influence of particle size on the MSW pyrolysis, it was
also been explored (Williams and Williams, 1997; Williams and not extensively investigated; but in general smaller particles
Williams, 1999b; Sørum et al., 2001; Grieco and Baldi, 2012; contributed to a larger surface area and faster HRs (Di Blasi,
Ding et al., 2013), but not as extensively. The previous researches 1996), therefore smaller particle size caused higher yields of liquid
indicated that the important parameters affecting MSW pyrolysis or gas products. Coarser particles correspond to the lower HR
included temperature, heating rate (HR), residence time in the therefore longer residence time is required. However, once the
reaction zone and materials’ size, etc.; and their effects on temperature is high enough, the difference in yields of products
Table 1
Pyrolysis behaviours and products under different reaction conditions.
Reaction conditions Feedstock Reactor type Main results respect to pyrolysis behaviours and the products Reference
MSW was decomposed in the 500–900 °C temperature MSW, almond shells, An analytical Pyroprobe When to investigate kinetics of the primary decomposition and the tar Font et al. (1995a,b)
range, and the lignin was decomposed in the range of lignin and apparatus, and a fluidised cracking, it was found that when there was no tar cracking, the increase in
600–900 °C polyethylene sand bed reactor yields are linear with time; and that tar cracking took place from the top of the
Sample mass for the fluidised-bed reactor was 1–3 g (at sand bed to the reactor head. In addition, the sample could continue
temperatures greater than 700 °C) or 0–30 g in the decomposing during the cooling period if the temperature is not too low, and
remaining cases. Particle size of PE was 0.5 cm. Almond this explains why flash pyrolysis in fluidised-bed reactor results in a high gas
shells was 0.297–0.500 mm in particle size. MSW sample yield
was 0.8–5 g and ground For pyrolysis products in the fluidised bed at 850 °C, almond shells
No information on residence time and heating rate (HR) 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 reactor was running at high nominal temperatures Dry pellets of MSW A helium fluidised sand-bed The heat transfer coefficients in the sand fluidised-bed reactor for MSW Garcia et al. (1995a,b)
(700–850 °C) batch by batch reactor 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 Around 70–80% of the primary tars can be cracked to low molecular weight gases
670 °C/s when the nominal temperature was 850 °C and When to study the production of gases from MSW pyrolysis at high nominal
approximately 425 °C/s if the nominal temperature is 700 °C temperatures (700–850 °C) and to explore the influence of pyrolysis
Sample mass: 0.8–5 g temperature and residence time of volatiles in the hot zone of reactor on the
Residence time: approximately 20 min 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%
The final temperature in the reactor was 850 °C. For fast 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)
pyrolysis, the reactor was heated to 850 °C first, and then, pre-treated kiln running at 3r min1 individual MSW components, the size of raw materials and the heating modes,
the sample was fed. For slow pyrolysis the MSW the authors found that the conversion of energy contained in MSW
components was heated together with the reactor wall components into syngas was much higher under the fast heating mode; PE
HR: 5–60 °C min1* was corresponded to the highest syngas yield of 720 L kg1 and vegetables had
Sample mass: 1000 g per batch the lowest syngas yield of 51 L kg1, but the latter corresponded to the highest
Residence time: 7–15 min 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
The reactor was heated up after materials were fed. The final 9 components in MSW, An electrically heated fixed- When investigate the yields of pyrolysis products varying with final Wang et al. (2005a,b)
temperature was changed from 300 to 700 °C crushed to less than bed reactor with N2 flush in temperature, the researchers found that the char yield decreased with the
HR: not mentioned 10 mm and then mixed the beginning increase of temperature, especially within the temperature range 300–550 °C,
Sample mass: 600 g per batch and that the pyrolysis liquid yield increased with the increase of temperature
Residence time: 55–180 min depending on the 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
The bed temperature was varied from 500 to 900 °C Wood, paper, An electrically heated fixed- When investigate the production distribution, the gas characteristics, the Jiang, 2006
Sample mass: 1000 g per batch municipal plastic bed reactor pyrolysis gas quality, the characteristics of the pyrolysis liquids and char, the
Sample size: less than 5 cm waste and crushed researchers found that the pyrolysis temperature is the top-drawer parameter
HR: not mentioned MSW affecting the pyrolysis of the MSW. With temperature increases, the gaseous
Residence time: up to 50 min 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

