Bioresource Technology 312 (2020) 123615

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Slow pyrolysis of municipal solid waste (MSW): A review T

a a b a,b,c,⁎
Jia-Shun Lu , Yingju Chang , Chi-Sun Poon , Duu-Jong Lee
a
Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan
b
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Hong Kong
c
Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan

A R T I C LE I N FO A B S T R A C T

Keywords: In recent years, extensive studies have been carried out to improve our knowledge of the reactor operations and
Municipal solid waste system performance in thermal pyrolysis of municipal solid wastes (MSW). However, the fundamentals of MSW
Co-pyrolysis pyrolysis and their engineering applications remain unsatisfactorily explored. This paper is a review of the
Syngas pyrolysis of MSW and synergistic co-pyrolysis of the constituents of MSW with reference to pyrolytic perfor-
Pyrolysis oil
mance, the distribution and energy content of the end products, and the mechanisms of the synergistic effects.
Biochar
The prospects for, and challenges of, the MSW pyrolysis process are provided. A MSW pyrolytic process with
Mechanisms
maximal energy recovery and minimal carbon footprint is proposed.

1. Introduction
Municipal solid wastes (MSW) are mixtures of various solid wastes
that are generated by human activities (Yan et al., 2020). The con-
stituents of MSW include food waste, paper, biomass, glass, metals,
plastics, rubbers and textiles. (Ashani et al., 2020), which are currently
managed by landfilling, composting and incineration (Katakojwala
et al., 2020). The annual rate of production of MSW currently exceeds
two billion tones (Shahabuddin et al., 2020), and will increase to four
billion tons before the next century (Ebrahimian and Karimi, 2020).
The constituents of MSW warrant recycling to help realize a circular
bioeconomy for modern societies (Mohan et al., 2020; Priyadarshini
and Abhilash, 2020).
The mitigation of environmental stresses in the handling increasing
amounts of MSW and depletion of municipal fuel supply have moti-
vated research into the conversion of MSW into renewable resources
(Kasataka et al., 2020). Thermal pyrolysis is an emerging MSW treat-
ment for decomposing complex organic substances into fragments with
solid residues, requiring an input of external energy (Zhang et al.,
2020). A Web of Science search on April/3/2020 with the subject
“pyrolysis and municipal solid waste” yielded 812 articles, which have
received a total of 21,379 citations and 18.9 hits per article, a value
higher than that approximately five for general engineering papers. A
search of this literature suggests that the pyrolysis of MSW is a focus of
engineering and scientific research.
The thermal pyrolysis process can be categorized into flash pyr-
olysis, fast pyrolysis, medium-speed pyrolysis, slow pyrolysis based on
the corresponding heating rates. The MSW is generally in large quantity
for treatment and can associated with high content of moisture;
therefore, the heating rates for industrial units would fall in the slow
pyrolysis category (Shie et al., 2003). The constituents of MSW can
yield various intermediates in a pyrolytic environment, and these may
interact with each other, causing synergistic pyrolysis (Chhabra et al.,
2019). To detail the mechanisms of the synergistic interactions in MSW
pyrolysis, co-pyrolysis tests of at least two constituents of MSW were
conducted in the laboratory and on a pilot scale (Ganesapillai et al.,
2016; Paukov et al., 2019; Yousef et al., 2019). Synergistic pyrolysis, if
it occurred, would accelerate the rate of the pyrolytic reactions and/or
shift the end products of the MSW pyrolysis to favor the formation of
more value-added products (van Nguyen et al., 2019; Hassan et al.,
2020; Gu et al., 2020).
The use of syngas and pyrolysis oil products of slow pyrolysis
(named pyrolysis hereinafter) of MSW as alternative fuels (Chen et al.,
2020; Mateo et al., 2020) and feedstocks for the production of fine
chemicals has been proposed (Hu and Gholizadeh, 2019; Moreno et al.,
2020). Its solid product, biochar, has been used as adsorbents (Yi et al.,
2020), chemical catalysts (Kumar et al., 2020), electron conductors in
enhanced anaerobic digestion processes (Lu et al., 2020), and carbon
sinks (Sun et al., 2020). In view of financial viability, maximizing the
benefits from the end products is also critical to the value of MSW
pyrolysis treatment in practice.
This review focuses on the current major research in slow pyrolysis
of MSW, including pyrolysis processes and the characterization of its
end products. Recent advances in slow pyrolysis research that involve

⁎
Corresponding author at: Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.
E-mail address: djlee@ntu.edu.tw (D.-J. Lee).

https://doi.org/10.1016/j.biortech.2020.123615
Received 9 May 2020; Received in revised form 29 May 2020; Accepted 30 May 2020
Available online 01 June 2020
0960-8524/ © 2020 Elsevier Ltd. All rights reserved.
J.-S. Lu, et al.
the pyrolysis of MSW and co-pyrolysis of various constituents of MSW
are outlined. The prospects for, and the challenges of, developing an
efficient MSW pyrolysis process with the smallest possible carbon
footprint are also summarized.
2. Pyrolysis of MSW
2.1. Compositions of feedstocks
The compositions of MSW feedstocks for pyrolysis that were col-
lected from different geographical regimes depend on local living
styles, the social-geographical status of the local human settlements,
and on whether the collected MSW is source separated and undergoes
resource recovery as part of its final disposal.
MSW that is collected from residential areas includes surplus food
waste, plastics and paper wastes (Tang et al., 2020). For example, Song
et al. (2018) performed pyrolysis tests on MSW that was collected from
Taiyuan, China, which contained 57.72% kitchen waste, 23.40%
plastic, and 10.7% paper. Fang et al. (2016, 2018a, 2018b) noted that
MSW that was collected from Guangdong, China contained 46.4% food
waste, 30.7% PVC, and 18.2% paper. Azam et al. (2019) obtained
mixed MSW from Lahore, the second largest city in Pakistan, which
contained 69% food waste and 26% paper and plastics. Sfakiotakis and
Vamvuka (2018) and Yang et al. (2018) collected MSW samples from a
solid waste management company in Chania and from a municipal
waste treatment plant in Leicester, UK. Chania is the second largest city
in Crete, whose economy is dominated by agriculture and tourism, so its
MSW contained 49.0% food waste, 31% paper, and 12% biomass. Lei-
cester is a medium size but well-developed city in the UK, from which
MSW contained 40% food waste, 28.8% paper, and 6.5% plastics. da
Silva Filho et al. (2019) sampled MSW in Joinville, Brazil, which con-
tained 80% plastics and small fractions of paper and metal, which were
generated by industrial manufacturing activities. Gandidi et al. (2018)
examined MSW samples from Bandarlampung, Indonesia, which is the
capital of the Lampung province with massive agriculture and light
industry sectors and found that the samples contained 52% plastics and
34% biomass. Wu et al. (2020) sampled MSW from Hangzhou, China,
and noted that biomass and textiles represented 40% of their total
weight, followed by metals (15%), rubber (10%), paper (10%), and
food waste (10%).
Pre-screening and treatment can change the composition of MSW.
For example, refuse-derived fuels (RDF) that are made in Waroclaw,
Poland, contain 31.57% yard waste, 30.26% plastics, and only 8.25%
food waste (Stępień et al., 2019) and those from Setúbal, Portugal
contain 29.5% yard waste and 22.2% plastics (Nobre et al., 2019).
These findings are the result of the screening protocol for selected
wastes to maximize the heating values of RDF. Wang et al. (2020b)
studied MSW samples that were collected from a landfill site in Eastern
China which contained 57% yard waste disposed of by the agricultural
sector.
MSW contains moisture unless it is intensively dried. For instance,
Tang et al. (2020) found 53.31% moisture in MSW that was collected
from households in Guangzhou. The samples of Wang et al. (2020b)
contained only 5.6% moisture because the MSW wastes were sun-dried
after collection. The correlation between moisture content and food
waste content of the MSW samples is (Moisture content
(%) = 0.856 × Food waste content (%)) with r2 = 0.954. This corre-
lation suggests the high affinity of moisture for food waste in MSW
samples.
Typical mixed MSW feedstocks contained > 80% C + O in the ul-
timate analysis (Vuppaladadiyam et al., 2019; Fang et al., 2018a; Song
et al., 2018). MSW that contained plastics (typically polyethylene (PE),
polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), poly-
ethylene terephthalate (PET)) had high carbon contents (> 60%)
(Özsin and Pütün, 2019, Sophonrat et al., 2018). MSW that was en-
riched with food waste (pork, rice, kitchen waste) contained > 70%
2
Bioresource Technology 312 (2020) 123615
Fig. 1. Compositional distributions (mol/mol) of typical MSW samples for ty-
pical recent pyrolysis studies listed in supplementary materials. 100% C is for
char; those without H are paper mill sludge (PMS) and printed circuit board
(PCB); those with low O are plastics waste (PS, PE, tire waste, and PP; those
locating close to central region are the unsorted MSW without resource re-
covery.
C + O (Ming et al., 2020; Chen et al., 2018a). Fig. 1 presents the
compositions of the MSW feedstocks that were used in the pyrolysis
studies. The 100% C point corresponds to char; the MSW samples
without H atoms characterize printed circuit boards, whereas those
samples with 0–4% O are plastic waste (PE, PP, PS, tire waste).
2.2. Pyrolysis tests
2.2.1. Pyrolyzing reactor
Over 40% of recent studies of the pyrolysis of MSW used thermo-
gravimetric analysis (TGA), probably because of its versatility and
ability to scan a range of temperatures in a single test. TGA tests are
frequently conducted with follow-up gas chromatography and/or mass
spectrometry to identify the products. Most studies involve tempera-
tures in a typical range from the ambient temperature to 900 °C and the
Coats-Redfern method is commonly used to fit the data with Arrhenius-
type empirical correlations (Wang et al., 2018, Stępień et al., 2019, Ali
et al., 2020, Wu et al., 2020). TGA tests are particularly useful for
screening potential feedstocks that are obtained from many possible
substrates/experimental conditions of interest. The main shortcomings
of the use of TGA include potential sampling bias and incapability to
generalize the results when other limiting factors such as mass transfer
constraints or poor local mixing applied in large pyrolyzers (Shie et al.,
2000).
The advantage of a fixed-bed reactor over TGA tests is that it can
accommodate larger samples. For example, Tekin et al. (2019) carried
out pyrolysis tests in a 0.59 L fixed-bed reactor; Veses et al. (2020) used
a fixed-bed reactor with an inner diameter (ID) of 5 cm and a length of
52.5 cm, and Onwudili et al. (2019) performed pyrolysis in a two-stage
fixed-bed reactor with an internal diameter (ID) of 4 cm and a length of
48 cm, which was equipped with two sequential 1.5 kW tubular elec-
trical furnaces. Wang et al. (2020b) used fixed-bed reactors each with
various temperature zones.
Another category of larger-than-TGA pyrolyzing testers consists of
tubular reactors, which have similar shapes to fixed-bed reactors but no
internal packing. Tokmurzin et al. (2020) used a tubular reactor that
was 100 cm long with an ID of 5.4 cm (volume of 2.3 L) and Ren et al.
(2018) performed pyrolysis in a horizontal tubular furnace that was
equipped with a quartz tube with an ID of 9.5 cm and a length of
100 cm.
 Table 1
Characteristics and proposed uses of end products from co-pyrolysis of MSW.
Feed Yield (w/w) Composition Quality Beneficial use Reference
J.-S. Lu, et al.