and 20 mm 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
Slow pyrolysis was performed up to 550 °C (with HR of 4 °C/ MSW cut in 2 mm A semi-batch reactor filled This research was to investigate the effect of reactor temperature and HR on Velghe et al., 2011
min) in a 2 h process pieces and oven dried with hot sand as a heat composition and yield/distribution of pyrolysis products; to investigate the
Fast pyrolysis was performed at 450, 480, 510 and 550 °C with at 110 °C before transfer medium under N2 distribution of metals present in MSW towards the pyrolysis products and to
few seconds of residence. pyrolysis atmosphere; A Archimedes’ investigate the obtained products for their use as fuel for energy production or
Sample mass: 70 g MSW in a flow rate of 24 g/min or 12 g/min screw ensures good mixing as raw chemical feedstock.
of the samples and the sand The important findings included: (1) The volatile matter was degraded
and creates a ‘fluidized bed between 200 °C and 560 °C at a HR of 20 °C min1, as revealed by
effect’ 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
Pyrolysis was performed up to 550 °C (with HR of 20–25 °C/ MSW fractions and Three-section reactor, with This research was to investigate the impact of impurities such as food wastes, Zhao et al. (2011)
min) in a 30 min process mixed waste plastics individual temperature paper, textile and especially soil on the pyrolysis of waste plastics. Emissions,
Sample mass: 1000 g per batch controls at different gas and liquid products from pyrolysis of waste plastics and impurities were
sections, batch run or studied. In addition, the transfer of elemental N, Cl, and S from the substrates
continuous operation 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
The temperature inside the reactor was electrically heated up PE (representative for A static batch reactor under This research was to investigate the effects of CaO additives and heating rates Pan, 2012
to 700, 800 and 900 °C respectively before feeding samples plastic materials in a N2 atmosphere on tar generation during MSW pyrolysis. It was found that CaO additives can
HR: assumed to be up to 1000 K min1 at 900 °C MSW), paper and reduce the content of acids, phenols and hydrocarbons in tar from bamboo and
Sample mass: 4 g bamboo paper pulp pyrolysis, but there was no obvious effect on PE. A higher heating
Residence time: 10 min (representative for rate resulted in more tar formation, consisting of acids, phenols and
wood & biomass in hydrocarbons within a wider temperature range
MSW) The LHV of syngas from PE pyrolysis varies between 37 and 51 MJ Nm3, more
than twice of that of bamboo or paper
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
*
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
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. incineration plant, ensuring the pyrolysis-involved process is a
clean one. Typical exhaust flue gas emission control devices
Installed with secondary treatment of products include particulate filters, cooling tower, wet scrubbers, etc., but
when compared to those adopted in incineration plants, they are
The commercial technologies listed in Table 3 are characterized reduced in dimension.
with the immediate utilization of their products in a combustion In addition to the commercial and semi-commercial pyrolysis
chamber or a gas engine, suggesting that those products are not technologies, some pilot or demonstration technologies are newly
standardized and not ready for the market. In those technologies developed with purpose to simply the pyrolysis system for MSW
with pyrolysis gases exported to gas engine, gasification acts as pri- through applying pyrolysis alone.
mary processing, and gas scrubbing is followed to ensure the qual- Fig. 2 shows a pilot MSW pyrolysis facility developed in Tianjin,
ity of the syngas. The char should have secondary treatment China (Li et al., 2007) with a capacity of 5 tons per day. Dealing
measures such as quenching, screening and separation of metals with unsorted MSW, it consisted of a main reactor and a subsidiary
when sold as carbon-rich material for industrial purposes. Some- reactor. The main pyrolysis reactor was a tubular reactor with a
time secondary treatment of pyrolysis products could be very rigid screw inside to push the MSW forward; the tube was heated from
depending on the feeding materials and the way to use products. outside by burning solid fuels such as coal or the charcoal pro-
To avoid extensive secondary treatment of products, high temper- duced in the pyrolysis process. The hot flue gas leaving the main
ature combustion inside the system is a suitable choice. reactor was then conveyed to the subsidiary reactor, and, after
cooling in a radiation duct, it mixed together with pyrolysis gas
Equipped with emission abatement devices and contacted MSW directly to heat up the latter for decomposi-
tion and gasification. The pilot tests were based on an artificially
As shown in Table 3, all of the commercial pyrolysis processes assembled MSW with the following composition: rubber 8.27%,
are equipped with emissions’ abatement devices similar to PVC 8.51%, PE 8.51%, kitchen waste 24.33%, pericarp14.60%, vegeta-
Table 3
Main pyrolysis involved units and technologies used in pilot, demonstration and industrial plants.
Process name Reactor & operation conditions Materials input & products Technologies Application Environmental protection
example device
PYROPLEQÒ process Rotary drum, pyrolysis at 450– Input: Pre-treated domestic Pyrolysis & The Ticino Canton Hot-gas filtration by means of
(Bracker et al., 1998; 500 °C; syngas was burnt at refuse; MPW combustion waste treatment ceramic filter cartridges. Lime is
Modern Power 1200 °C and the hot gas from the Output: The char with centre in Switzerland added to the reactor for acid gas
Systems, 2014) combustion chamber heats the calorific value of around removal. Conventional flue gas
pyrolysis drum from the outside 10 GJ t1. Power from steam clean up with a bag filter for fly
turbine 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
ConThermÒ technology Rotary kilns, pyrolysis taking Input: Shredded MSW, Pyrolysis & The Hamm power- The pyrolysis gas passed through
(Tech Trade, 2014; place at 500–550 °C for about automotive shredder residues combustion plant, Germany, with a cyclone before boiler
Hauk et al., 2004) 1 h, gas combustion in a as well as up to 50% waste capacity of 100 kt/ Flue gas scrubbing system of the
pulverised coal (PC)-fired boiler, plastics year. Stopped coal-fired power plant
see Fig. 1 Output: Power from steam
turbine
Gibros PEC Process or Rotary kiln, pyrolysis at 500– Input: MSW, industrial waste, A combination Aalen, Germany, with Gas scrubbing unit to wash out
PKA technology in 550 °C, for approximately 45– spent tyres, industrial and of pyrolysis, capacity of 25,000 inorganic acid pollutants,
Germany (IEA 60 min, the kiln was externally plastic waste as well as gasification tons per year followed by a bag filter to
Bioenergy, 2004) heated with part of the gas contaminated soil (thermal remove the remaining dust; and
produced in the process cracking), and a basic and a biological washer
The pyrolysis gases containing Output: CO/H2-rich fuel gas, smelting to remove H2S. Finally, an active
tars are subsequently gasified in metals, basalt coal filter to absorb dioxins,
a high temperature (1200– furans, and Hg
1300 °C) gasifier; char is smelted
(at 1400–1500 °C)
EDDITh process A rotary kiln running at 450– Input: Shredded MSW, Pyrolysis & Arras, France, with The flue gases produced by the
(Martin et al., 1998; 600 °C for 45 min; gas is industrial waste and sludge combustion capacity of 50,000 tpa combustion of the thermolysis
Malkow 2004) combusted at approximately Output: Gas (12 MJ kg1), gases need a deduster and
1100 °C with air coming from coke (16 MJ kg1, CARBORÒ), rational scrubbing system
the dryer while the char metals, salts, mainly CaCl2
undergoes separation and and NaCl, APC residues. Gas is
materials filtering burnt for heat and power
generation
Noell-KRC conversion A rotary kiln and a gasifier, Input: MSW, other feedstocks Pyrolysis and Freiberg, Germany, Pyrolysis gas is dedusted and
process (now Future pyrolysis at approximately (dried sewage sludges) may entrained flow with capacity of dewatered before entering the
Energy) (Malkow, 550 °C, gasification at 1400– be co-gasified gasification 12,000 tpa sewage gasifier. There are two scrubbers
2004; Jaeger and 2000 °C and 2–50 bars Output: Medium calorific sludge + 5760 tpa to clean gas from the gasifier.
Mayer, 2000) value gas; a part of the MSW. Demonstration The first stage removes H2S and
cleaned gas is used to heat the plant heavy metals, and the second
kiln. Metals and slag can be stage washes all of the other
used as construction contaminants
materials
Serpac technology Two interconnected chambers of Input: Mixed waste, MSW, Pyrolysis, Keflavic, Iceland, with Rational scrubbing techniques
(Malkow, 2004) cylindrical and conical shape, industrial and hospital waste gasification & capacity of 45 tons for fuel gas and flue gas
inclined and rotary. Pyrolysis at Output: steam; ash and combustion per day
600–700 °C, char gasification metals
with air at about approximately
800 oC; gas is combusted at
approximately 1100–1200 °C
Siemens Schwel-Brenn A rotating drum and a high Input: Tyres, MSW, sewage A combination Fürth, Germany, with Dust collection and flue gas
technology temperature furnace coupled sludge, industrial wastes of pyrolysis and capacity of 100.000– scrubber
(Malkow, 2004; with a steam boiler, pyrolysis at Output: Energy in form of high 150.000 kt/y, Shut
Richers and 450 °C for approximately 1 h; steam or power. Metals, glass temperature down August 1998
Bergfeldt, 1996) the finer carbon-enriched (30%) and ash combustion after accident with
fraction is ground to 0.1 mm and pyrolysis gas
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 A combination Yame Seibu Plant, Flue Gas cooler followed by two
branch of Siemens gas combustion at 1300 °C less than 200 mm in length of pyrolysis Japan, with capacity bag filters in series: No.1 for
Schwel-Brenn Output: power generation gasification & of 220 t/d, etc. particulate collection and
technology. (IEA from pyrolysis gas melting process recycling of ashes to the
Bioenergy, 2002) combustion; char, ferrous and combustor, and No. 2 with dry
non-ferrous metals; lime injection for acid gas
production of a fused ash emission control, with landfill
product. disposal of the solid residues
Takuma SBV(Kawai, Rotary kiln and ash-melting Input: MSW, industry waste, A combination Kakegawa Plant, Flue gas quencher followed by
2009) (Derived from system. Pyrolysis at 500–550 °C sewage sludge, etc. of pyrolysis and Japan, with capacity two scrubber stag
the above Siemens in the rotary kiln; pyrolysis gas is Output: Energy (power & gasification & of 140 t/d MSW
Schwel-Brenn burnt in a high temperature steam), iron, aluminium melting process
process) chamber
Table 3 (continued)
Process name Reactor & operation conditions Materials input & products Technologies Application Environmental protection
example device
Thermoselect process Moving channel bed. The process Input: Unsorted domestic A combination Mutsu, Japan, with A water jet quenching section is
(Malkow, 2004; consists of shredding, in the waste, shredded of pyrolysis and capacity of 50,000 tpaused to avoid the formation of
Thermoselect S.A., ‘channel’ MSW is heated from 50 Output: Medium calorific gasification & dioxins, and an acid gas scrubber
2000) to 600 °C and pyrolyses, value gas, a part of cleaned melting process unit is used to remove the HCl
followed by gasification at 1200– gas is used to heat the and HF; an alkaline scrubber unit
2000 °C channel. Mineral and metals with an aqueous sodium
from the smelt slag 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
Von Roll RCP A forward reciprocating grate Input: Pre-treated MSW, A combination Bremerhaven, Particulate emission control
technology furnace as a pyrolysis residual waste from recycling, of pyrolysis and Germany, a pilot systems and acid gas scrubbing
(Malkow, 2004; (degassing) chamber; the industrial waste melting & plant with capacity of equipment used in a common
Hesseling, 2002) pyrolysis temperature in the Output: Metal, slag; energy in combustion 6 t/h MSW power generation system
chamber is heated by partial form of steam or power
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 Input: Dewatered sewage Pyrolysis, Avonmouth, UK, with Dry scrubber with sodium
process (now Ethos reactors at 800 °C; the char is sludges, pre-treated MSW, gasification and capacity of 8000 tpa. bicarbonate and Selective
Renewables reacted with steam and air in a clinical wastes, scrap tire high (Mainly clinical waste Catalytic NOx Reduction (SCR).
Avonmouth (ERA) fixed bed gasifier, and gas crumbs; temperature now) The solid residues from the dry
Limited) (Malkow, combustion is in a cyclone Output: Energy in form of combustion scrubbing unit are sent for
2004) chamber at 1200–1250 °C steam or power; Char/ash landfill disposal
material from the gasification
unit
A gasification-coupled pyrolysis
Pilot pyrolysis process Input: pre-treated MSW Pyrolysis & Tianjin, China, with Gas cooler and filter
process. The main reactor is a
in Tianjin, China (Li Output: syngas with partial capacity of 200 kg h1
et al., 2007) screw-bed reactor, and moderate to low calorific gasification
gasification takes place in the value, char, metals and ash
subsidiary reactor. No
information on pyrolysis
temperature. See Fig. 2
Honghoo technology Multi-sectional rotary kilns, Input: Raw MSW with bottles, Pyrolysis alone Shanghai, China, with Pyrolysis gas was scrubbed
(Chen et al., 2013) pyrolysis at lower temperature stones, bricks and glass capacity of 100 ton/d, before burning. Char was
of approximately 400–450 °C, separated demonstration plant quenched and separated from
none-catalytic pyrolysis, indirect Output: Oil, char, cleaned gas metals
heat transfer; the gas is burnt (for power generation)
online to supply the heat. See
Fig. 3
CNRS thermo-chemical A tubular rectilinear reactor Input: Ground MSW Pyrolysis alone Pilot test facility Not mentioned
convertor heated by circulation of hot flue- Output: Syngas or flue gas
(Marculescu et al., gases (natural gas burner) within depending on whether
2007) an external double envelope. The comburant or inert gas is
solid continuously advances by supplied; accordingly char or
vibro-fluidised transport ash output
Flow rate up to 50 kg/h
Running from pyrolysis to
combustion with temperature
changing from 400 to 1000 °C.
See Table 2
bles 7.30%, cloth 5.35%, paper 18.25% and sawdust 4.87%. The temperatures from 300 °C in section I to 500 °C in section III. The
results revealed that as the temperature in the main reactor chan- demonstration plant was feeding with unsorted MSW, syngas, oil
ged from 500 to 700 °C, the gas yield increased from 24.4% to and char are output as products. According to a previous testing
38.9%, and the oil yields changed from 21% to 16.4%. At around operation analysis (Chen et al., 2013), the moisture-free oil yield
600 °C, the averaged calorific value of the gas was 7.5464 MJ m3. and the char yield were approximately 3% (moisture separated)
The H2 content was 15.2%, and the total C2H4, C2H6, C3H6 and CH4 and 20% of the feedstock, respectively, whereas the moisture and
content was 10%. No recommendation was given for the end prod- syngas gases accounted for approximately 77% of the feedstock.
ucts; but syngas seemed to be the most valuable product. There However, as the input wastes were raw MSW with a moisture con-
was none sequel to this pilot MSW pyrolysis facility, possibly due tent of approximately 60%, the moisture condensate in the liquid
to the fact that tubular reactor with a screw inside cannot deal products was more than 50% of its income in the feedstock, and
with unsorted and unprepared MSW. the vaporisation heat of the moisture in the reactor consumed
The Honghoo technology shown in Fig. 3 is a ‘‘pure’’ pyrolysis most of the reaction heat, reducing the treatment capacity from
process with multi-section rotary reactors, which run under the the designed 100 tons per day to the actual value of less than
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 3.2. Pyrolysis reactor
syngas was cleaned and used for power generation. Oil was
planned to replace the cleaned gas for heating the system after The reported reactors for MSW pyrolysis include fixed-bed
being upgraded with distillation, the heavy residue would be sent reactors, rotary kilns, fluidised bed reactors and some innovative
back to the reactor. Presently Honghoo technology is on the way to reactors, the concepts of these reactors are shown in Table 2. In
be commercialized, yet its char product needs to be standardized regards to the reaction conditions, most pyrolysis processes have
and it should be equipped with MSW pre-treatment devices to been conducted at atmospheric pressure. Vacuum pyrolysis has
ensure the stable operation and improve the quality of products. 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,
achieving vacuum pyrolysis is difficult in practice. Therefore, all of rial from coke, along with its external heating and recirculation, is
the following discussions in this review are based on atmospheric complicated. However, providing uniform products is usually
pressure. The reactors used in studies and at industrial scale are expected for a polymer cracking process, and polymer pyrolysis
summarised. in a fluidised-bed reactor can provide remarkable advantages over
other reactors wherein heat is not as properly transferred for the
3.2.1. Fixed-bed reactor cracking of polymers because polymers have a very low thermal
The fixed-bed reactor is characterized by a low HR, as the result conductivity and high viscosity. Therefore, fluidised-bed reactors
of its low heat transfer coefficient, as shown by Eq. (4). Therefore, are widely adopted as pyrolysis reactors for MPW, such as in, for
when a greater sample mass is tested, the temperature is not uni- example, the Hamburg process developed by Kaminsky (1992,
form inside the sample (Wang et al., 2006), and the feedstock is 2006) and BP polymer cracking process (Botom, 1993; Al-Salem
decomposed at different temperatures simultaneously. Fixed-bed et al., 2010). Arena and Mastellone (2006) summarised all of those
reactors have mainly been used to identify governing parameters processes for MPW pyrolysis and their commercial states, conclud-
affecting pyrolysis products, as discussed previously and shown ing that the fluidised-bed technology appears mature and particu-
in Table 1, but few comparisons have been reported with changed larly attractive for plastic waste pyrolysis. As for its application to
sample masses. Due to its inefficiency this reactor is seldom MSW pyrolysis, in addition to the problems of bed material separa-
adopted in scale-up facilities. tion, external heating and recirculation, fluidising agent (gas)
choice and MSW pretreatment should be dealt with thoroughly,
3.2.2. Rotary kiln reactors and their systems as they are expensive steps.
The rotary kiln is more efficient than the fixed-bed reactor in
heating up the feedstock. The slow rotation of an inclined kiln
3.2.4. Tubular reactors
enables good mixing of wastes. The rotary kiln reactors are widely
Tubular reactors include a family of reactors with fixed walls in
used, but they are typical reactors used for conventional pyrolysis
a tube shape, but for which, the materials move inside via various
(slow pyrolysis), which proceeds under a slow HR with significant
driving modes. Tubular reactors are generally heated externally,
product portions of char, liquid and gas. The reported HRs are not
and they studies featuring them reported different forms, such as
higher than 100 °C min1 as shown in Table 1 and the residence
a screw pyrolyser (Aguado et al., 2002), a tubular rectilinear reactor
time is up to 1 h, as shown in Table 3. This is because during pyro-
with solid driven forward by a vibro-fluidised transport
lysis, only the reactor wall serves to transport heat from outside to
(Marculescu et al., 2007), as shown in Fig. 4; and a tube with an
the particles; the small wall surface distributed to the unit mass of
inner mixer (Walendziewski, 2002). In Table 3, the pyrolysis reac-
feedstock and coarse size of the particles result in a low HR. How-
tors in the Thermoselect process, the Compact Power process and
ever, most reported MSW pyrolysis technologies are based on
CNRS thermo-chemical convertor are all tubular reactors. The
rotary kiln pyrolysers, as shown in Table 3, because the rotary kiln
advantages of these systems include continuous coke and gas
reactor has many unique advantages over other types of reactors.
removal from the reactor tubes free from leakage, larger heat
In addition to the good mixing of wastes, the flexible adjustment
transfer surface in a unit volume and convenience for syngas
of residence time and larger channel for the waste stream allow
reforming. It is easy to design and run a tubular reactor if the heat
feeding of heterogeneous materials, and thus, extensive pre-treat-
transfer coefficient is known because of its simplicity and safety. As
ment of wastes is not required, and its maintenance is also simple.
a typical tubular reactor, the screw tube, with its lower construc-
Rotary kilns for pyrolysis are externally heated using com-
tion and operation costs, has great future prospects. For this design,
busted pyrolysis gas. The calculation of heat and mass transfer
the screw speed can be varied within 0.5–25 rpm, thereby chang-
and design of the kiln have been extensively investigated for
ing the residence time of the materials; this reactor system has
homogeneous materials (Donald and Rosseman, 1962; Rutgers,
been found to be useful for both the thermal and catalytic cracking
1965; Bridgewater, 1985; Boateng and Barr, 1996; Li et al., 2005).
of waste plastics (Aguado et al., 2002). However, tubular reactors
For MSW pyrolysis, Li et al. (2002) performed comparative studies
have the same rigid requirements for MSW pretreatment as the
of homogeneous sand and irregular MSW in a rotary kiln in a cold
fluidised-bed reactors due to the small channel for passage of
state; examined the impacts of material characteristics, kiln geom-
MSW. In addition, erosion caused by sand and other hard solids
etry characteristics (i.e., roughness of kiln wall, exit end dam and
contained in the MSW can be a risk for this reactor, and heat trans-
internal structures) and operational parameters (i.e., kiln inclina-
fer coefficients are not well defined for different waste types.
tion and rotational speed) on both material residence time (MRT)
In a conclusion, adaptability of different reactors to MSW pyro-
and material volumetric flow (MVF); and then proposed a set of
lysis can be summarised in Table 4, from Table 4 it can be predicted
simplified formulas for the proper prediction of the MRT and
that rotary kiln will still serve as the main reactor type for MSW
MVF of MSW during pyrolysis (Li et al., 2002). But there is not
pyrolysis. However, for small and moderate scale, tubular reactor
much information in the literature on their heat transfer coeffi-
can be competitive. The operation temperatures are dependent
cients for heterogeneous MSW with changing particle size and
on product choice.
composition.
3.2.3. Fluidised-bed reactors 3.2.5. Other pyrolysis reactors and technologies