MSW Char: 48.1–49.7%; Gas: 38.3–43.6%; Tar: NA Syngas > 80 vol% CO and H2 with Gas as syn-gas or Veses et al. (2020)
6.8–13.1% heating value of 16 MJ/Nm3 produced at chemicals; char as fuel
> 900 °C.
Litchi peels NA Gas: CO2, CO; Oil: terpenoids/steroids (71.87%), Added MgCO3 reduced aliphatic Terpenoids and Liu et al. (2020)
lignin-derived phenols (15.51%), aliphates compounds and increased terpenoids and steroids are products
(9.95%) steroids in oil.
Corrugated cardboard Oil: 47.0% (450 °C); Tar: 8.5–47.0% Methanol from hemicelluloses and lignin is six NA Oil has high Sotoudehnia et al.
times concentration at 350 °C than at 400/450 °C oxygenates (2020)
PE NA Simple analyses on pyrolysis oil Oil: pH 5.9, density 0.809 g/cm3, API Oil replace diesel. Quesada et al. (2019)
gravity of 42.85, cetane index 74.07.
Organic fraction of MSW + coal char:39–42%; Tar:22–24%; Gas: 33–38%; HVC: Gas: CO2, CO, H2, CH4, C2H6 NA Syngas/oils for further Tokmurzin et al.
char: 61–73%; Tar:12–24%; Gas:14% Tar: Heavy and light tar process (2020)
Food waste Gas: 45.1–51.3%; Solid: 28.3–37.3%; Condensable Gas: H2, CO, CH4; condensable: pyrrolidines, CO2 decreased content of condensable by NA Lee et al. (2018)
hydrocarbons: 17–19% nitriles, allose, isomannide, fatty acids 6.6% and by 6.2% at 600 °C and at 700 °C.
Food waste (pork/rice) Char:16–20% Pyrolysis oil: 3-butenamide:12–15%; NA Oil as phenolic Ming et al. (2020)
hydrocarbons:4–10%; acids:7–25%; Nitriles and compounds.
amines: 22–31%; saccharides:0–19%
MSW Gas: 22–44%; pyrolysis oil: 13–32% Gas: CO2, H2, CO, CH4; oil: oxygenates followed Low acidity of oil (pH > 8), H2/CO Char as adsorbent Wang et al. (2020b)
by aromatics, light polyaromatics molar ratio of 2, high concentration of
light aromatics.
Pine sawdust + LDPE Gas: H2 (63–88 mol%) Gas: H2, CO, CO2, CH4 H2 composition 86.74 mol% NA Chai et al. (2020)
Kitchen waste + Tire waste NA Gas: CO2, CO, NO, NH3, SO2, C–H, C = C groups; 10.8% PAHs for improved quality Oil as biofuels and Chen et al. (2020)
oil: olefins, aromatics, OCs pyrolytic oils. chemicals
Waste jeans Untreated: 37.59% oil, 44.62% gas, 17.19% char; Gas: H2, CO, CO2, CH4; oil: alcohol, furfural, NA 1617$/ton; carbon Yousef et al. (2019)
Treated: 30.25% oil, 48.15% gas, 21.6% char propyl nitrite, ethanol, 2-(1-methylethoxy)- footprint: −836 kg

3
octaethylene glycol, ethane, acetophenone CO2-eq/ton of waste.
Xylan + PVC Gas: 57–84%, oil: 2–12%, Char: 12–22% Oil: aromatic hydrocarbons (to 92.29%) and NA NA Wang et al. (2019b)
oxygenated compounds.
Methyl cellulose/ Spirulina/ Sludge NA Gas: H2, CO, CO2, CH4 NA H2 as energy Wang et al. (2019a)
MSW + Woodchip Char: 10.19%; gas:75.98% Gas: CO, NOx, SO2, BTEX, PAHs. char: inorganic MSW + WC had HHV of 23.93 MJ/kg. Char and volatiles as da Silva Filho et al.
elements Pyrolysis and post-combustion minimize fuels; gas for heat (2019)
generation of HCl, dioxins and furans.
Plastics (PE, PP, PS, PET) 500 °C: gas (8–22%), oil (68–86%), char (3–5%); Gas: H2, CH4, CO, CO2, alkanes, alkenes; oil: C1- NA Aromatic from plastics. Onwudili et al. (2019)
600 °C: gas (28–52%), oil (44–67%), char (3–5%) C4: 50–60%, C16+: 30–50%
Crude oil + MSW Liquid: 11–39%, gas:15–37%, solid: 6–46% Gas: hydrocarbon gas, solid: solid carbon residue, Solid residue: 93–95% C; diesel index of Solid as fuel. Liquid as Paukov et al. (2019)
liquid: liquid hydrocarbon distillate distillate 18. diesel fuel.
PS NA NA NA. Products at lower Ali et al. (2020)
energy cost.
HDPE Liquid: 60–70%, gas: 15–30%, char: 2–8% Gas: alkenes and alkanes (C2–C4), Oil: aliphatic > 96% of oil: aliphatic (C8–C12). > 70% Products as liquid fuel Al-Salem (2019)
oil, aromatic HC of gas: C2 to C4 hydrocarbons oil
woody materials Char: (400 °C): 24–35% ; (600 °C):16–26% NA Char: > 60$ fixed carbon with Cl, N and Biochar for land use. Ayiania et al. (2019)
S compounds but no PAHs. AA as solvent.
MSW Char yield: coal: 31.8%, MSW: 10.2%; RDF: 9.3% NA NA Renewable energy Azam et al. (2019)
source
plastic lunch box (PP) W/o catalyst: gas (47.8%), oil (10.3%), solid W/o catalyst: gas: 33 vol% H2, 23 vol% CH4, NA Use as fuel cell fuel Cai et al. (2019)
(30.3%); w/ catalyst: gas (90.2%), oil (0%), solid 44 vol% C2-C4; w/ catalyst: 58 vol% H2, 29 vol%
(5.7%) CO2
MSW Gas:4.8%; oil:38.5%, solid: 29.2% Gas: 42% CH4, 22% C2H6, 8.8% C3H8 47,923 BTUs in gas, 49,446 BTUs in oil, Oil: burner fuel; solid Fox et al. (2019)
13,972 BTUs in 86% caloric content into as brown coal
end products
Food waste Pyrolysis oil:18–30% Oil: 18.75% 2-ethoxyethylamine, 20.8% NA. Use as biofuel. Kadlimatti et al.
phosphine, methyl-; 10.57% (2019)
carbonothioicdihydrazide
(continued on next page)
Bioresource Technology 312 (2020) 123615
 Table 1 (continued)

Feed Yield (w/w) Composition Quality Beneficial use Reference

J.-S. Lu, et al.