Fluidised-bed reactors are characterized by a high HR and good In addition to the above single-stage reactor types, whose prod-
blending of the feedstock. Therefore, such reactors are more fre- ucts must be post-treated outside the reactors, some multi-stage
quently used to describe the influence of temperature and resi- reactor types have also been adopted, and they are mainly for
dence time on pyrolysis behaviour and products (Williams and reforming or improving products. For example, a two-stage tube
Williams, 1999a; Mastral et al., 2002, 2003; Dai et al., 2001a,b). reactor was used to investigate the effect of steam reforming on
Typically, fluidised-bed reactors are used to investigate the behav- the tar produced in the first reactor stage (Ohmukai et al., 2008),
iours of fast pyrolysis (or flash pyrolysis) and to explore the sec- as the two stages can be controlled under different conditions.
ondary cracking of tar at longer residence times. For a similar purpose, Zhao et al. (2011) proposed a three-stage
Although fluidised-bed reactors have been extensively adopted reactor, in the first stage, HCl can be extracted immediately,
in laboratory studies, their industrial application is not common whereas the volatiles generated in the second stage can be
for MSW pyrolysis. The reason is that the separation of bed mate- extracted out or passed through the third stage and vice versa
Table 4
Adaptability of different reactors to MSW pyrolysis.
Reactor type Running experiences Requirements on Capacity Maintenance Flexibility to Application recommendation
material requirement operation parameters’
preparation change
Fixed-bed reactor Running in batch, only Almost no Small, may not Low, but batch by Excellent flexibility Not recommended for
in laboratory requirements exceed several batch operation industrial application
researches except for energy- tons per day demanding manual
saving purpose labour
Rotary kiln Most common Not rigid Large, up to Low to moderate Good flexibility Recommended but efficiency
150,000 tpa should be improved; multi-
sectional reactor suggested
Fluidised-bed Only for laboratory Very rigid Large Highest Very limited to size Heating system should be
reactor researches, no theoretically change; good improved before application
practical experiences flexibility to to MSW pyrolysis
for MSW temperature, etc.
Tubular reactor A few Rigid Moderate, up Moderate to high Limited to size and Recommended, especially
to 50,000 tpa temperature change the multi-sectional tubular
reactor
for product reforming. Those multi-stage reactors give hope for the In addition pyrolysis with various catalysts was adopted to
independent running of pyrolysis technology. improve products. Process catalysts have been widely used in
In a traditional thermal pyrolysis, in which process the heat Q in MPW pyrolysis in literatures. Pure polymer thermal degradation
Eq. (1) is supplied externally by hot flue gas, alternatively Q can be in the absence of catalyst produces a high boiling point wax-like
supplied through volumetric heating as performed in the new mixture that requires further upgrading via conventional refinery
technologies such as plasma pyrolysis (George, 1994; Hrabovsky processes. The use of catalysts in pyrolysis presents some advanta-
et al., 2006) and microwave pyrolysis (Cho et al., 2009; ges compared with simple thermal processes: i.e., lower energy
Macquarrie et al., 2012) . consumption, shorter reaction time and good selectivity to
Plasma pyrolysis is the process of heating waste to a very high higher-valued products. In addition, the liquid products formed
temperature over 1000 °C using plasma torches without an air sup- are in the boiling point range of commercial motor engine fuel,
ply, which converts waste into a synthetic gas (mainly CO and H2) eliminating the necessity for an upgrade process as well as the
and other end-products, such as a vitrified matrix. The highly effi- necessity for the whole process to be installed near existing refin-
cient delivery of heat for simultaneous rapid promotion of both eries (Gulab et al., 2010). For MSW pyrolysis, the summary listed in
physical and chemical changes in waste materials results in better Table 1 shows that catalysts improved oil quality and enhanced gas
control of process temperature, higher process rates, lower reac- generation, but only cheap catalysts such as calcined dolomite (Yi,
tion volume and especially optimum composition of produced syn- 2007; He et al., 2010) and CaO (Pan, 2012) can be used, as the cat-
gas. The properties of plasma pyrolysis products are predictable, alysts cannot be subsequently recycled. In addition, the catalytic
suitable for energy and material recycling, and harmless in terms effects are usually not sufficient; more significant effects can be
of public health and the environment (Huang and Tang, 2007), achieved for MPW than for MSW under the same conditions
but plasma pyrolysis requires a large amount of secondary energy, (Miskolczi et al., 2013) because of the poor contact between the
for example,1 kW h kg1 for arc plasma technology (George, 1994; MSW and the catalysts. To improve the MSW pyrolysis process,
Wang and Huang, 2008). Presently, plasma pyrolysis is being cheap catalysts that can absorb acidic gases at the same time are
tested mainly for hazardous waste disposal. For its MSW applica- more preferred than highly effective and expensive catalysts.
tion, a life cycle assessment comparison of the whole process with
a thermal cracking system is suggested, even a facility is available.
4. Products from pyrolysis of typical MSW components and
Microwave pyrolysis is being investigated mainly for homoge-
MSW
nous wastes such as sludge, shredded plastics and tyres. It is a type
of microwave dielectric heating method, and its main advantages
A great advantage of pyrolysis technology over incineration is to
include rapid, efficient in-core volumetric heating for direct cou-
export high quality products of oil or gas instead of heat, especially
pling of microwave energy with the molecules that are present
for the small-scaled systems. As the information on MSW pyrolysis
in the reactants, easily controlled and maintained desired temper-
products is very limited, and composition of MSW changed from
ature of pyrolysis for desired product raising, lower temperatures
place to place, a brief survey of products of principal MSW compo-
for the reaction vessel (or material surface) and higher tempera-
nents will help to elucidate the products from practical MSW pyro-
tures for the reaction mixture (or material interior), etc.
lysis process.
(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- 4.1. Pyrolysis products from waste paper
trol in a microwave reactor is dependent on accurate dielectric
data in the microwave frequency range as a function of tempera- Paper represents a mainstream combustible in MSW. As its
ture, which is not available for most of waste components. In addi- principal components are semicellulose and cellulose, waste paper
tion, solid-laden vapour has to be swept out of a microwave reactor is an important representative of biomass in MSW. Wu et al. (2002,
very rapidly to reduce secondary cracking of organic vapour in the 2003) investigated newspaper, uncoated printing and writing
freeboard and to drive water vapour and water-soluble small polar paper in MSW and found that paper begins to decompose around
molecules out of the reactor (Yin, 2012). Together with its rela- 488 K with the HR of 5 K min1, and at 583 K essential matrix
tively small treatment capacity, the application of microwave decomposition takes place already. The major pyrolysis in their
pyrolysis to heterogeneous MSW is not practical in the near future. studies included non-hydrocarbons (HCs) (H2, CO, CO2, and H2O)
and hydrocarbons (C1–3, C4, C5, C6, 1-ring, C10–12, levoglucosan,
C13–15, and C16–18), and the concentrations of both non-HC and HC the heavy oils into useful hydrocarbons. Many catalytic cracking
products increased with temperature. The percentage of volatiles processes have been tested and were summarised by Masuda
increased from 4.75% to 90.56% when the temperature increased and Tago (2006). According to their recommendation, catalytic
from 310 °C (583 K) to 665 °C (938 K) at a low heating rate of hydrolysis reactors with steam as a carrier gas and FeOOH as a
5 min K1. Tar formation occurred within the moderate tempera- catalyst followed by a catalytic cracking reactor with zeolite as a
ture range of 290–540 °C (563–813 K). The tar yield was approxi- catalyst could be a promising solution for fuel oil upgrading.
mately 47.03% at 450 °C and a heating rate of 10 °C min1. There In regards to components, there are six main plastics in MSW:
were four main different compounds they identified in the tar: high-density polyethylene (HDPE), low-density polyethylene
anhydrosugars, carboxyl compounds, carbonyl compounds and (LDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride
aromatic compounds. As temperature increased to 665 °C (PVC) and polyethylene terephthalate (PET). PE (including LDPE
(938 K), the char was reduced to less than 10% for the newspaper. and HDPE) and PP account for 70 wt% of the waste plastics stream
Ahmed and Gupta (2009) founded that waste paper pyrolysis had a in MSW in China (Wang et al., 2013), most important plastic com-
considerable overlap with its gasification, especially at higher tem- ponents in UK (Waste watch, 2008) and also worldwide (APME,
perature, but pyrolysis was more flexible compared with gasifica- 2004). Table 5 gives the product yield from the pyrolysis of PE
tion regarding the temperature. In a relatively large-scale and PP plastics, as summarised by Williams (2006). It can be seen
laboratory study based on a fixed-bed reactor, Jiang (2006) found that single PE and PP pyrolysis results in a yield of liquid products
the LHV of syngas from waste paper pyrolysis reached a maximum varying from 5% to 95%. In vacuum reactor or a fluidised-bed reac-
of 17.5 MJ N m3 at approximately 600 °C with a yield of tor running at moderate temperature (approximately 500 °C), the
301.4 L kg1, and the gas yield increased from 25.12% to 47.14% volatiles can be extracted immediately before the secondary crack-
as the pyrolysis temperature increased from 600 to 900 °C. The ing takes place, and a higher yield of liquid products can be
liquid product yield decreased from 44.47% to 32.08% at the same expected. Whereas in a high-temperature fluidised bed (for exam-
time, but 67.4% of liquid product was moisture at 600 °C. As the ple higher than 800 °C) or a fast pyrolysis reactor, the volatiles will
temperature increased, the moisture fraction also increased. be subjected to secondary cracking before leaving the hot zone,
The LHV of the syngas was between 10 and 17.5 MJ N m3 within resulting in high gas yields. Grieco and Baldi (2012) showed that
the temperature range of 400–850 °C, which is much higher than the oil yield of PE pyrolysis performed in a fixed-bed reactor
the LHV of syngas from gasification, the latter was reported to vary decreased from 90.9% to 86.2% as the HR increased from
from 1.8 to 2.5 MJ N m3 within the temperature range of 400– 0.1 °C s1 to 1 °C s1, while the gas yield increased from 9.1% to
700 °C (Xiao et al., 2007). All of these results indicate that syngas 13.7%. However, a very slow HR would result in a higher char prod-
will be an important product from waste paper pyrolysis and the uct, as shown in Table 5 for the two lower temperature cases
reaction temperature should not be lower than 600 °C. (430 °C for HDPE and 380 °C for PP). The major gaseous products
were H2, methane, ethane, ethylene, propylene, butadiene, ben-
4.2. Pyrolysis products from MPW zene and toluene without CO, CO2 or HCl appearance for PE, PP
and PS. Therefore, gas products are of high calorific value. PVC is
MPW is the most important energy contributor to MSW. A regarded as a harmful component in the MPW, as HCl evolves dur-
number of important studies on polymers and MPW pyrolysis ing pyrolysis, contaminating the products and causing apparatus
were summarised by Al-Salem et al. (2010). The main purpose of corrosion, its separation is desired. All of the reported polymer
MPW pyrolysis is to recover liquid products in many processes. cracking processes include an HCl abatement step to separate chlo-
For example, the famous BP polymer cracking process, Fuji process rine from HCs.
(Fuji Electric, 2001) and Hamburg process are all designed to In contrast to biomass, MPW in MSW requires a higher
recover oil products. To obtain high-quality, market-ready oil, the temperature to finish its pyrolysis. Within the conventional pyroly-
pyrolysis recycling of MPW usually consists of two processes. sis temperature range of 500–550 °C for rotary kilns oil is the main
The first is the degradation of MPW for the production of heavy product of MPW; and MSW rich in MPW components would inev-
oils, and the second is a catalytic cracking process that converts 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 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.
4.3. Pyrolysis products from wood and woody mass 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 -
Yard wastes, chopsticks, used furniture, etc. contribute kg1 at 850 °C (0.380 N m3 kg1on a dry basis) when the moisture
wood and woody mass in MSW. In terms of components, wood content was 86.86%, and the char yield was 4.5%; the residues were
and woody mass contain cellulose, hemicelluloses and lignin. water and tar. At the same rotary kiln, Li et al. (2000a) reported
Yang et al., 2007 studied the pyrolysis of biomass hemicelluloses, that gas yield of vegetables was 0.388 N m3 kg1 (dry basis) at
cellulose and lignin, and they demonstrated that hemicelluloses, 850 °C, when the initial moisture content was 17.86%; the tar pro-
with higher carboxyl content, accounted for a higher CO2 yield; cel- duction was 17.6%, and the char production was 32%. Li et al.
lulose provided higher CO yields, which were mainly attributed to (2000a) also reported that for the fallen leaves, the gas yield was
the thermal cracking of carboxyl and carbonyl, whereas lignin 0.353 N m3 kg1 (dry basis; initial moisture content: 11.49%) at
released more H2 and CH4. The components of gas products from 850 °C; the tar yield was 21.5%, and char production was 35.4%,
wood pyrolysis are mainly H2, CO, CO2, CH4, C2H4, C2H6, C3H8 and comparable to waste paper. In general, fallen leaves and vegetables
water (Kinata et al., 2013). In addition, C4H10 also appeared in are biomass with little lignin content, although the dry matter is
the gas products (Xiao et al., 2007). The pyrolysis products from suitable pyrolyser feedstock for syngas production, the high mois-
wood chips or sawdust are summarised in Table 6, in most cases, ture content is their main thermal treatment limitation and they
the density of the syngas was not reported, so that the yields were are suggested to be separated from MSW before pyrolysis.
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 4.5. Pyrolysis products from RDF from MSW
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 Pyrolysis of MSW in the form of RDF has been extensively inves-
are suitable contributors for syngas with moderate LHVs, and tigated. Buah et al. (2007) studied pyrolysis of RDF with a gross cal-
higher temperature benefits the gas production. Ni et al. (2006) orific value of 18.9 MJ kg1 in a fix-bed reactor and found that the
compared the wood pyrolysis and its gasification in a fluidised- main weight loss within the lower temperature zone (240–380 °C)
bed reactor and found that the pyrolysis gas yield at 600 °C was was due to the degradation of the cellulosic fraction in the RDF,
0.26 m3 kg1 with an LHV of 17.5 kJ m3; under the same temper- whereas the second peak of weight loss, occurring between 410
ature, syngas from gasification was 2.01 m3 kg1 with a LHV of and 500 °C was due mainly to degradation of plastic components.
5.8 MJ N m3; showing pyrolysis gas has much higher LHV and Chen et al. (2008) adopted thermogravimetric analysis–Fourier
small volume than that of syngas from gasification, which is bene- transform infrared spectrometer (TG–FTIR) to investigate the
fit for its utilization. High-quality chars with satisfactory LHVs in pyrolysis of two different RDFs, and they found similar weight
Table 6 are natural for the wood, which are the target products loss-temperature behaviours. The temperature zones were
for thousands of years. But wood and woody mass are not a good 220–430 °C for biomass degradation, 430–520 °C for plastics
feedstock for liquid product increases. In addition, considerable decomposition and higher than 650 °C for carbonates. Buah et al.
amount of moisture appeared in the liquid products, which would (2007) also found that the pyrolysis gases from RDF were H2O,
lead to very expensive post treatment of these liquid products. So CO2, CO, CH4 and other HCs. The yield of char fell as the pyrolysis
the recommended products from wood & woody waste pyrolysis temperature rose from 400 to 700 °C, and the oil/wax and gas
are syngas and char. products increased. The chars recovered were also found to have
BET surface areas that increased with temperature, but this effect
4.4. Pyrolysis products from fallen leaves and vegetables 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
Fallen leaves and vegetables are putrescibles in MSW. There are and 11.2 MJ kg1, respectively, with a yield decrease from 50% to
a very limited number of studies examining their pyrolysis behav- approximately 31%, which suggests those chars can be used as a
iours, and the products of fallen leaves and vegetables are similar 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.
the char with the proper particle size can be improved for purposes 1 and 7, it can be seen that the gas yield is usually lower than 1
such as activated carbon production. The gross calorific values of Nm kg1, and its averaged LHV is approximately 15 MJ N m1
the syngas from 400, 500, 600 and 700 °C were 5.1, 13.7, 16.2, when the pyrolysis temperature is not lower than 600 °C, which
and 16.7 MJ m3, respectively; and their yields were all approxi- is quite different from gasification, where the gas yield can be
mately 20%. The yield of oil products increased from 30% to 50% higher than 1 N m kg1 but with a lower calorific value (Hwang
as the temperature increased, and there was an increase in the aro- et al., 2014).
matic groups and a decrease in aliphatic groups at the same time.
The most recent research of Hwang et al. (2014) demonstrated that 4.6.2. Liquid products
the char from RDF pyrolysis had a similar BET surface area to the Liquid products often contain a high moisture fraction, which
results of Buah et al. (2007), and the RDF used by Hwang et al. makes them difficult to apply. To improve liquid product quality,
(2014) had a higher heat value (HHV) of 17.9 MJ kg1. Its pyrolysis the research of Velghe et al.(2011), based on an MSW with an aver-
produced chars with a specific surface area, changing from 24.6 to age calorific value of 27 MJ kg1, found that to produce oil, the
30.4 m2 g1 as the temperature increased from 500 to 900 °C. The optimal pyrolysis conditions are fast pyrolysis at approximately
values were much lower than that of chars from wood, waste paper 510 °C with a proper feeding rate. Under such conditions, the asso-
or plastics. The HHVs of the pyrolysis gas from this RDF were 10.4, ciated liquid product contains the highest yield of waxy material
17.0 and 19.1 MJ kg1 for temperatures of 500, 700 and 900 °C, and oil and the lowest water content, the lowest O/C value and a
respectively. These values were also very close to the results of high heat value, which makes it a promising fuel. In regards to
Buah et al. (2007). the composition, the oil fraction is rich in C8–C28 aliphatic carbons
The available results on RDF have proven that during pyrolysis (63.5% with 44.1% alkenes) in addition to 23.5% aromatic com-
interactions between different components did not change the pounds. They also found that no waxy material existed in the liquid
essential pyrolysis behaviours of individual components, and fractions of the slow pyrolysis products up to 550 °C. Under the
the target pyrolysis products can be expected by controlling the slow pyrolysis conditions, the oil yield was low, with 70.2% of
MSW components when producing RDF. But because of the energy the composition being C8–C28 aliphatic carbons.
consumption involved in the segregation process for making RDF, Miskolczi et al. (2013) compared pyrolysis oil from MSW and
MSW in the form of RDF may greatly reduce the energy generation MPW at 500 °C with a commercial oil (a so-called standard
potential according to Chakraborty et al. (2013). When disposed of product) and found that pyrolysis oil from MPW with or without
through pyrolysis, the benefits of RDF may include its adaptability catalysts meets most of the requirements in commercial oil,
to all types of reactors, steady operation and production of uniform whereas pyrolysis oil from MSW has a much higher water content
gas, oil and char products. To obtain the valuable syngas the pyro- and cannot meet the requirements in terms of the cetane index and
lysis temperature should be 600 °C or higher. corrosion test, in addition to the issue of its unqualified distillation
data. Water in liquid products mainly comes from biomass pyroly-
4.6. Pyrolysis products from MSW sis, so if oil production is desired, it is suggested that MPW instead
of whole MSW be pyrolysed.
Roughly pretreated MSW or MSW with source separation col-
lection have been adopted in pyrolysis processes in practice, as 4.6.3. Solid products
seen in Table 3. In most processes, a gasification or combustion The data in Table 7 show that char from MSW pyrolysis could be
process is followed because of the fact that energy in the form of a valuable fuel due to its relatively high LHV. However, few pro-
heat and power is a market-ready product. To help standardize cesses listed in Table 3 (other than the EDDITh process) output
gas, liquid and char products from MSW pyrolysis, these products energy in the form of char. In most cases, char is gasified in a later
are characterized here. 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
4.6.1. Properties of gas products from MSW product, a pretreatment step, such as sorting out metals and peb-
The properties of pyrolysis products from some trials with bles, is needed; this increases the cost and weakens its competition
unsorted MSW are summarised in Table 7. As MSW varies largely with rational fuel.
in components, the pyrolysis yields also vary significantly. In gen- Zhang (2012) explored the potential of adopting char from
eral, a higher temperature and catalyst addition will increase the MSW pyrolysis as biochar and found that the properties of the char
gas yield and reduce the char yield. Combining the data in Tables from MSW pyrolysis are similar to those of normal biochar from
Table 7
Pyrolysis products from MSW.
Ref. Product yields Temperature Reactor type/feedstock