Sewage sludge Single stage @ N2: gas (39%), oil (20%), char Gas: CO2, CO, H2, CH4; oil: toluene, acetic acid, 39% CO in N2; 44% CO in CO2; 20% tar in Solid residues as soil Kim et al. (2019)
(41%); Two stage @ N2: gas (55.8%), oil (5.2%), butanoic acid, acetamide, phenol; char: Ca, K, Mg N2, 17% tar in CO2 amendments.
char (39.0%); Single stage @ CO2: gas (43.4%), oil
(17.3%), char (39.3%); Two stage @ CO2: gas, oil,
char
MSW Gas: 0.4–4.1%, oil: 9.3–68%, char: 26.5–89.7% Gas: CO2, CO; oil: levoglucosan, anhydrosugars, NA NA Kumagai et al. (2019)
C2-C4 fragments; Solid: char, PE melts
RDF NA Char: bio-char, mineral composition: Ca, Si, Fe, Chars with HHV 20.1–26.2 MJ/kg, with RDF as fuel Nobre et al. (2019)
Na, Al energy yield 84.5–91.7%, energy
efficiency 70.8–79.2%.
Walnut shell, peach stones/ PET, PS, Polymer: Tar: 15–65%, gas:35–85%; biomass: char Pyrolysis oil: phenol, benzene, PAHs derivatives, Oil with decreased oxygenated Oil as chemical feed Ozsin et al. (2018)
PVC (25–30%), tar (15–20%), gas (25%); blend: char ketones, acids, esters, alcohols compounds and increased calorific values stock/ fuel
(15–25%), tar (8–45%), gas (10–50%)
Paper board/PVC/ Saw dust/ cotton NA Paperboard: styrene, D-allose, methyl Benzenoid compounds in PVC, NA Ma et al. (2018)
cloths/ vegetables methacrylate; PVC: benzene derivative, PAHs; paperboard, and vegetables of 65.03%,
sawdust: acetic acid, phenols, ketones; cotton 32.9%, 21.91%, respectively.
cloths: alcohols, D-allose; vegetables: toluene,
acetic acid
MSW NA MSW: gas (CO2: 48%, CO: 28.6%, H2: 28.6%); NA NA Vuppaladadiyam et al.
DMSW: gas (CO2: 33.3%, CO: 28.0%, H2: 27.1%); (2019)
SWD: gas (CO2: 20%, CO: 30%, H2: 40%)
RDF NA NA Energy demand of 400–600 °C pyrolysis is No use of char as Stępień et al. (2019)
63.62 kJ/kg energy
Sludge + organic fines Gas (19–29%), oil (25–32%), char (45–48%); OF: Gas: CO, CH4, C2H4, C2H6, H2 (62–72%); char: ash LHV for gas: 11.8–21.0 MJ/m3. As fuels Agar et al. (2018)
gas (33%), oil (14%), char (52%) (64–69%), fixed C (27–31%)
Chlorella vulgaris + kitchen waste NA CV: oil has 23–26% hydrocarbons, 10–17% BTEX, NA Oil for biofuel/ Chen et al. (2018a)

4
15–24% N-compound; OF: oil has 13–24% chemicals
saccharides, acids hydrocarbon
PVC Char (23–90%), oil (10–60%), gas (2–18%) Pyrolysis oil: toluene, xylene, ethylbenzene, 3- NA controlling harmful Lee et al. (2018)
ethyltoluene, 1,3,5-trimethylbenzene, chemicals.
phenancerene, benzapyrene
MSW + PS NA Pyrolysis oil: 15–40% hydrocarbon, 20–30% Hydrocarbon and benzene compounds Long treat time to low Fang et al. (2018a)
benzene, 25–65% oxygenates compounds decreased with PS content. oxygenates
Horse manure Gas (35.4, 41.4, 46.2%), oil (17.0, 11.5, 7.0%), solid Gas: H2, CO, CO2, CH4; oil: toluene, octane, 2- NA High content CaO in Jeong et al., 2018)
(47.6, 47.1, 46.8%) methylpentane; solid: char biochar
Wood NA Gas:H2, CH4, CO; pyrolysis oil: phenol, cresol, With CO2, generation of CO significantly Char for soil Kim et al. (2019)
guaiacol, 2,6-dimethoxy-phenol, 4-methyl- increased at > 480 °C. remediation/
sryngol, 2,6-di methyl-3-(methoxymethyl)-p- adsorption
benzoquinone and 2,6-dimethoxy- 4-(2-propenyl)-
phenol
Sewage sludge CaCO3/sludge = 0,0.1,0.5; gas (25–28%), oil Gas:H2, CH4, CO, CO2; oil: PAHs; Solid: char CO at 700 °C was increased when CaCO3 Has environmental Kwon et al. (2018)
(26–35%), Solid (48–35%) was added. Aromatic compounds in oil benefits.
was increased.
Biomass, PE, PS @ N2: gas (15–42%), oil (30–70%), Solid (5–30%) Pyrolysis oil: @ N2: benzene (25–68%), PAHs Gaseous products increased from 15.2% utilizing a potent Lee et al. (2017a)
@ CO2: gas (42–65%), oil (25–40%), Solid (5–25%) (10–55%), hydrocarbons (5–55%) to 66.3% for B2PE1PS1. 71.7 wt% and greenhouse gas.
@ CO2: benzene (20–60%), PAHs (8–50%), 26.4 wt% of oils from B2PE1PS1 in N2 and
hydrocarbons (26–65%) CO2
Paper mill sludge NA Gas: H2, CH4, CO; oil: 2-cyclopenten-1- Carbon residue after pyrolysis of PMS Tar could be expedited Lee et al. (2017c)
one,furanone, 1-methyl-1-cyclopenten-3-one, 3- exhibits magnetic properties. by minerals as catalyst.
ethyl-2-cyclopenten-1-one, benzeneacetonitrile,
3,4-xylenol, octadecane
Printed circuit boards @ N2: gas (5%), oil (25%), solid (70%); @ CO2: gas Gas:H2, CO, CH4; oil: brominated compounds; Few brominated compounds were Treatment of PCBs Lee et al. (2017b)
(22%), oil (10%), solid (68%) benzene derivatives, phenolic compounds, PAHs detected in oil
Solid: char
(continued on next page)
Bioresource Technology 312 (2020) 123615
 Table 1 (continued)

Feed Yield (w/w) Composition Quality Beneficial use Reference

J.-S. Lu, et al.