(°C)
Gas (yield/LHV in MJ Nm3) Liquid (yield/LHV Char (yield/LHV in
in MJ kg1) MJ kg1)
Wang et al., 2005b Approximately Approximately 40%1 34.83% 550 Fixed bed Rubber, PVC, PE, rice, fruit husks,
0.15 N m3 kg1 vegetables, cloth, paper, wood chips. Sample
mass: 600 g LHV: 19.9 MJ kg1
Jiang, 2006 8.92% 61.261 29.82%, 18.317 500 Fixed bed, mixture of kitchen waste, paper,
13.41% 59.98 26.61%, 21.471 600 cloth, bamboo, plastics and glass, air-dried, size
19.85% 58.73 21.42%, 28.154 700 less than 5 cm, 1000 g
31.16% 52.61 16.23%, 29.915 800
34.84% 50.59 14.57%, 30.362 900
Yi, 2007 0.33 N m3 kg1, 14.6 5.12 15% 600 Fixed bed, mixture as above with addition of
0.52 N m3 kg1, 15.3 4.82 10.4% 700 calcined dolomite, air-dried to moisture
0.81 N m3 kg1, 15.1 4.22 8.1% 800 content of 8.8%, 1237 g
0.96 N m3 kg1, 14.1 3.62 7.8% 900
1: moisture included; 2: tar yield.

biomass: the char from MSW pyrolysis was rich in hydroxy-OH, From Table 8, it can be seen that the combined pyrolysis & gas-
fatty C-H, carboxyl group-COOH, aromatic rings CAH and C@C ification technology is a good choice for taking advantage of fuel
bonds on its surface, and the application of the char to the soil output other than heat from the pyrolysis system; however, the
could increase the cation exchange capacity and pH of the soil single pyrolysis stage is cheaper in general, the qualities of the
and improve soil fertility. However, the accumulation of heavy products should be stipulated to facilitate its application. It is rec-
metals in the char and their mobility to the soil may hinder this ommended that the combined pyrolysis & gasification technology
application. be used as the distributed MSW treatment method in cities that
can afford it. Pyrolysis alone may be adapted to the undeveloped
4.6.4. Standardized product places, and measures such as raising the operation temperature,
Presently, there is no ‘‘standardized product’’ from the MSW separation of inappropriate components in the feedstock and adop-
pyrolysis process that is ready for the market, with the exception tion of efficient reactor should be taken to improve the product
of the electricity or heat produced by burning syngas, oil or char qualities. To set up standards for the gas and/or the char is impor-
in the facilities. Syngas, oil and char converted from MSW in the tant to make those technologies practical.
pyrolysis process cannot meet any standards for conventional fuels
and materials. However, the existing commercial pyrolysis pro- 5. Environmental effects of MSW pyrolysis
cesses coupled with gasification or combustion facilities (see
Table 3) are too complicated and expensive, limiting the applica- Traditional charcoal production kilns typically vent volatiles to
tion of pyrolysis to the places where it is highly demanded due the atmosphere during operation, which gave this industry a bad
to the desire to prevent long-distance transport and the increased environmental reputation (Laird et al., 2009). In the modern pyro-
difficulty in finding new sites for incinerators and landfills. As an lysis process, all of the products are collected or recycled. Com-
effective waste-to-energy convertor, MSW pyrolysis is receiving pared to incineration, the use of the MSW pyrolysis process
increased attention in many counties and towns in China because makes it markedly easier to reduce or avoid corrosion and emis-
gas, oil and even char are needed in small cities and towns where sions by retaining alkali and heavy metals (except mercury and
scarcity of commercial fuels is common. Defining standardized cadmium), sulphur and chlorine within the process residues, pre-
products from MSW pyrolysis will help to normalize the pyrolysis vent large PCDD/F formation and reduce thermal NOx formation
technology and enhance its application. Syngas, with a moderate due to the lower temperatures and reducing conditions used in
LHV and huge market, is a potential standardized product, espe- the process. Advantageously, the smaller fuel gas volume associ-
cially in the places where fuel gas is needed for utility boilers ated with pyrolysis requires lower-dimensioned gas cleanup
and domestic gas, a definition of syngas standard for its market devices, which reduces investment and operation costs. However,
is necessary. Accordingly, the MSW pyrolysis process should be Cl and S species such as HCl and SO2 (or H2S) may still occur in
formulated to provide high-quality gas and avoid oil output. In this the fuel gas yielded, and other contaminants may exist in the liquid
case, the multi-sectional reactor has the advantage of providing a and solid products. In this section, the emissions from the pyrolysis
chance for product reforming, as indicated by Ohmukai et al. process and the potential environmental impact related to pyroly-
(2008) and Zhao et al. (2011), and hot char can be used in one of sis product utilization are reviewed.
the reactor section to modify oil and promote gas yield (Wang
et al., 2014). 5.1. Emissions and contaminants associated with the MSW pyrolysis
At the same time quality normalization for the char is also nec- process
essary if the pyrolysis alone is adopted.
MSW pyrolysis is combined with Cl, S and N emissions due to
4.7. Considerations for pyrolysis technology and product choice the volatility of those elements. With the help of TG-FTIR, Chen
et al. (2008) found that, during the pyrolysis process of RDF, HCl
Based on the above discussions, considerations for pyrolysis emission is completed at the low temperature stage (230–
technology and product choice for MSW pyrolysis can be summa- 400 °C), while the release of NH3 begins at 260 °C and goes through
rised in Table 8: 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.
to 600 °C, a large amount of SO2 was detected. Therefore, not only As shown in Table 3, industrial pyrolysis apparatuses adopting
gas but also liquid products can be contaminated with NH3 and gas engines are always installed with gas improving & scrubbing
SO2. Miskolczi et al. (2013) investigated contaminants in pyrolysis devices because gas turbine or gas engine has more rigid require-
products from MSW and MPW and found that pyrolysis oils had K, ments for syngas cleaning than boiler combustion (Arena, 2012).
S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; in the gas phase, S, An example of a gas improving & scrubbing system is the Thermo-
Cl and Br occurred. K, S, P Cl, Ca, Zn, Fe, Cr, Br, Sb and Pb were also select process list in Table 3; the Thermoselect process uses gasifi-
found in water scrubbing the gas. Compared with MSW oil, MPW cation for tar cracking and reforming. After completion of the
oil had much less S, Cl, Ca, Zn, Br and Sb. One of the most important gasification stage, the synthesis gas exits the gasifier at approxi-
research studies conducted by Mohr et al. (1997) regarding the mately 1200 °C and flows into a water jet quench where it is
behaviour of PCDD/F during the pyrolysis process compared the instantaneously cooled to below 95 °C The rapid cooling prevents
PCDD/F input/output in a rotary kiln operating as a disposal facility the formation of dioxins and furans. Entrained particles, heavy
with that obtained with a laboratory-scale batch reactor and deter- metals, chlorine (in the form of gaseous HC1) and fluorine (in the
mined that approximately half of the input amount was found in form of gaseous HF) are also abated in the quench. The pH value
the pyrolysis products in both cases. More importantly, the forma- of quench water is maintained at around 2 to ensure that heavy
tion of PCDD/F did occur even under the full-scale operating condi- metals are dissolved as chlorinated and fluorinated species, so that
tions, and due to the high levels of less chlorinated dioxins and they are washed out of the crude synthesis gas. Following the
furans appearing in the process products of the rotary kiln, the tox- quench process, the synthesis gas flows into a demister and then
icity equivalent (TE) of the output was approximately threefold into alkaline scrubbers, where the remaining particulates and
higher than that of the input, and 57% (by mass) of the total input HC1/HF are removed. Then the gas passes through a desulfuriza-
PCDD/F was in the oily condensate; for a batch-run laboratory- tion scrubber for the removal of hydrogen sulfide by direct conver-
scale reactor, the TE of the output was almost 11-fold higher than sion into elemental sulphur (H2S). The H2S scrubber is a packed
that of the input. Although the effects of temperature, residence bed that is sprayed with scrubbing liquor consisting of water and
time and other conditions on the fate of PCDD/F during pyrolysis a dissolved Fe (3+) chelate that oxidizes the H2S to elemental S0
need to be further investigated, the results of Mohr et al. (1997) and water. In the last step the syngas is dried in a countercurrent
demonstrate that pyrolysis cannot be safely believed to be a packed bed scrubber using tri-ethylene glycol liquor. The fully
PCDD/F-inhibiting process. However, oil products should be used cleaned syngas has very low concentrations of impurities; it can
with care because they can be contaminated with PCDD/F, and then be conveyed to engines or turbines for electricity production.
the output of oil from MSW pyrolysis should either be avoided or Alternatively, the cleaned syngas can be converted to higher
its destination stipulated beforehand. molecular weight fuels in liquid state (Thermoselect, 2014). Not
PVC is an inevitably harmful component in MSW, which emits all of the gas cleaning system is as comprehensive as that of Ther-
HCl during pyrolysis, would cause corrosion to the facility and con- moselect process, if a conventional power plant is situated in the
taminate the gas and liquid products. Yuan et al. (2014) found that near, the possibility to use the syngas in existing steam boilers
HCl emission begins as soon as the melting of PVC occurs. How- makes the cleaning step much simpler and cheaper.
ever, HCl emission behaviour would be significantly changed by To improve oil quality, Miskolczi et al. (2013) reported that the
other components in the MSW, depending on whether these com- concentrations of K, S, P, Cl and Br in the oil products could be
ponents enhanced or hindered heat transfer to PVC. In addition, decreased by using catalysts. Bhaskar et al. (2002) investigated
during MSW pyrolysis, HCl can be formed through the reaction the effect of catalysts on HCl removal from PVC pyrolysis and found
NaCl + H2O ? HCl + NaOH at higher temperatures, which is why a that Ca–C composite had a very strong absorbing effect on HCl,
diversity of HCl emission behaviours has been reported during reaching 63% of the theoretical value. Brebu et al. (2005) investi-
MSW pyrolysis (Bockhorn et al., 1998; Slapak et al., 2000; Kim, gated the effect of catalysts on the pyrolysis of a plastics mixture
2001; Ma et al., 2002; Zhu et al., 2008; Ren et al., 2009). containing PE, PP, PS, a acrylonitrile–butadiene–styrene copolymer
The char from MSW pyrolysis is accepted as a low grade fuel with a brominated flame retardant and antimony oxide synergist
instead of a waste stream. However the char from certain waste (ABS–Br) and PVC and reported that iron (FeOOH and Fe–C com-
pyrolysis processes can be toxic. Bernardo et al. (2010) reported posite) gave best results for the removal of bromine from the
that char residues produced in the co-pyrolysis of different wastes decomposition oil, whereas catalysts based on calcium (CaCO3
(plastics, pine biomass and used tyres) contained inorganic con- and Ca–C composite) exhibited high efficiency for chlorine
taminants (Cd, Pb, Zn, Cu, Hg and As) and organic contaminants removal; however, both Fe- and Ca-catalysts were found to have
(volatile aromatic hydrocarbons, alkyl phenols, etc.) and were clas- a low effect in nitrogen removal.
sified as hazardous and ecotoxic wastes. Therefore industrial waste Dehalogenation prior to the decomposition of plastics is an
streams are not suggested to mix with MSW in pyrolysis facilities effective and simple procedure. The method of dehalogenating
where char is output. first and then decomposing plastics is essentially a two-stage
Due to contaminants appearing in the pyrolysis products, a sin- pyrolysis method characterized by the release of halogen
gle pyrolysis process should be equipped with products improving hydrides at the low pyrolysis temperature region and the
facilities, that’s why for commercial pyrolysis plants, combined decomposition of polymer matrixes at the relatively high tem-
pyrolysis and gasification or/and combustion technologies were perature region. Many dehalogenating reactors are screw melting
adopted; in addition emission control devices were installed for devices. To remove HCl more efficiently at the lowest possible
syngas or flue gas scrubbing. 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
5.2. Pyrolysis-associated emission control technologies than 99% of HCl can be removed at temperatures not higher than
300 °C within just a few minutes.
Numerous measures have been reported to alleviate the envi- In addition, the separation of certain key components from
ronmental effects associated with pyrolysis, including the inter- MSW would upgrade the pyrolysis quality. Zhao et al. (2011) inves-
ception of HCl, SO2, and NH3 from the gaseous phase, the use of tigated the transfer of Cl, S and N from food waste, paper and fibre
catalysts to upgrade the quality of the products and the avoidance to the oil products in a MPW pyrolysis process and found that the
of certain special components in the feedstock. presence of food waste would result in higher contents of Cl and S
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Waste Management 37 (2015) 116–136