MSW + char + pine MSW: gas (10–20%), oil (18–30%), solid (40–65%); MSW: gas: CO (21.42%), CO2 (70.16%), H2 Tar and gas yields reached 25.94% and NA Song et al. (2018)
w/ additives: gas (17–22%), oil (30–20%), solid (1.44%), CH4 (3.75%); oil: ethanol (27.19%), 20.26%, respectively, with 5% CaO.
(45%) PAHs (22.55%), carboxylic acids (19.37%); w/
additives: gas: CO (3.09%), CO2 (52.21%), H2
(14.11%), CH4 (10.21%); oil: ethanol (7–10%),
PAHs (23–25%), carboxylic acid
Cellulose powder Cell: PS - single step @500 °C: gas: 5%, oil :60%, Single step@500 °C: gas: CO2 (45.9%), CO Lower total liquid and wax yields NA Sophonrat et al.
solid: 11%. @300/500 °C: gas:7%, oil: 53%, solid: (44.5%), H2 (2.8%), CH4 (5%); oil: single-ring compared to the single step pyrolysis. (2018)
17% hydrocarbon (30%), multiple-ring hydrocarbon Stepwise pyrolysis increased yield of CO2,
(21%) H2, CH4.
PS + PE Cell: PS:PE single step @500 °C: gas: 5%, oil: 57%, Single step @500 °C: Gas: CO2 (37.7%), CO Oxygenated compounds in oil is benzoic NA Sophonrat et al.
solid: 4% (32.7%), H2 (4.0%), CH4 (6.5%); oil: single-ring acid from impurity in PE. This causes TAN (2018)
HC (21.6%), multiple-ring HC (15.6%) at high temperature
Olive kernel + MSW + sludge OK/SS @600 °C: gas (21.9%), oil (34.4%), Solid OK/SS @600 °C- gas: H2 (7.38%), CO (18.6%), Light gases including C2, C3 is greater for NA Sfakiotakis and
(34.9%); OK/MSW @600 °C: gas (24.1%), oil CO2 (49.4%), CH4 (13.9%), C2 (6.5%), C3 (4.0%); OK and lesser for SS. Gross calorific value Vamvuka (2018)
(31.1%), solid(36.7%) OK/MSW @600 °C-gas: H2 (10.5%), CO (16.8%), of syngas from OK (14.4 MJ/Nm3)
CO2 (52.1%), CH4 (12.5%), C2 (5.5%), C3 (2.6%)
Waste tire NA Gas: C4H10, H2, toluene, styrene, ethylbenzene; Formation of PAHs in CO2 atmosphere CO2 as reaction Kwon et al. (2012)
oil: p-xylene, 1-methyl-4-ethylbenzene, benzene was decreased. medium
derivatives
OFMSW Gas: 23.2%, oil: 10.6%, solid: 51.7%, water: 7.5% Oil: phenolic compound, aliphatic acid, ketone pyrolysis oil is a shearing thinning non- Oil for road Yang et al. (2018)
and esters, benzene based and long-chain aliphatic Newtonian fluid construction
compound
Bamboo Bamboo w/o CaO: gas (82%), tar (4%), char (12%); Bamboo: gas w/o CaO- H2 (18%), CO (45%), CH4 CaO reduced tar contents and NA Zheng et al. (2018)
w/ CaO: gas (90%), tar (2%), char (8%) (17.5%), CO2 (13%), C2 (5%); w/CaO- H2 (22%), naphthalene content and increased CH4 in
CO (42%), CH4 (18%), CO2 (15%), C2 (3%) gas.

5
Paper pulp Paper pulp w/o CaO: gas (83%), tar (3%), char Paper pulp: gas w/o CaO- H2 (21%), CO (47%), Yield of naphthalene rose from 4.33 to NA
(13%); w/ CaO: gas (90%), tar (2%), char (8%) CH4 (15%), CO2 (10%), C2 (4%); w/ CaO-H2 8.4% after paper pulp blended with CaO.
(22%), CO (49.5%), CH4 (13%), CO2 (9.5%), C2
(3%)
PE PE w/o CaO: gas (95%), tar (4.5%), char (0.5%); w/ PE: gas w/o CaO- H2 (17.5%), CO (5%), CH4 NA NA
CaO: gas (96%), tar (4%) (31%), CO2 (0%), C2 (35%), C3 (7.5%); w/ CaO-
H2 (21%), CO (7.5%), CH4 (32.5%), CO2 (0%), C2
(32.5%), C3(5%)
MSW + PS NA MSW/PS w/o MgO- oil: aliphatic HC (13–2%), Raising PS ratio reduces pollutant and NA Fang et al. (2018c)
aromatics (25–18%), oxygenates (60–79%); w/ increase oxygenates yields. Adding MgO
MgO- oil: aliphatic HC (16–11%), aromatics decreases pollutant and decreases
(32–21%), oxygenates (50–67%) oxygenates yields
Chlorella + tire Blends of CH and TI @N2 gas (23–32%), oil Pyrolysis oil: @N2: oxygenates (5.3–30.2%), HC HC decreased from 58.04% to 10.96% NA Fang et al. (2018b)
(22–53%), solid (22–45%); @CO2: gas (24–33%), (43–57%), benzene (13–48%); @CO2 oxygenates with tire, unsaturated HC and aromatics
oil (20–50%), solid (25–50%) (5.75–41.47%); HC (28–51%), benzene (30–45%) increases
MSW w/o zeolite: Gas: 48.2%, oil: 15.2%, solid: 34.6%; w/ catalyst: parafin 35%, olefin: 42%, aromatic: Activated zeolite increases small HC. Used as fuel Gandidi et al. (2018)
w/ zeolite: gas: 50%, oil: 21.4% 7.5%, alcohol: 4%; w/ catalyst: parafin 38%,
olefin 45%, aromatics 4%.
Food waste NA NA Plastics decomposition becomes difficult Feedstock for pyrolysis Giwa et al. (2018)
PP @700 °C- gas: 25%, oil: 65%, solid: 10% Gas: H2 (13.9%), CH4 (26.7%), CO2 (35.1%); oil: LHV (40.8 MJ/kg) is slightly lower than Diesel engine oil-diesel Kalargaris et al.
benzene derivative (27.42%), xylene (4.88%) diesel (42.9 MJ/kg). Engine brake blends (2018)
thermal efficiency decreased by 1–2%
when oils were used in comparison to
diesel.
Sewage sludge Char: w/ Ca(OH)2–82–68%; w/o Ca(OH)2–80–67% NA Carbon 71.57–41.57% in biochar; Carbon sequestration Ren et al. (2018)
75.17–38.77% with Ca(OH)2
(continued on next page)
Bioresource Technology 312 (2020) 123615
 Table 1 (continued)

Feed Yield (w/w) Composition Quality Beneficial use Reference

J.-S. Lu, et al.

PP + PET + HDPE @ 500 °C with MgO/polymer = 6 - gas: 40%, oil:
35%; solid: 25%
PP + PE w/o catalyst- gas (18%), oil (55%), solid(27%); w/
HZSM-5: gas (10–36%), oil (18–87%), solid
(0–54%); USY: gas (15–30%), oil (65–70%), solid
(4–15%); NH4ZSM-5: gas (30–65%), oil (10–47%),
solid (0–60%)
Rural solid waste + Chlorella Pure RSW- gas (19%), oil (48%), solid (31%); Pure
vulgaris CV- gas (18%), oil (53%), solid (28%); mixed -gas
(19–21%), oil (46–50%), solid (29–32%)
Cellulose + HDPE NA
Wet sewage sludge + saw dust Gas (24–60%),oil (20–25%), solid (52–15%)
25% crude glycerol-olive kernel Microwave: gas (10–30%), oil (57–40%), solid
(32%)
NA Gas: H2, CO, CO2, CH4, C2–C5 HC. Oil: As porous carbons Ma et al. (2018)
aliphatic fractions (C10 to C44) accounted
for 72.3% and most alkenes were alpha-
olefins.
Oil: w/o catalyst- olefins (99%); w/HZSM-5: BHZSM-5 zeolite is the best for oil NA Santos et al. (2018)
olefins (5–99%), alkylbenzene (1–94%), production without forming char.
naphthalene (0–3%); USY: olefins (76–99%), LNH4ZSM-5 and BNH4ZSM-5 zeolites
alkylbenzene (1–18%), naphthalene (0–3%); favor syngas production.
NH4ZSM-5: olefin (7–60%), alkylbenzene
(35–76%), naphthalene (2–15%)
Oil: Pure CV: alkane, alkenes, HC, acids, CV with CaO reduced nitrogenous from Pyrolysis oil of higher Tang et al. (2020)
nitrogenous, oxygenates; RSW: alkane, alkene, 28.72% to 11.46% and carboxylic acids quality.
HC, acid, nitrogenous(3/0/13/5), oxygenate; from 30.85% to 0%. Alkanes
mixed: alkane, alkene, HC, acid, nitrogenous, 6.58%–14.62%, alkenes 12.88%–28.72%,
oxygenate oxygenated 14.16–37.99%.
Oil: pure CE- carbohydrate (60%), ester (5.0%), HDPE enhanced decomposition of NA Yuan et al. (2019)
ketone (6.5%), aldehyde (5.56%), furan (2.5%); oxygenate-containing compounds; CE
pure HDPE-alkane (22.3%), alkene (64%); mixed: stimulated production of alkanes and
carbohydrate (8–30%), alkene, alkane; gas: H2O, alkenes groups.
CO/C2H4, CO2
Gas: H2 (29–44%), CO (26–32%), CH4 (18–8%), Quality of syngas was improved. Syngas NA Zhu et al. (2018)
CO2 (24–13%), C2Hn (1.12–1.37%); oil: aliphatic from 1 kg raw material increased HHV of
(55–80%), aromatics (25–15%), oxygen 4 MJ/kg and carbon conversion increased
heterocyclic (10–2.5%), nitrogenous 13%,
microwave: gas- H2 (40.8–46.13%), CO Pyrolysis gas had enhanced syngas NA Ganesapillai et al.
(39.8–32.98%), CO2 (12.2–5.55%), CH4 production compared to the non- (2016)