Contents lists available at ScienceDirect

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

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

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

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

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

Miskolczi et al., 2013

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

volatile matter diffuses from inner particle to the outside.

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

3. Pyrolysis technologies and the reactors

3.1. Pyrolysis technologies

The concept of pyrolysis technology can be represented by

RWE-ConThermÒ process (Hauk et al., 2004), as shown in Fig. 1,

the point view of technologies details and emissions abatement.

are characterized with the following conﬁgurations:

The existing commercial pyrolysis technologies seldom run

are combined with gasiﬁcation, combustion and smelting; and the

The same as above

combination with gasiﬁcation produces moderate-caloriﬁc-valued

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

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

2007; Ohmukai et al., 2008) and will be a competitive choice in

Fully decomposition of MPW pyrolysis have higher time

necessity than MSW in absence of catalyst; 6652 s at

Fed with pre-treated materials

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

All of those MSW pyrolysis technologies accept pre-treated

ation after the chimney collapse in December 2009. The accident

The same as above

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

feed composition did not match the process as designed, resulting

Pyrolysis reactor and system in researches Reference

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

waste separation Metals, paper, organic

Li et al. (1999a,b), Li et al. (2000a,b)

TC Gas sample bag

Pyrolysis reactor and system in researches Reference

Fluidised-bed pyrolysis system

Treatment gas inlet

Integrated Pyrolysis for Power Plants

pyrolysis gas to boiler

1.Tipping bunker 2. Shredder

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

gasiﬁcation stage and independent utilization of the pyrolysis

Collecting and seperating systems for

3.2.3. Fluidised-bed reactors 3.2.5. Other pyrolysis reactors and technologies

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

Ref. Product yields Temperature Reactor type/feedstock

1: moisture included; 2: tar yield.

Technology Oil/wax Gas Char Heat & power Capacitya

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