6
(4.8–12.82%), C2H4 (2.5%) microwave pretreated samples.
Cellulose Gas: 46.01–53.06%; oil: 30.42–36.18%; solid: gas: H2 (39–33%), CO (37–44%), CO2 (8–10%), > 20% yield of aromatics; non- aromatics, hydrogen- Zhang et al. (2015)
15.46–16.12% CH4 (2–3%), C2H4 (2–7%); oil: aromatic condensable gases (46.01–53.06%) were rich gas
oxygenates (2–4%), phenols (4–10%), aromatic H2, CO, CO2, CH4. Coke yield was
HC (88–94%) 0.74–3.27%
Rice husk Gas:3.39–25.47%; oil: 6.03–39.84%; solid: NA Temperature is important to produce used as fuel. Vieira et al. (2020)
38.05–70.56% biochar; residence time is most on energy
consumption.
PE, PP, PS, PET, PVC Gas (14.2%), oil (75.8%), solid (10.0%) Oil: C5-C9 (39.3%), C10-C14 (24.10%), C15-C19 Oil density 743 kg/m3. Heating rate gas used for heating Singh et al. (2019)
(6.57%), > C19 (3.2%); gas: H2 (2.99–12.10%), affects product quality
CO2 (1.31–1.44%), CO (2.84–1.61%), CH4
(0.11–13.94%)
Waste tetra pak + waste motor oil @500 °C- pure WTP- gas (28%), oil (9%), solid Oil: pure WTP- benzene derivatives (7.48%), TOC content of oil 11.65%. Heavy HHV of solid close to Tekin et al. (2019)
(25%); pure WMO- gas (15%), oil (84%), solid phenols (19.66%), aldehydes/ketones (46.10%); naphtha fraction was 60% in oi. sub-bituminous coal.
mixed gas, oil, solid pure WMO-alkenes, alkanes; mixed–alkenes,
alkanes
Corn brake + wheat straw + nut NA Gas: CB-H2 (43%), CO (14%), CH4 (43%); HS-H2 High temperature with CO2 to produce hazelnut shell as fuel. Janković et al. (2020)
shell (45%), CO (20%), CH4 (35%); WS- H2 (50%), CO CO-rich syngas.
(17%), CH4 (33%)
Coffee husk 450 °C- gas (33.38%), oil (31.94%), solid (34.68%) Gas: H2, CO2, CO, CH4; oil: HC, PAHs, ketone, High temperature (450 °C) favors oil chemical products. Setter et al. (2020)
acid, ester, phenolic, nitrogen compounds; solid: production. Coke formation occurred
volatile, ash, fixed carbon 200–400 °C.
Bioresource Technology 312 (2020) 123615
J.-S. Lu, et al.
Muffle furnaces (da Silva Filho et al., 2019, Nobre et al., 2019) have
been used to pyrolyze larger waste samples, and the results thus ob-
tained can be used in designing and planning pilot-scale or large-scale
tests.
Novel pyrolysis reactors have been used to improve MSW pyrolysis
performances. For example, Kadlimatti et al. (2019) performed micro-
wave-assisted pyrolysis tests in a microwave oven. Fang et al. (2018a)
claimed that use of ultrasound in the pyrolysis system suppressed the
formation of oxygenated compounds in oil products, improving their
quality as alternative fuels. Al Arni (2018) demonstrated that heating
rates in MSW pyrolysis could largely shifted the yields of syngas after
pyrolysis.
2.2.2. End products: Yields and quality
The major end-products of the slow pyrolysis of organic feedstocks
include syngas, pyrolysis oil, and bio-char. Table 1 presents recent
studies of end products of MSW pyrolysis tests.
2.2.2.1. Syngas. Syngas contains the light fractions of the pyrolyzed
fragments, including H2, CO and CO2. Agar et al. (2018) noted that the
gas products from sewage sludge and organic fines had lower heating
values (LHV) of 11.8–19.1 and 18.2–21.0 MJ/m3, respectively, which
were high enough for them to be used as alternative fuels. Onwudili
et al. (2019) noted that high temperature increased gas yields, owing to
the highly endothermic nature of the generation of syngas from
biomass. For example, Veses et al. (2020) noted that at > 700 °C,
syngas was generated with > 80% CO + H2 and a heating value of
16 MJ/Nm3.
The co-pyrolysis of a few types of biomass has been shown to pro-
duce H2 faster than the mono-pyrolysis of biomass of a single waste
type (Wang et al., 2019a). Also, adding CO2 promoted reforming re-
actions with steam and increase the CO content of syngas that was
formed by the pyrolysis of sewage sludge (Kim et al., 2019). The
combination of reforming reactions with pyrolysis reactions has been
widely considered to improve the yield and quality of syngas (Cai et al.,
2019; Wang et al., 2020b). In particular, a Ni catalyst, added by Chai
et al. (2020), has been shown to accelerate effectively the reforming
reaction to increase the yield and H2 content of syngas.
2.2.2.2. Pyrolysis oil. Pyrolysis oil comprises hydrocarbons, aromatic
hydrocarbons, benzene derivatives and oxygenates (Quesada et al.,
2019). A right pyrolysis temperature must be set for oil production. Al-
Salem (2019) found that most (> 96%) of the pyrolysis oil that was
formed by pyrolyzing PDFE at 500–800 °C was aliphatic C8-C12, with
more C13 at higher temperatures. Sotoudehnia et al. (2020) noted that
the amounts of methanol in the pyrolysis oil that was formed by the
demethylation of hemicellulose and lignin at 350 °C were almost six
times of that at 400–450 °C. The metals released by the pyrolyzed
products could increase the yield of the pyrolysis oils (Yousef et al.,
2019).
Feed composition significantly influences the oil quality. Lam et al.
(2019) generated pyrolysis oil from co-pyrolyzed plastics and cooking
oil with a yield of up to 84% and a higher heating value (HHV) of
49 MJ/kg, which exceeded those of diesel and gasoline. Kumagai et al.
(2019) demonstrated that the production of levoglucosan and meth-
oxyphenols was enhanced by factors of 1.7 and 1.4, respectively, to
mono-pyrolysis tests during the co-pyrolysis of beech wood in the PE
melt. Chen et al. (2020) showed that the percentage of polycyclic
aromatic hydrocarbons (PAHs) in pyrolysis oil was reduced from 17 to
10.8% when 25% tire waste was added. The presence of certain com-
pounds such as HCl from PVC plastics reduced the quality of the oil by
reducing the yields of aromatic compounds (Wang et al., 2019b) or
promoted the production of dioxins and furans (da Silva Filho et al.,
2019). Wang et al. (2019b) showed that adding xylane to be co-pyr-
olyzed with PVC effectively inhibited the release of HCl.
7
Bioresource Technology 312 (2020) 123615
2.2.2.3. Bio-char. The solid residues of MSW pyrolysis are in a char
form, containing principally carbon, followed by inorganic materials,
metals, or transition elements. An excessively high temperature
disfavors the formation of solid residues. The pyrolysis of MSW at
800 °C yielded 39.2% char (Tokmurzin et al., 2020) while nine woody
wastes that were pyrolyzed at 400 °C yielded 10–15% more biochar
than those pyrolyzed at 600 °C (Ayiania et al., 2019). The production of
char can be increased by adding an external source of carbon in the
pyrolysis process (Song et al., 2018).
The bio-char mostly comprises C, with a C content of > 60%, as
found by Ayiania et al. (2019), or up to 95% as reported by Paukov
et al. (2019). The C-rich matrix with low ash content would has high
heating values that make it suitable for use in alternative fuels. Nobre
et al. (2019) produced chars with HHVs of 20–26 MJ/kg, accounting for
84.5–91.7% of the energy in MSW feedstocks before pyrolysis.
Kim et al. (2019) indicated that the solid residues immobilized ex-
cess Ca, K, and Mg into its matrix. Therefore, the solid residues can be
used as soil additives.
3. Synergistic co-pyrolysis
Studies of the pyrolysis of specific constituents of mixed MSW, such
as litchi peels (Liu et al., 2020), sewage sludge (Kim et al., 2019), food
waste (pork and rice) (Ming et al., 2020), sawdust and LDPE plastics
(Chai et al., 2020) have been performed. To pyrolyze MSW, the sy-
nergistic effects on reaction rates and end product quantity and quality
in the co-pyrolysis of the various constituents of MSW, food waste,
paper, sludge, yard waste, plastics and other organic fractions, must be
understood, considering the complex reactions that occur among the
numerous intermediates generated from the pyrolyzed constituents(van
Nguyen et al., 2019; Hassan et al., 2020; Gu et al., 2020). This section
lists recent studies of these synergistic effects in co-pyrolysis tests with
typical constituents of MSW.
3.1. Co-pyrolysis of food waste
Food waste is one of the major constituents of MSW. The excess
oxygen atoms in food waste caused the produced pyrolysis oils to ex-
hibit high levels of oxygenates of low biostability and low heating va-
lues. Co-pyrolyzing biomass with other MSW constituents with low O/C
ratios yields pyrolysis oils with various compositions. For example,
Chen et al. (2019a) carried out co-pyrolysis tests on 50:50 kitchen
wastes and tire wastes at heating rates of 10–30 °C/min and noted in
their Py-GC/MS analysis that co-pyrolysis increased the proportion of
generated hydrocarbons, especially olefins, from 13% to 37%, and in-
hibited the formation of non-hydrocarbon compounds in the oil pro-
ducts relative to mono-pyrolysis. The co-pyrolysis of food waste with
lignocellulosic materials can accelerate the pyrolysis rates for both
substrates. Wang et al. (2017) noted the accelerated pyrolysis of
cooking oil and tea residue blends. But on the contrary with the same
pyrolysis feedstocks and conditions, an atmosphere of CO2 reduced
(rather than increased) the rate of pyrolysis by unknown mechanisms
(Chen et al., 2018b).
The co-pyrolysis of food waste with other constituents of MSW also
shifted the end product distributions. Chen et al. (2018a) revealed that
the co-pyrolysis of food waste with algae biomass increased the gas
yield and reduced the pyrolysis oil yield, but the HHV of the pyrolysis
oil was increased to 33.9 MJ/kg. Tang et al. (2018) performed a co-
pyrolysis test of soybean protein and PVC and noted that tar yield was
2–69% lower than that obtained in mono-pyrolysis tests. Qureshi et al.
(2020) conducted the co-pyrolysis of food wastes with PET bottles
blends in a mass ratio of 3:2 at heating rates of 5–15 °C/min. The blends
had a close-to-commercial coal energy content of 22.2 MJ/kg and 12
times lower activation energy in reaction kinetics in comparison with
pure PET.
The synergistic effects of the co-pyrolysis of food waste with other
J.-S. Lu, et al.
constituents on reaction rates and end product distributions are sig-
nificant. They are generally welcome as they improve the quality of the
produced pyrolysis oils.
3.2. Co-pyrolysis of plastic waste
Plastic waste is one of the major constituents of MSW. Plastic wastes
have high C and H contents but commonly negligible O contents. The
co-pyrolysis of plastic wastes with other constituents of MSW can alter
feedstock compositions and generate possible synergistic effects in a
pyrolytic environment. For example, van Nguyen et al. (2019) noted
that the pyrolysis oil formed by the co-pyrolysis of 75:25 waste polymer
foam and pine sawdust had a 63.31% yield and an HHV of 39.65 MJ/
kg, making it superior to the oil product of the mono-pyrolysis of
sawdust. Akyürek (2019) co-pyrolyzed recycled polyester and cattle
manure and showed that the free energy change of the blend was high
enough for it to be used in the production of a green energy carrier.
The pyrolytic temperature influences the end products of the co-
pyrolysis of plastic waste and biomass. Sophonrat et al. (2018) co-
pyrolyzed plastics and paper at 350–500 °C and found that the pyrolysis
oil contained more oxygenated and acidic products at low temperatures
and a higher portion of hydrocarbons with a lower acid number at high
temperatures. Phetyim and Pivsa-Art (2018) also showed that
400–425 °C was the optimal temperature for the co-pyrolysis of plastic
blends (HDPE and PP) with lubricant oil at HDPE:PP:oil = 30:20:50 to
form a pyrolysis oil with diesel-like fuel properties. Kai et al. (2019)
noted that the co-pyrolysis of HDPE and corn stalk promoted the release
of H2, CO/C2H4 and C3H6 from the blends at 150–400 °C, but inhibited
the release of aliphatic hydrocarbons at 400–850 °C.
Synergistic effects were observed in the co-pyrolysis of plastic waste
and other MSW constituent blends. Wan Mahari et al. (2018) revealed
that the co-pyrolysis of used plastic waste and frying oil had a positive
synergistic effect, with the production of an increased fraction (81%) of
pyrolysis oil with a lower oxygen content and higher energy content
(42–46 MJ/kg). Sanahuja-Parejo et al. (2018) co-pyrolyzed waste tire
and grape seed at a heating rate of 100 °C/min to 550 °C. The waste
tires (40%) underwent pyrolysis with high oil yield (73%) with high
HHV (27.3 MJ/kg).
The synergistic effects of individual types of plastics on co-pyrolysis
performance vary. Navarro et al. (2018) found that the co-pyrolysis of
waste tire, PET, PP or PDPE with pine woodchips involved no or neg-
ligible interactions; PLA interacted weakly with woodchips, and PS
interacted strongly with woodchips at above 400 °C. The tendency of
adding plastics to form char followed the order PVC > PS > PE
(Ephraim et al., 2018; Lu et al., 2018; Zheng et al., 2018; Chen et al.,
2019c; Wang et al., 2019b; Déparrois et al., 2019). Wang et al. (2019c)
observed increased soot formation by the co-pyrolysis of PU and bio-
mass (wood or straw) with an increased biomass ratio and reduced
pyrolytic temperature, and wood exhibited stronger synergistic effects
than straw since the former has higher alkali metal contents than the
latter. Contradictory results have also been reported: Braden and Bai
(2018) performed co-pyrolysis tests with PVC and cellulose in THF/
water co-solvent, which resulted in a high yield of pyrolysis oil of 40%.
Shen et al. (2018) co-pyrolyzed waste printed circuit board with rice
husk in a TGA test and found that the cellulose increased the pyrolysis
efficiency. The activation energy of pyrolysis of the printed circuit
board varied with the lignin fraction. Different constituents in mixed
plastics had difference effects on co-pyrolysis performance. Suriapparao
et al. (2018) performed co-pyrolysis tests on PP and PS with five lig-
nocellulosic biomasses. The yields of pyrolysis oils from the PS-biomass
were higher (73–81%) than those from the biomass alone (37–63%).
The PP-husk blend yielded a pyrolysis oil with a higher HHV
(38–42 MJ/kg) than for that obtained from the biomass alone
(20–30 MJ/kg). PS boosted the production of aromatic hydrocarbons
(48–54%), while PP increased that of aliphatic hydrocarbons (19–33%)
in the co-pyrolysis.
8
Bioresource Technology 312 (2020) 123615
The pyrolysis rate was synergistically increased in blends of PLA/
wood fiber (Sun et al., 2019), PE/lignocellulose (Fan et al., 2019), PS/
grape seed (Sanahuja-Parejo et al., 2019), PET/food waste (Qureshi
et al., 2020), PET/biomass (Mishra et al., 2019), tetra pak/motor oil
(Tekin et al., 2019), PP/tobacco stalk (Chen et al., 2019c), PU/lig-
nocellulose (Wang et al., 2019c) to above that of mono-pyrolysis.
Conversely, Salman et al. (2019) noted an increased activation energy
of the co-pyrolysis of sachet-water plastics and oil palm bunch. Clearly,
as stated above, the interactions of plastics in co-pyrolysis tests are
complex and warrant further investigation.
3.3. Co-pyrolysis of biomass wastes
Biomass waste is a major constituent of MSW. The components of
biomass waste are cellulose, hemicellulose and lignin fractions that
have different thermal degradation behaviors, although all have high O
contents, associated with cells and extracellular compounds.
The co-pyrolysis of biomass with plastics can change the distribu-
tion and quality of the end products (Üresin et al., 2019; Krutof and
Hawboldt, 2019). The pyrolysis of biomass with a high lignin fraction
tends to yield char. The co-pyrolysis of lignocellulosic biomass with
short-chain organic compounds can shift the production of char to that
of pyrolysis oil and/or syngas. Li et al. (2020) found that the co-pyr-
olysis of rice hush and plastic films led to increased yields of oil with
higher hydrocarbon contents. Bartocci et al. (2018) co-pyrolyzed saw-
dust wood and crude glycerol and noted the reduction of char yield
from 28% to zero and an increase in syngas yield from 34% to 86% as
the glycerol dose increased. The HHV of the syngas products was in-
creased from 12.6 to 16.1 MJ/kg. The presence of a lignin fraction
improved the quality of the end products under specific circumstances.
Özsin and Pütün (2019) performed co-pyrolysis tests on 50:50
cherry seed to PVC and found that the presence of cherry seed and PVC
alters the pyrolytic degradation behaviors for both. Iftikhar et al.
(2019) co-pyrolyzed sugarcane bagasse and PS with catalyst HZSM-5
and MgO or CaO and found that adding 1:3 HZSM-5:MgO increased the
production of mono-aromatic hydrocarbon up to 56.8% and reduced
that of PAH (to 20.8%), improving the quality of the pyrolysis oil. Lin
et al. (2019a) noted that the presence of coal influenced the rate of co-
pyrolysis of the corn stalk and lignite and bituminous coal blends. Zhao
et al. (2020) performed co-pyrolysis tests on wheat straw and lignite
coal in a tubular reactor. Synergistic co-pyrolysis can occur in the
presence of steam, which strengthens the catalytic activities of alkali
and alkaline earth metals and increases the number of free radicals
produced from chars. Wang et al. (2020a) demonstrated that the sy-
nergistic effects in the co-pyrolysis for blends of cow dung and bitu-
minous coal in the presence of CaO yield excess benzene and nath-
thalene in the pyrolysis oil. Conversely, the co-pyrolysis of these blends
without CaO produced more chars, reducing the values of the end
products. Wei et al. (2020) demonstrated that the co-pyrolysis/co-ga-
sification of bituminous coal and rice straw hydrochar prepared at
hydrothermal temperatures of 200–220 °C was accelerated by the po-
tassium ions released during hydrochar preparation.
Co-pyrolysis of biomass with other MSW constituents does not al-
ways proceed positively. Cao et al. (2019) found that the co-pyrolysis of
the macroalga Enteromorpha clathrata and PVC led to reduced yields of
pyrolysis oil (0.43–2.57% lower) and increased yields of chars
(1.28–4.93% higher). Terrell and Garcia-Perez (2019) demonstrated
that NH3 can react with cellulose to generate excess biochars. He et al.
(2018) revealed the co-pyrolysis of rice straw and bituminous coal had
a lower activation energy than expected, owing to the reactions induced
by the deposition of biomass ash on the surface of the coal char.
Up to the present stage the synergetic effect has no general in-
dicator. This is since there are numerous aspects of synergy, including
the enhancement in reaction rate, shift to preferred product distribu-
tions, improvement of product quality as fuel or chemicals, and in-
hibition of production of hazardous materials. This review is the first
J.-S. Lu, et al. Bioresource Technology 312 (2020) 123615

trial to summarize these efforts while the future studies should be done modified Dulong formula, considering the associated moisture content
correspondingly. (m), as follows.

HHV(kJ/kg) = [(337 C+ 1418(H−O/8))] ∗ (1−m) (1)

4. Discussion
4.1. Energy sufficiency of MSW feed
The energy sufficiency of MSW feed is defined as the surplus energy
that can be generated by the pyrolysis process and stored in the end
products, which is determined by the original energy content of the
feed (wet basis) and the energy conversion performance of the reactor.
Based on the data of 24 full-scale incinerators for wet MSW in
Taiwan in 2018 (https://swims.epa.gov.tw/Statistics/Statistics_Year_
Table.aspx?_Year=2019), the energy recovered from a total of 6.5 M
tons of wet MSW with an average HHV of 10.4 MJ/kg was calculated
and is 18.2% on the basis of electricity generated and 14.7% on the
basis of electricity sold to the public grid. Restated, the energy suffi-
ciency of MSW incineration in Taiwan is positive, and represents 45.5%
(=18.2%/0.4, using a generator efficiency of 40%) of the energy con-
tent of the fed wet MSW, considering all energy that is required to dry
the MSW and to run all facilities, including blowers and pollution
control units.
MSWs collected from various sampling sites have very different
compositions (Fig. 2). Based on the chemical composition data in lit-
erature, the HHV of the waste samples can be estimated using the
where C, H and O are the dry weight percentages of carbon, hy-
drogen and oxygen in the MSW. The LHVs of these samples can also be
calculated considering the heat effects of the involved moisture. Fig. 3
presents the results. The heating values of the MSW samples varied
greatly between the highest of 45 MJ/kg and the lowest of less than
4 MJ/kg.
Waste incineration can be regarded as a two-stage process with
pyrolysis at 500 °C to form intermediate end products, which are then
completely combusted to form CO2 and water with the generation of
reaction heat. The energy contents of the intermediate end products are
86% (Fox et al., 2019) or 84.5–91.7% (Nobre et al., 2019) of the caloric
contents of the fed MSW. Therefore, if an average 90% of the energy
content of fed MSW on a dry basis is converted to the end products of
pyrolysis, and since the entire incineration process from wet MSW
yields an energy surplus of 45.5%, the minimum energy that is required
to support the pyrolysis process is 4.6 MJ/kg. Since energy is stored in
the end products, external energy is required to dry and raise the
temperature of MSW to the pyrolysis temperature, and this must exceed
4.6 MJ/kg considering all the irreversibility that may be encountered in
the pyrolysis applications. Therefore, a threshold heating value of
10 MJ/kg of the MSW feedstocks is proposed to ensure energy

Fig. 2. Constituents in typical MSW samples for typical recent pyrolysis studies listed in supplementary materials. (Top) Left: Nobre et al. (2019) black; Zhou et al.
(2014) red; Fang et al. (2016) green; Fang et al. (2018a) blue. Right: Fang et al. (2018c) black; Gandidi et al. (2018) red; Sfakiotakis and Vamvuka (2018) green; Song
et al. (2018) blue. (Down) Left: Yang et al. (2018) black; Azam et al. (2019) red; da Silva Filho et al. (2019) green; Stępień et al. (2019) blue. Right: Tang et al. (2020)
black; Azamet al. (2019) red; Wang et al. (2020b) green; Wu et al. (2020) blue. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

9
J.-S. Lu, et al.
Fig. 3. (Top) The higher heating value (HHV) for different solid wastes listed in
Supplementary Materials. The HHV values are calculated based on modified
Dulong formula. (Bottom) Correlations between HHV and molar fractions of C,
H, O in the samples. The straight lines are obtained from linear regression of
literature works.
sufficiency in pyrolysis treatment. This value is close to that estimated
for the MSW collected by Wang et al. (2020b) with C = 46.31%,
O = 16.85%, H = 5.86%, and m = 50%. Apparently, a higher HHV
corresponds to greater feasibility of the thermal process.
Fig. 3 presents the calculated HHV as a function of the molar frac-
tions of C, H, and O in the MSW samples. Those samples with almost no
oxygen atoms, mostly plastics, commonly have heating values of over
40,000 kJ/kg, while those with high O (MSW enriched with food waste)
have low heating values. The intercept at x-axis of HHV vs. O fraction
line is about 37% and about 30% with HHV = 10,000 kJ/kg on a dry
basis. Equivalently, at 50% moisture, the O content in the MSW sample
would be about 17% for an HHV of zero and about 14% for an HHV of
10,000 kJ/kg. If the C, H, O or moisture content is increased by 1%
from its original value, then the HHV, based on Eq. (1), would increase
by + 0.75%, −0.14%, +0.40%, or −0.5%, respectively, revealing the
importance of screening MSW constituents with high calorific values
and pre-drying the feedstocks to maximize the total energy recovered
from the MSW during pyrolysis. Similar conclusions are also applicable
to other thermal treatment processes of MSW, such as MSW incinera-
tion.
4.2. Assisted pyrolysis
4.2.1. Catalytic pyrolysis
Methods for manipulating the distribution of end products by ad-
justing the operating conditions of the co-pyrolysis tests have been
examined. Cai et al. (2019) used a Ni-Al-Mg catalyst in plastic waste
pyrolysis to decompose alkanes and alkenes (C2 to C4) to H2, CO, and
CO2. The gas products, with the use of the applied catalysts, increased
the generation of power by a solid oxide fuel cell that received the
obtained syngas from 710 to 2800 W/m2 at 800 °C. Chai et al. (2020)
utilized a Ni-CaO-C catalyst to LDPE and pine sawdust blends to im-
prove gas yield and increase the H2 content of the syngas product.
10
Bioresource Technology 312 (2020) 123615
Onwudili et al. (2019) used Y-zeolite (ZY-1) and ZSM-5 zeolite (ZS-1) as
catalysts to increase by factors of 1.5 and 1.8 gas yields from the pyr-
olysis of mixtures of plastics (PP, PE, PS, and PET) at 600 °C. At 500 °C,
the ZY-1 and ZS-1 catalysts reduced oil yields by 24% and 37%, re-
spectively, below those obtained by conventional pyrolysis of mixed
plastics, but increased gas yields were enhanced by 2.5 and 1.5 times,
respectively.
As stated above, studies on the use of catalysis for improving MSW
pyrolysis performance are few. Further works to explore the efficiency
for applying catalysts, particularly those generated from wastes and can
become part of the end products, are needed.
4.2.2. Additive-assisted pyrolysis
Metal salts (K, Na, Ca, Mg, Al, Cu, Ni) and inorganic additives
(zeolites, biochars) were added as catalysts or reactants to alter the
pyrolysis process.
Lin et al. (2019b) identified synergistic effects in the co-pyrolysis of
cellulose and HDPE because the involved alkalis and alkaline earth
metals (AAEMs) promoted the formation of alkenes and reduced that of
anhydrosugar. Potassium was found to exhibit negative effect in co-
pyrolysis, reducing the yields of anhydrosugars and hydrocarbons but
increasing those of furans and ketones. Li et al. (2020) used AAEMs in
TGA tests on MSW and cotton straw briquettes blend and found that
they inhibited volatile release from cotton straw briquettes at lower
temperatures and increased the pyrolysis rates at higher temperatures.
Yuan et al. (2019) co-pyrolyzed 50:50 blends of lignocellulosic biomass
and calcium-rich waste. The calcium-rich eggshell had the lowest ac-
tivation energy for char formation. The AAEMs in the eggshell were
thought to positively affect char combustion, favored CO2 capture and
enhanced CO production. Also, adding MgO reduced yield but in-
creased the surface area and pore volume of the solid residues (Fang
et al., 2018a; Ma et al., 2018), reduced the proportion of oxygenates
and increased the proportion of aliphatic hydrocarbon in the pyrolysis
oil (Fang et al., 2018c). CaO has been shown to reduce tar yield and oil
yield but increase the H2 and CO contents of the syngas (Zheng et al.,
2018; Song et al., 2018); and it has been used to reduce the acid value
and increase the aliphatic hydrocarbon content of the pyrolysis oil
(Chen et al., 2018b). It has been found that the addition of MgO in-
creased the rate of pyrolysis of MSW while that of CaO reduced it (Tang
et al., 2020). One interesting development is the use of waste-derived
catalyst to improve the quality of the products of MSW pyrolysis (Wang
et al., 2019a).
4.2.3. Microwave-assisted pyrolysis
Microwave irradiation can promote the pyrolysis of various con-
stituents of MSW (Chen et al., 2019b). Zhang et al. (2018) studied the
co-pyrolysis of 50:50 waste agricultural plastic mulching films and
dried grains from distilleries in a microwave-assisted reactor and
showed that under microwave irradiation, plastics promoted the pro-
duction of pyrolysis oil and retarded the formation of coke. Prathiba
et al. (2018) co-pyrolyzed PS and activated carbon blend in a 10:1 ratio
in a microwave oven and found that the yield of the pyrolysis oil was
93.04% and it had a heating value of 45 MJ/kg. Bu et al. (2019) con-
ducted microwave-assisted co-pyrolysis tests on LDPE and torrefied
lignin and found that the pyrolysis rate and the aromatic hydrocarbon
contents in the pyrolysis oil were increased over those of the control
without using the microwave. Abdelsayed et al. (2019) noted that the
microwave-assisted co-pyrolysis of 1:3 blend of pine wood sawdust and
lignite coal increased tar and syngas yields with high aromatic-to-ali-
phatic fraction ratios. The microwave assisted the formation of excess
aromatics and graphene in the pyrolysis oil from feedstocks with a high
O/C ratio and a low fixed carbon content.
As stated above, microwave irradiation increased the yields and
hydrocarbon fraction of the pyrolysis oils obtained from co-pyrolysis
systems with the waste plastics.
J.-S. Lu, et al.
Fig. 4. A multiple-feeding co-pyrolyzer that can process MSW blends with
maximum synergistic effects and the flexibility to produce end products with
maximal energy recovery and minimal carbon footprint.
4.2.4. CO2-assisted co-pyrolysis
In some studies, CO2 has been introduced as a reactive medium to
replace the inert N2 in the pyrolysis tests. Adding CO2 not only increases
syngas yields and reduces the fraction of pyrolysis oil formed but also
reduces the amount of greenhouse gas. For example, the presence of a
carbonate salt that can generate CO2 in the reactive atmosphere ac-
celerated the devolatilization of coke burnout (Liu et al., 2020). Kim
et al. (2019) found that using CO2 as a reactive medium in the pyrolysis
of crude oil sludge increased the yield of syngas and reduced the yield
of pyrolysis oil, indicating that CO2 enhanced the thermal cracking and
dehydrogenation of hydrocarbons released from crude oil. Kwon et al.
(2019) showed that the pyrolysis of chitin yielded a maximum con-
centration of 27% of CO in an atmosphere of CO2 - much more than that
in an atmosphere of N2, showing that CO2 was a source of C and O
atoms in reactions that involved volatile hydrocarbons. Kwon et al.
(2018) proposed that using 0.5% CaCO3 in the pyrolysis of sewage
sludge increased significantly the CO content of the syngas and reduced
the PAH content by 7%. Lee et al. (2018) found that the concentration
of CO in the CO2-assisted pyrolysis of cattle excreta was 4,000 times of
that in an atmosphere of N2. Meanwhile, using CO2 as a reactive
medium reduced the production of hydrocarbons and benzene deriva-
tives in the oil products by 40.0% and 27.2%, respectively.
5. Prospects
Recent studies of MSW pyrolysis have focused on different aspects
of the process, but they generally direct to the development of a value-
added and technically feasible co-pyrolysis system, as schematically
shown in Fig. 4. A multiple-feeding co-pyrolyzer that can process MSW
blends with a wide range of waste mixing ratios with maximum sy-
nergistic effects and the flexibility to produce marketable end products
should be developed. The waste heat from the product streams or other
renewable energy sources, such as solar heating, can be used to pre-dry
and pre-heat feedstocks before pyrolysis to maximize energy recovery.
Catalysts and/or additives (including the obtained biochars after
modification) that can promote synergy in co-pyrolysis should be used.
The CO2 in the syngas stream can be recycled to the pyrolyzer to im-
prove its performance and mitigate greenhouse gas emissions. An ex-
ternal energy field, such as microwave irradiation, can be used
11
Bioresource Technology 312 (2020) 123615
efficiently to improve the quality of the end products.
The energy surplus that is generated in MSW pyrolysis can be mostly
retained in its end products, including syngas, pyrolysis oil and bio-
chars. The market values of these products are important. In general,
the use of end products as raw materials in chemical manufacturing
yields higher profits than the use of alternative fuels. Synthesis studies
that use the pyrolysis end products for the Fisher-Tropsch synthesis of
hydrocarbons should be carried out, for example. The adverse effects of
adding the pyrolytic end products to chemical manufacturing, such as
the trace sulfur compounds that may poison the catalyst, should be
considered. Also, thermodynamic analysis on the individual enhance-
ment strategy needs careful examination. For instance, CO2 is the end
product of organic combustion and to convert it back to a renewable
resource by reforming reaction needs input of external free energy.
Because of process irreversibility the energy gained must be lower than
the energy input; therefore, the overall benefits for using CO2 as a re-
actant to shift the end products during pyrolysis need more detailed
analysis.
For large-scale MSW pyrolysis applications, cost, carbon footprint
and environmental impact must be considered. Pilot-scale and full-scale
tests should be conducted to establish the economic and environmental
sustainability of MSW pyrolysis, based on a comprehensive techno-
economic analysis that considers environmental impact.
6. Conclusion
Advances in fundamental understanding of the co-pyrolysis of
constituents of MSW caused increased interests in the use of thermal
pyrolysis to convert MSW to value-added end products. An energy-ef-
fective pyrolysis process with the lowest possible carbon footprint
should be able simultaneously to realize the recycling of organic wastes,
the generation of renewable energy, and release of minimal quantities
of greenhouse gas and pollutants. This mini-review discussed the out-
comes of recent research on the pyrolysis of MSW and the synergistic
co-pyrolysis of its constituents. Discussions on the energy efficiency of
MSW pyrolysis and the assisted MSW pyrolysis are provided.
CRediT authorship contribution statement
Jia-Shun Lu: Data curation. Yingju Chang: Data curation. Chi-Sun
Poon: Conceptualization, Writing - original draft. Duu-Jong Lee:
Supervision, Writing - original draft. : .
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
Duu-Jong Lee appreciates the visiting appointment offered by
Department of Civil and Environmental Engineering, The Hong Kong
Polytechnic University to perform this research.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biortech.2020.123615.
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